JP2726777B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material containing a bleach accelerator-releasing compound and a processing method thereof.

[0002]

BACKGROUND OF THE INVENTION Photographic materials which form dye images by a process involving a bleaching step are well known and used on the market. Such materials and methods include, for example, The Celery®
Of the photographic process (The T
heavy of the Photographic
Process), 4th edition, T.M. H. Edited by James,
462-463 and 335-361. In recent years, photographic materials are required to be quickly desilvered within a shorter bleaching time in accordance with the demand for shortening the processing time.However, when trying to increase the sensitivity of the emulsion, desilvering is unlikely to occur. This is one of the dilemmas in developing photosensitive materials.

[0003] In order to solve this problem, the use of a bleaching accelerator releasing type coupler in a photographic light-sensitive material to increase the bleaching speed has been studied by Research Disclosure.
1973, No. 11449, 1984, No. 2
4241 and JP-A-61-201247.

However, utilizing bleach accelerator releasing couplers has several problems. one,
As described in JP-A-2-93454, the bleach accelerating effect is reduced in a running processing solution. On the other hand, in order for the bleaching accelerator releasing type coupler to form a dye when the bleaching accelerator is released, it is necessary to change the structure of the coupler according to the color sensitivity of the emulsion to be bleached. In order to solve these problems, it is effective to use an oxidation-reduction type bleaching accelerator releasing compound disclosed in JP-A-2-93454.

According to our studies, this type of bleaching accelerator releasing type compound does not cause a color reaction when the bleaching accelerator is released. For example, the same compound is used in each of the blue, green and red emulsion layers. Can be added. It is also possible to add an accelerator to the light-sensitive layer adjacent to each emulsion layer and effect the accelerator from the adjacent layer. When a bleaching accelerator releasing compound is placed in an adjacent layer, a bleaching accelerator can be applied to a single layer to a plurality of emulsion layers, storage stability is improved, and a color mixture inhibitor added to a non-photosensitive layer. It also has the advantage that it can also be used as such.

[0006] However, redox bleaching accelerator releasing compounds characteristic of bleaching accelerator releasing couplers as described above have not yet been entirely satisfactory. Improvements have been desired in that the bleach accelerating ability is not sufficient (particularly when added to the layer adjacent to the emulsion layer), and the storage stability is not one step better.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a photographic material having a short bleaching time and excellent color separation, and a processing method therefor. A second object of the present invention is to provide a photographic material having excellent storage stability. A third object of the present invention is to provide a photographic material containing an oxidation-reduction type bleach accelerator releasing compound having excellent bleach accelerating ability and stability.

[0008]

The object of the present invention is to provide a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, which is represented by the following formula (I):
This has been attained by a silver halide photographic material characterized by containing at least one compound represented by the following formula (II) or (III) .

[0009]

Embedded image In the formula, R ₁ represents an amide group, a ureido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamide group or a sulfamoylamino group,
R ₂ and R ₃ represent a hydrogen atom or a substituent which may be the same as or different from R ₁ . R ₄ represents an alkyl group, an aryl group or a heterocyclic group, and R ₄ further has at least one carboxyl group, sulfo group or hydroxyl group. P
₁ , P ₂ represents a hydrogen atom or a protecting group. TIME represents a timing group, and n is 0 or 1.

That is, the present inventors have made intensive studies to overcome the drawbacks of the conventional bleaching accelerator releasing type compounds, and as a result, have a broadly defined amide group represented by the formula (I). It has been found that a photographic material having high bleach accelerating ability and excellent storage stability can be obtained by using a redox type bleach accelerator releasing compound. Further, among the compounds represented by the formula (I), the compound represented by the following formula (I)
It has been found that the compounds represented by I) and the formula (III) of the following formula 4 give particularly high bleach accelerating ability and excellent storage stability.

[0011]

Embedded image In the formula, R ₄ has the same meaning as in formula (I), and R ₅ has 12 carbon atoms.
Represents the above alkyl group or aryl group.

[0012]

Embedded image In the formula, R ₄ has the same meaning as in formula (I), and R ₆ has 12 carbon atoms.
Represents the above alkyl group or aryl group.

The present invention will be described in more detail.

In the formula (I), R ₁ is a substituted or unsubstituted amide group (for example, acetylamino, benzoylamino, butanamide, dodecanamido, 4-octadecyloxybenzoylamino) having 2 to 80 carbon atoms in total. ,
2-hexyldecaneamide), ureido group (for example, N-
Methylureide, N-phenylureide, N, N-dihexylureide, N- (4-hexadecylcarbamoylphenyl) ureide, N-hexadecylureide), alkoxycarbonylamino group (for example, butoxycarbonylamino, 2-ethylhexyloxycarbonyl) amino,
Eicosiloxycarbonylamino, phenethyloxycarbonylamino), aryloxycarbonylamino group (for example, phenoxycarbonylamino, 4- (octyloxy) phenoxycarbonylamino, 3- (tetradecanamido) phenoxycarbonylamino), sulfonamide group (for example, methanesulfone) An amide, benzenesulfonamide, 4- (dodecyloxy) benzenesulfonamide, hexadecanesulfonamide) or sulfamoylamino group (for example, sulfamoylamino, N-methylsulfamoylamino, N, N-dioctylsulfamoylamino, N- (2-dodecylthiophenyl) sulfamoylamino). These groups may have any substituents such as a halogen atom, a carboxyl group, a sulfo group,
It may be substituted by a hydroxyl group, a cyano group, a nitro group, an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, an amide group, a sulfonamide group, a heterocyclic group, and the like. It may be further substituted by another substituent.

R ₂ and R ₃ are a hydrogen atom or a group having a total of 2 to 80 carbon atoms, and any substituent which may be the same as or different from R ₁ , for example, an amide group, a ureido group, an alkoxycarbonylamino Group, aryloxycarbonylamino group, sulfonamide group, sulfamoylamino group, halogen atom, carboxyl group, sulfo group, hydroxyl group, cyano group, nitro group, alkyl group, aryl group, amino group, alkoxy group, aryloxy group , An alkylthio group or a heterocyclic group. These may be substituted, if possible, by further substituents as in R ₁ . R ₄ has a total of 1 to 20 carbon atoms and has at least one carboxyl group, sulfo group or hydroxyl group, and an alkyl group (eg, carboxymethyl, carboxyethyl, sulfopropyl, hydroxyethyl, 2,3-dihydroxypropyl) ), An aryl group (eg, 2-carboxyphenyl, 4-carboxyphenyl) or a heterocyclic group (eg, 5- (carboxymethylthio) -1,3,4-thiadiazol-2-yl, 4- (carboxymethyl) -5-
Methyl-1,2,4-triazol-3-yl).

P ₁ and P ₂ represent a hydrogen atom or a protecting group. The protecting group may be any group as long as it is a group that can be deprotected in the developing step. Examples of protecting groups include acyl groups (eg, acetyl, chloroacetyl, dichloroacetyl, benzoyl, 4-cyanobenzoyl, 4-oxopentanoyl), alkoxycarbonyl groups (eg, ethoxycarbonyl, phenoxycarbonyl, 4-methoxybenzyloxycarbonyl) ), Aminocarbonyl groups (e.g., methylaminocarbonyl, 4-nitrophenylaminocarbonyl, 2-pyridylaminocarbonyl, 1-imidazolylcarbonyl), and JP-A-59-1970.
37 and JP-A-59-201057. Further, this protecting group may be bonded to R ₁ , R ₂ or R ₃ when possible to form a 5- to 7-membered ring.

TIME represents a timing group linked to the hydroquinone nucleus via a sulfur, nitrogen, oxygen or selenium atom. Examples of TIME include, for example, U.S. Pat. Nos. 4,248,962 and 4,409,323.
No. 4,146,396, British Patent No. 2,09
No. 6,783, JP-A-51-146,828 and JP-A-57-56,837. The TIME may be a combination of two or more selected from those described therein, for example, as shown below. n is 0 or 1.

[0018]

Embedded image R ₅ and R ₆ in the formulas (II) and (III) each represent a substituted or unsubstituted alkyl group having 12 or more carbon atoms (eg, dodecyl,
2-hexyldecyl, octadecyloxycarbonylethyl) or an aryl group (eg, 4- (decyloxy) phenyl, 3,5-bis (2-hexyldecanoylamino)
Phenyl), which may be substituted with any substituent as in R ₁ .

In formula (I), R ₂ and R ₃ are preferably the same groups or hydrogen atoms as R ₁ , P ₁ and P ₂ are preferably hydrogen atoms, and n is preferably 0.

In the formulas (I), (II) and (III), R ₄
Is preferably an aryl group or a heterocyclic group. Further, R ₄ preferably has a carboxyl group or a sulfo group, and particularly preferably has a carboxyl group.

Specific examples of the bleaching accelerator releasing compound used in the present invention are shown below, but the present invention is not limited to these. In addition, among the compounds listed below,
Compounds (4) to (7), (11), (12), (1)
6), (21), (22) and (24) are reference examples.
It is a thing to cite.

[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

Embedded image Hereinafter, typical synthesis examples of the bleaching accelerator releasing compound used in the present invention will be described. Other compounds can be easily prepared by a method analogous thereto.

Synthesis Example 1 (Synthesis of Exemplified Compound (10)) 1-a): Synthesis of 2- {3,5-bis (2-hexyldecanoylamino) benzoylamino} benzoquinone (A) 3,5-bis (2-hexyldecanoylamino) -N- synthesized by the method described in No. 103053
(2,5-dihydroxyphenyl) benzamide 73.
6 g (0.1 mol) was added to 700 mL of toluene together with 50 g of manganese dioxide, and the internal temperature was 80 ° C. while stirring.
, And allowed to cool, and manganese dioxide was filtered off. After toluene was distilled off under reduced pressure, the residue was purified by column chromatography to obtain 58 g of compound A as yellow crystals.

1-b): Synthesis of exemplified compound (10) 14.7 g (0.02 mol) of compound A obtained in 1-a)
And 0.4 g of p-toluenesulfonic acid monohydrate were added to 100 mL of methylene chloride at room temperature, and the mixture was stirred to dissolve Compound A, and then gradually 3.1 g of thiosalicylic acid (0.0 g) was added.
2 mol) was added into the system. After about one hour, the system was solidified. Ethyl acetate was added to dissolve and extract, and then purified by column chromatography to obtain 9.3 g of Exemplified Compound (10) as a light brown solid. NMR, MS supported the structure.

Synthetic Example 2 (Synthesis of Exemplified Compound (15)) According to Synthetic Example 1-b), instead of thiosalicylic acid, 5-
(Carboxymethylthio) -2-mercapto-1,3,3
Using 4.2 g (0.02 mol) of 4-thiadiazole, the reaction was followed by purification by column chromatography.
Exemplified compound (15) was obtained as pale brown crystals in an amount of 11.2 g. NMR, MS supported the structure.

The amount of the bleaching accelerator releasing type compound according to the present invention added to the light-sensitive material is 1 × 10 ⁶ per m ² of the light-sensitive material.
^-7 mol to 1 × 10 ^-1 mol is preferred, and especially 1 × 10 ^-4 mol.
A mole to 5 × 10 ^-2 mole is preferred.

The bleaching accelerator releasing compound according to the present invention can be added to any layer of the light-sensitive material.
That is, it may be added to the photosensitive emulsion layer, or may be added to an intermediate layer, antihalation layer or protective layer containing no photosensitive emulsion. Further, any combination thereof may be used. Preferred is when it is added to the non-light-sensitive layer adjacent to the light-sensitive emulsion layer.

Since the bleaching accelerator releasing type compound according to the present invention has a large bleaching accelerating effect, it can be bleached in a shorter processing time than a known bleaching accelerator releasing type compound. Specifically, when a known compound is used, bleaching treatment 3
Although the bleaching level practically acceptable (less than about 0.1 in terms of concentration) could not be achieved with the compound of the present invention below 3 minutes, the processing time of 3 minutes or less sufficiently reached the acceptable level when the compound of the present invention was used. It is possible to bleach.

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

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

The intermediate layer has a structure described in JP-A-61-43748.
No. 59-113438, No. 59-113440
Couplers, DIR compounds and the like described in JP-A Nos. 61-20037 and 61-20038 may be contained, and a color mixture inhibitor may be contained as usually used.

As described in West German Patent No. 1,121,470 or British Patent No. 923,045, a plurality of silver halide emulsion layers constituting each unit photosensitive layer may be composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer. A two-layer constitution of an emulsion layer 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. JP-A-57-112751, JP-A-62-20035
As described in JP-A Nos. 0, 62-206541 and 62-206543, a low-speed emulsion layer may be provided on the side farther from the support, and a high-speed emulsion layer may be provided on the side closer to the support. .

Explaining based on a specific example, from the side farthest from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / The order of low-sensitivity green photosensitive layer (GL) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL /
GH / RH / RL or BH / BL / GH / GL
/ RL / RH and so on.

Further, as described in JP-B-55-34932, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. JP-A-56-25738 and JP-A-62-63
As described in JP-A-936-936, an order of blue-sensitive layer / GL / RL / GH / RH can be arranged from the side farthest from the support.

As another specific example, Japanese Patent Publication No. 49-1549
As described in JP-A-5, the upper layer has a silver halide emulsion layer having the highest sensitivity, the middle layer has a silver halide emulsion layer having a lower sensitivity, and the lower layer has a halogen having a lower sensitivity than the middle layer. By arranging the silver halide emulsion layer, the sensitivities were sequentially lowered toward the support.
An arrangement composed of layers is mentioned. Even in the case of three layers having different sensitivities, Japanese Patent Application Laid-Open No.
As described in JP-A-02464, a medium-speed emulsion layer /
They may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer.

In addition, a high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or a low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer may be arranged in this order. Also, 4
The arrangement may be changed as described above even in the case of more than layers.

In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, and 4,707,436, JP-A-62-160448.
And BL and G described in the specification of JP-A-63-89850.
It is preferable that a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as L and RL is disposed adjacent to or close to the main photosensitive layer.

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

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is about 30 mol%.
It is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing the following silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% of silver iodide.

The silver halide grains in the photographic emulsion include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystal forms such as spherical and plate-like,
It may have a crystal defect such as a twin plane or a composite form thereof.

The grain size of the silver halide may be fine grains 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 usable in the present invention is described, for example, in Research Disclosure (RD) No.
17643 (December 1978), 22-23,
"I. Emulsion preparat
ion and types) ”and No. 1871
6 (November 1979), p. 648, ibid. 30710
5 (November 1989), pp. 863-865, and "The Physics and Chemistry of Photography" by Grafkid, published by Paul Montel (P. Glafkids, Chemie et Phi).
size Photographique, Paul
Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin,
Photographic Emulsion Che
mistry (Focal Press, 1966),
"Manufacture and Coating of Photographic Emulsions", by Zerikman et al., Published by Focal Press (VL Zelikman et a.)
l. , Making and Coating Pho
graphical Emulsion, Focal
Press, 1964) and the like.

US Pat. Nos. 3,574,628;
655,364 and British Patent 1,413,748.
Monodisperse emulsions described in Nos. 1 and 2 are also preferred.

Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering (Gutoff, Photograph).
ic Science and Engineerine
g), Vol. 14, pp. 248-257 (1970); U.S. Patent Nos. 4,434,226 and 4,414,310.
No. 4,433,048, 4,439,520 and British Patent No. 2,112,157.

The crystal structure may be uniform, the inside and the outside may have different halogen compositions, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining,
Further, 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.

The above emulsion may be of a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which a latent image is formed inside a grain, or a type having a latent image on both the surface and the inside. It must be a negative emulsion. In the case of the internal latent image type, a core / shell type internal latent image type emulsion described in JP-A-63-264740 may be used. A method for preparing this core / shell type internal latent image type emulsion is disclosed in
No. 133542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 × 40 nm, particularly preferably 5 to 20 nm.

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. 17643, ibid. No. 18716 and the same No. 307105, and the corresponding portions are summarized in the table below.

In the light-sensitive material of the present invention, the grain size, grain size distribution, halogen composition,
Two or more emulsions differing in at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer.

The fogged silver halide grains described in US Pat. No. 4,082,553, and the inside of the grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are covered. Silver halide grains and colloidal silver can be preferably used for a light-sensitive silver halide emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer.
The term "silver halide particles having a fogged inside or surface thereof" means silver halide grains which can be uniformly (non-imagewise) developed regardless of unexposed portions and exposed portions of the photosensitive material. . The method for preparing silver halide grains having the inside or the surface thereof fogged is described in U.S. Pat. No. 4,626,498 and JP-A-59-214852.

The silver halide forming the internal nucleus of the core / shell type silver halide grains whose inside is fogged may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but the average grain size is 0.01 to 0.7.
5 μm, particularly preferably 0.05 to 0.6 μm, is preferred. Also,
The particle shape is not particularly limited, and may be regular particles. The emulsion may be a polydisperse emulsion, but is preferably a monodisperse emulsion (in which at least 95% of the weight or the number of silver halide grains has a grain size within ± 40% of the average grain size).

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. .

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or
Alternatively, it may contain silver iodide, and preferably contains 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average of the equivalent circle diameter of the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

The fine silver halide grains can be prepared in the same manner as in the case of ordinary light-sensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in the layer containing fine silver halide grains.

The coated silver amount of the light-sensitive material of the present invention is 6.0 g.
/ M ² or less are preferred, 4.5 g / m ² or less is most preferred.

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

Type of Additive RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 right column page 866 2. Sensitivity increasing agent, page 648, right column 3. Spectral sensitizers, pages 23 to 24, page 648, right column 866 to 868, super sensitizers, page 649, right column Brightener page 24 page 647 right column page 868 5. 5. Fogging prevention page 24-25 page 649 right column 868-870 page Agents, stabilizers 6. Light absorbers, pages 25 to 26, page 649, right column, page 873, filters-page 650, left column, dyes, ultraviolet absorbers 7. Stain page 25 right column 650 page left column 872 inhibitor ~ right column 8. Dye image page 25 page 650 left column page 872 stabilizer 10. Hardener page 26 page 651 left column pages 874-875 Binder page 26 page 651 left column pages 873 to 874 11. 11. plasticizer, page 27, page 650, right column, page 876, lubricant; Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876 Surfactant 13. Static 27 pages 650 page right column 876-877 Inhibitors 14. Matto, pp. 878-879 Also, in order to prevent deterioration of photographic performance due to formaldehyde gas, immobilization by reacting with formaldehyde described in U.S. Pat. Nos. 4,411,987 and 4,435,503. It is preferable to add a compound that can be used to the light-sensitive material.

In the light-sensitive material of the present invention, US Pat.
0,454 and 4,788,132
It is preferable to include a mercapto compound described in JP-A-18539 and JP-A-1-283551.

The light-sensitive material of the present invention can be prepared irrespective of the amount of developed silver produced by the development processing, as described in JP-A-1-10605.
It is preferable to contain a fogging agent, a development accelerator, a silver halide solvent or a compound capable of releasing a precursor thereof described in No. 2.

The light-sensitive material of the present invention may be added to International Publication W088 /
No. 04794, a dye dispersed by the method described in JP-A-1-502912, or EP 317,308A.
No. 4,420,555, JP-A-1-259
No. 358 is preferably contained.

Various color couplers can be used in the present invention, and specific examples thereof are described in Research Disclosure No. 17643, VII-CG and N
o. 307105, VII-CG.

As the yellow coupler, other than those represented by formulas (1) and (2) of the present invention, for example, US Pat. Nos. 3,933,501 and 4,022,620
No. 4,326,024 and 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107
No. 39, British Patent Nos. 1,425,020 and 1,4
No. 76,760; U.S. Pat. Nos. 3,973,968; 4,314,023; 4,511,649;
Those described in EP 249,473A and the like are preferred.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferable. US Pat. Nos. 4,310,619 and 4,351,897
No. 3,073,636; U.S. Pat.
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984
), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, and JP-A-60-72238.
No. 35730, No. 55-118034, No. 60-18
No. 5,951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, and W088 / 04795 are particularly preferable.

Examples of the cyan coupler include phenolic and naphthol couplers. Among them, for example, U.S. Patent Nos. 4,052,212 and 4,146,3
No. 96, No. 4,228,233, No. 4,296,
No. 200, No. 2,369,929, No. 2,80
No. 1,171, No. 2,772,162, No. 2,8
No. 95,826, No. 3,772,002, No. 3,
Nos. 758,308, 4,334,011, 4,327,173, and West German Patent Publication 3,329,7.
29, European Patent Nos. 121, 365A and 249,
No. 453A, U.S. Pat. Nos. 3,446,622, 4,333,999, 4,775,616, 4,451,559, 4,427,767,
Nos. 4,690,889 and 4,254,212
No. 4,296,199, JP-A-61-4265.
No. 8 is preferable. Further, Japanese Patent Application Laid-Open No. Sho 64-5
No. 53, No. 64-554, No. 64-555, No. 64
A pyrazoloazole coupler described in -556 and an imidazole coupler described in U.S. Pat. No. 4,818,672 can also be used.

Typical examples of polymerized dye-forming couplers are described in US Pat. Nos. 3,451,820 and 4,084,820.
No. 0,211, No. 4,367,282, No. 4,4
Nos. 09,320, 4,576,910, British Patent 2,102,137, and European Patent No. 341,188A.

Examples of couplers in which a coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent No. 2,125,570, and European Patent No. 96,570.
Those described in West German Patent (Published) No. 3,234,533 are preferred.

A colored coupler for correcting unnecessary absorption of a coloring dye is described in Research Disclosure No.
No. 17643, section VII-G; VII of 307105-
Section G, U.S. Pat. No. 4,163,670, JP-B-57-
39413, U.S. Pat. Nos. 4,004,929 and 4,138,258, British Patent 1,146,368.
Those described in the above item are preferred. Also, U.S. Pat.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in No. 4,181,
It is also preferable to use a coupler having a dye precursor group capable of forming a dye by reacting with a developing agent described in US Pat. No. 4,777,120 as a leaving group.

Compounds which release a photographically useful residue upon coupling can also be preferably used in the present invention. The DIR coupler releasing the development inhibitor is the same as described above for R
No. D17643, VII-F and the same No. 307105, VI
Patents described in section IF, JP-A-57-151944
No., No. 57-154234, No. 60-184248
And JP-A-63-37346 and JP-A-63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred.

R. D. No. 11449, 24241,
The bleaching accelerator releasing couplers described in JP-A-61-201247 and the like are effective in shortening the processing time having a bleaching ability. In particular, the effect is great when it is added to a photographic material using the above-mentioned tabular silver halide grains. Examples of couplers which release a nucleating agent or a development accelerator in an image-like manner during development include British Patent 2,097,140.
No. 2,131,188, JP-A-59-1576.
Nos. 38 and 59-170840 are preferred. Also, JP-A-60-107029 and JP-A-60-25
No. 2340, JP-A-1-44940 and 1-4568.
The compounds described in No. 7 which release a fogging agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized form of a developing agent are also preferable.

Other compounds usable in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
No. 4,283,4.
No. 72, No. 4,338,393, No. 4,310,
No. 618, etc .;
No. 5950, Japanese Patent Application Laid-Open No. 62-24252, and the like.
R redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds or DIR redox releasing redox compounds, couplers capable of releasing dyes which discolor after release as described in EP 173,302A and EP 313,308A A ligand releasing coupler described in U.S. Pat. No. 4,555,477, a leuco dye releasing coupler described in JP-A-63-75747, and a fluorescent dye described in U.S. Pat. No. 4,774,181. Emitting couplers and the like.

The coupler used in the present invention can be introduced into a 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, for example, US Pat. No. 2,322,027. Specific examples of high-boiling organic solvents having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include, for example, phthalic esters (eg, dibutyl phthalate,
Dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t
-Amylphenyl) phthalate, bis (2,4-di-t)
-Amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate); esters of phosphoric acid or phosphonic acid (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri- 2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate); benzoic acid esters (for example, 2
-Ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate); amides (eg, N, N-diethyldodecaneamide, N, N-diethyllauramide, N-tetradecylpyrrolidone); alcohols or phenols ( For example, isostearyl alcohol, 2,4-di-tert
-Amylphenol); aliphatic carboxylic acid esters (e.g., bis (2-ethylhexyl) sebacate, dioctylazelate, glycerol tributyrate, isostearyl lactate, trioctylcitrate); aniline derivatives (e.g., N, N-dibutyl- 2-butoxy-5-tert-octylaniline); and hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene). As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or more, preferably 50 ° C. or more and about 160 ° C. or less can be used. Typical examples thereof include, for example, ethyl acetate, butyl acetate, 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, for example, in US Pat.
9,363, West German Patent Application (OLS) No. 2,541,
274 and 2,541,230.

The color light-sensitive material of the present invention includes, for example, phenethyl alcohol and 1,2-benzisothiazoline-3-one described in JP-A-63-257747, JP-A-62-272248 and JP-A-1-80941. On, n
-Butyl p-hydroxybenzoate, phenol,
It is preferable to add various preservatives or fungicides such as 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, 2- (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, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers.

Suitable supports that can be used in the present invention are described, for example, in RD. No. No. 17643, page 28, ibid. 18
No. 716, from the right column on page 647 to the left column on page 648; 3
No. 07105, page 879.

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 preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less, more preferably 16 μm or less.
Further, the expansion and swelling speed T _1/2 is preferably 30 seconds or less,
Seconds or less are more preferred. The film thickness is 25 ° C and relative humidity 55%
It means the film thickness measured under humidity control (2 days). The film swelling rate T _1/2 can be measured according to a method known in the art. For example, A Green (AG
reen) et al.
And Engineering (Photogr. Sci.
Eng. ), Vol. 19, No. 2, pp. 124-129 can be used for measurement. Further, T _1/2 is 30 ° C., 3
90% of the maximum swollen film thickness reached when the treatment is performed for 15 minutes is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness.

The swelling speed T _1/2 can be adjusted by adding a hardener to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is preferably from 150 to 400%. The swelling ratio is calculated from the maximum swelling film thickness under the conditions described above by the following formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.

In the light-sensitive material of the present invention, a hydrophilic colloid layer having a total dry film thickness of 2 μm to 20 μm (referred to as a back layer) is preferably provided on the side opposite to the side having the emulsion layer. The back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent, and the like. The swelling ratio of this back layer is 150
~ 500% is preferred.

The color photographic light-sensitive material according to the present invention is prepared according to the RD. No. No. 17643, pp. 28-29, ibid. 18
No. 716, left column to right column, and No. 716. 307105
880-881.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used. Representative examples are 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline,
-Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluene Sulfonates and the like. Among these, in particular, 3-methyl-4
-Amino-N-ethyl-N-β-hydroxyethylaniline sulfate is preferred. These compounds are used depending on the purpose.
More than one species may be used in combination.

The color developing solution may be a pH buffer such as an alkali metal carbonate, borate or phosphate, or a chloride, bromide, iodide, benzimidazole, benzothiazole or mercapto compound. It generally contains a development inhibitor or an antifoggant such as If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine, catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, benzene alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting And various chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid. Among them, chelating agents include, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1
-Diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N. , N-tetramethylenephosphonic acid, ethylenediamine-di (o-
Hydroxyphenylacetic acid) and their salts.

When the reversal process is performed, color development is usually performed after black and white development. In this black and white developer,
For example, a known black-and-white developing agent represented by dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol is used alone. Alternatively, they can be used in combination. The pH of the color developer and the black-and-white developer is 9 to 12.
It is common that The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the photographic material, and 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also When the replenishment amount is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air.

The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [capacity of treatment liquid (cm ³ )] The above-mentioned aperture ratio is preferably 0.1 or less, more preferably 0. 0.001 to 0.05. As a method of reducing the aperture ratio in this manner, in addition to providing a shield such as a floating lid on the surface of the photographic processing solution in the processing tank, Japanese Patent Application Laid-Open No.
No. 033, a method using a movable lid,
And a slit developing method described in JP-A-216050. Reducing the aperture ratio is not only in both the color development and black-and-white development steps, but also in the subsequent steps,
For example, it is preferably applied in all steps such as bleaching, bleach-fixing, fixing, washing with water, and stabilization. Further, by using means for suppressing the accumulation of bromide ions in the developer, the replenishing amount can be reduced.

The time for the color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of the color developing agent. .

The photographic emulsion layer after color development is usually subjected to bleaching. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further, processing in two continuous bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are organic complex salts of iron (III) such as amino acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid. A complex salt of a polycarboxylic acid and iron (III), or a complex salt of citric acid, tartaric acid or malic acid and iron (III) can be used. Among these, iron (III) complex salts of aminopolycarboxylate, such as iron (III) complex salt of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate, are used in view of rapid treatment and prevention of environmental pollution. Is preferred. Further, iron (III) aminopolycarboxylate is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually from 4.0 to 8, but the processing can be carried out at a lower pH for speeding up the processing.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleaching accelerators are described in the following specifications: U.S. Pat. No. 3,893,858, West German Patents 1.29.812, 2,059,988, JP Nos. 53-32736, 53-57831, 53
No. 37418, No. 53-72623, No. 53-95
No. 630, No. 53-95731, No. 53-10423
No. 2, No. 53-124424, No. 53-141623
No. 53-28426, Research Disclosure No. No. 17129 (July, 1978); compounds having a mercapto group or disulfide group; thiazolidine derivatives described in JP-A-50-140129; JP-B-45-8506, JP-A-52-20832.
No. 53-32735, U.S. Pat. No. 3,706,5
No. 61; thiourea derivative; West German Patent No. 1,12
7,715, JP-A-58-16,235; West German Patents 996,410, 2,748,4
Polyoxyethylene compounds described in No. 30, JP-B-4
Polyamine compounds described in JP-A-5-8836; and JP-A-49-40,943, 49-59,644, and 53.
Nos. -94,927, 54-35,727 and 55-
Compounds described in Nos. 26,506 and 58-163,940; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and in particular, US Pat.
No. 58, West German Patent No. 1,290,812,
Compounds described in -95,630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing color photographic materials for photography.

The bleaching solution and the bleach-fixing solution preferably contain an organic acid in addition to the above compounds for the purpose of preventing bleaching stain. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, specifically acetic acid, propionic acid and hydroxyacetic acid.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodides. Use is common, especially ammonium thiosulfate being the most widely used. It is also preferable to use a combination of a thiofluoate with a thiocyanate, a thioether-based compound, or thiourea. As a preservative of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct, or a sulfinic acid compound described in EP-A-294769A is preferable. Further, it is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixing solution or the bleach-fixing solution contains a compound having a pKa of 6.0 to 9.0 for adjusting pH.
Preferably, imidazole, 1-methylimidazole,
It is preferable to add imidazoles such as 1-ethylimidazole and 2-methylimidazole in an amount of 0.1 to 10 mol / l.

It is preferable that the total time of the desilvering step is shorter as long as the desilvering failure does not occur. Preferred time is 1 minute to 3
Minutes, more preferably 1 to 2 minutes. Further, the processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 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, it is preferable that the stirring is strengthened as much as possible. As a specific method of enhancing stirring, a method described in JP-A-62-183460, in which a jet of a processing solution is made to impinge on the emulsion surface of a photosensitive material, or a method using a rotating means described in JP-A-62-183461, is used. A method for improving the effect, a method for moving the photosensitive material while bringing the wiper blade provided in the liquid into contact with the emulsion surface, and making the emulsion surface turbulent to improve the stirring effect, and a circulation of the entire processing solution. There is a method of increasing the flow rate. Such stirring improving means include a bleaching solution, a bleach-fixing solution,
It is effective in any of the fixing solutions. It is considered that the improved 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 stirring is more effective when a bleaching accelerator is used, and can remarkably increase the accelerating effect or eliminate the fixing inhibition effect of the bleaching accelerator.

The automatic developing machine used for the light-sensitive material of the present invention is described in JP-A-60-191257 and JP-A-60-19125.
No. 8, No. 60-191259.

As described in the above-mentioned JP-A-60-191257, such a transport means can significantly reduce the carry-in of the processing solution from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing solution 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.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely.
Among them, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in Journal-of-the-Society.
ty of Motion Picture T
ele-vision Engineers Vol. 64,
P. 248-253 (May, 1955). According to the multi-stage countercurrent method described in the document, the amount of washing water can be significantly reduced, but bacteria increase due to an increase in the residence time of water in the tank, and the generated suspended matter adheres to the photosensitive material. Problems arise. In the processing of the color tourism material of the present invention, such a problem is solved as disclosed in Japanese Patent Application Laid-Open No. 62-288,838.
The method for reducing calcium ions and magnesium ions described in (1) can be used very effectively. Also, chlorinated fungicides such as isothiazolone compounds, thiabendazoles, chlorinated sodium isocyanurate, etc., and benzotriazoles described in JP-A-57-8542, Hiroshi Horiguchi, "Antibacterial and antifungal agents" Chemistry "(1986)
Sankyo Shuppan, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Antimicrobial and Antifungal Society, Ed. Can also be used.

Washing water in processing the light-sensitive material of the present invention
The pH is between 4 and 9, preferably between 5 and 8. The washing temperature and washing time can also be variously set according to the characteristics of the photosensitive material, the use, etc., but generally at 15 to 45 ° C. for 20 seconds to 1 hour.
A range of 0 minutes, preferably 30 seconds to 5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization process, Japanese Patent Application Laid-Open No. 57-8543
, 58-14834 and 60-220345 can all be used.

In some cases, a stabilization process may be performed subsequent to the water washing process. An example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photography. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the washing and / or replenishment of the stabilizing solution can be reused in other steps such as a desilvering step.

In the processing using an automatic developing machine or the like, when the above-mentioned processing solutions are concentrated by evaporation, it is preferable to add water to correct the concentration.

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, Research Disclosure No. 14, 850 and the same. 15,159, Schiff base compounds, aldol compounds described in JP-A-13,924, metal salt complexes described in U.S. Pat. No. 3,719,492, and urethane-based compounds described in JP-A-53-135628. be able to.

The silver halide color light-sensitive material of the present invention comprises:
If necessary, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339 and JP-A-57-14.
Nos. 4547 and 58-115438.

Various processing solutions in the present invention may be used at a temperature of 10 ° C. to 50 ° C.
Used at ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature promotes the processing and shortens the processing time, and a lower temperature achieves an improvement in the image quality and an improvement in the stability of the processing solution. be able to.

The silver halide light-sensitive material of the present invention is disclosed in US Pat. No. 4,500,626 and JP-A-60-1334.
No. 49, 59-218443, 61-23805
No. 6, EP 210,660 A2 and the like.

[0112]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a sample 101 as a multilayer color photosensitive material. (Composition of photosensitive layer) The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer. (Sample 101) First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.18 Gelatin 1.00 Second Layer (Intermediate Layer) 2,5-Di-t-pentadecylhydroquinone 0.18 EX-1 0.18 EX-3 0.020 EX-12 2.0 × 10 ^-3 U-1 0.060 U-2 0.080 U-3 0.10 HBS-1 0.10 HBS-2 0.020 Gelatin 1.04 Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion A silver 0.25 silver iodobromide emulsion B silver 0.25 sensitizing dye I 6.9 × 10 ^-5 sensitizing dye II 1.8 × ^10-5 sensitizing dye III 3.1 x ^10-4 EX-2 0.17 EX-10 0.020 EX-14 0.17 U-1 0.070 U-2 0.050 U-3 0.070 HBS-1 0.060 Gelatin 0.87 Fourth layer (second red-sensitive emulsion layer) Silver iodobromide emulsion G Silver 1 Sensitized 00 sensitizing dye I 6.6 × 10 ^-5 Sensitizing dye II 1.8 × 10 ^-5 dye ^{III 3.0 × 10 -4 EX-2} 0.20 EX-3 0.050 EX-10 0 0.015 EX-14 0.20 EX-15 0.050 U-1 0.070 U-2 0.050 U-3 0.070 Gelatin 1.30 Fifth layer (third red-sensitive emulsion layer) Silver Emulsion D Silver 1.60 Sensitizing Dye I 7.6 × 10 ⁻⁵ Sensitizing Dye II 2.0 × 10 ⁻⁵ Sensitizing Dye III 3.4 × 10 ⁻⁴ EX-2 0.097 EX-30 0.010 EX-4 0.080 HBS-1 0.22 HBS-2 0.10 Gelatin 1.10 6th layer (intermediate layer) EX-5 0.040 HBS-1 0.020 Gelatin 0.60 7th layer (First green-sensitive emulsion layer) Silver iodobromide emulsion A silver 0.15 silver iodobromide emulsion B silver 0.15 sensitizing dye IV 3.0 × 10 ^-5 sensitizing dye V 1.0 × 10 ^-4 sensitizing dye VI 3.8 × 10 ^-4 EX-1 0.021 EX-6 0.26 EX-7 0.030 EX-8 0.025 HBS-1 0.10 HBS- 3 0.010 Gelatin 0.63 Eighth layer (second green-sensitive emulsion layer) Silver iodobromide emulsion C Silver 0.45 Sensitizing dye IV 3.0 × 10 ^-5 Sensitizing dye V 9.8 × 10 ^{− 5} Sensitizing dye VI 3.6 × 10 ^-4 EX-6 0.094 EX-7 0.026 EX-8 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.50 Ninth layer (third green-sensitive emulsion layer) Silver iodobromide emulsion E Silver 1.20 Sensitizing dye IV 4.9 × 10 ⁻⁵ Sensitizing dye V 9.5 × 10 ⁻⁵ Sensitizing dye VI 4.2 ^{× 10 -4 EX-1 0.013 EX} -11 0.065 EX-13 0.019 HBS-1 0.25 HBS-2 0.10 gelatin 1.54 10th layer (Ye -Filter layer) yellow colloidal silver silver 0.050 EX-5 0.080 HBS-1 0.030 gelatin 0.50 eleventh layer (first blue-sensitive emulsion layer) silver iodobromide emulsion A silver 0.080 iodobromide Silver emulsion B Silver 0.070 Silver iodobromide emulsion F Silver 0.070 Sensitizing dye VII 4.5 × 10 ^-4 EX-8 0.042 EX-9 0.72 HBS-1 0.28 Gelatin 1.10 Twelfth layer (second blue-sensitive emulsion layer) Silver iodobromide emulsion G Silver 0.45 Sensitizing dye VII 5.5 × 10 ^-4 EX-9 0.15 EX-10 7.0 × 10 ^-3 HBS- 1 0.050 gelatin 0.78 thirteenth layer (third blue-sensitive emulsion layer) silver iodobromide emulsion H silver 0.77 sensitizing dye VII 7.0 × 10 ^-4 EX-9 0.20 HBS-10 0.070 Gelatin 0.69 Fourteenth Layer (First Protective Layer) Silver Iodobromide Emulsion I Silver 0.20 U-4 0.1 U-5 0.17 HBS-1 5.0 × 10 -2 Gelatin 1.00 15th layer (second protective layer) H-1 0.40 B-1 ( diameter 1.7μm) 5.0 × 10 ^{- 2} B-1 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20 Further, all layers have storability, processability, pressure resistance, antifungal / antibacterial properties, In order to improve antistatic properties and coating properties, W-1,
W-2, W-3, B-4, B-5, F-1, F-2, F
-3, F-4, F-5, F-6, F-7, F-8, F-
9, F-10, F-11, F-12, and F-13, and iron salts, lead salts, gold salts, platinum salts, iridium salts, and rhodium salts.

(Samples 102 to 109) The compound EX-5 in the sixth layer of the sample 101 was replaced with the comparative compound, the reference compound or the compound of the present invention in the table shown in Table 1 in an equimolar amount. To 109 were produced.

(Samples 110 to 112) Samples 101 and 10
In the fifth layer of 5,107, as shown in Table 1, 0.005 g of the compounds (13), (10) and (15) of the present invention, respectively.
/ M ^{2 was} added to prepare Samples 110 to 112.

Each of the samples was exposed to red imagewise light, and the following color development was performed. The value obtained by subtracting the magenta density in the cyan fog density from the magenta density in the cyan density 2.0 was determined as the color turbidity.

After white imagewise exposure, the following color development was performed to measure the density. Then, in order to remove the silver remaining as a desilvering (bleaching) defect, immerse in a dark place in the following bleaching mother liquor for 30 minutes, washing with water for 5 minutes, fixing mother liquor for 5 minutes, washing with water for 5 minutes and stable mother liquor for 2 minutes. After drying, the concentration was measured again. Since the change in the yellow density was the largest for all samples, the reduced density at the initial yellow density of 3.0 is shown in Table 1 as the defective desilvering density.

Further, after white imagewise exposure, the film was allowed to stand for 7 days under conditions of 25 ° C., 65% relative humidity and 80 ° C. (forced deterioration condition) at 45 ° C., respectively, and then subjected to the following color development to obtain a cyan density (fog +0). The relative sensitivity fluctuation obtained from the logarithmic value of the reciprocal of the exposure amount giving 2) was determined.

The color development was performed using an automatic developing machine by the following method until the cumulative replenishment amount of the liquid became three times the capacity of the mother liquor tank.

Processing method Step Processing time Processing temperature Replenishment amount Tank capacity Color development 3 min 15 sec 38 ° C 33mL 20L Bleaching 2min 30sec 38 ° C 25mL 40L Rinse 2min 10sec 24 ° C 1200mL 20L Fix 4min 20sec 38 ° C 25mL 30L Water washing (1) 1 minute 05 seconds 24 ° C From (2) to (1) 10L countercurrent piping method Water washing (2) 1 minute 00 seconds 24 ° C 1200mL 10L Stability 1 minute 05 seconds 38 ° C 25mL 10L Drying 4 minutes 20 seconds 55 ° C Replenishment amount per 35 mm width 1 m length Next, the composition of the processing solution is described. (Color developing solution) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg-Hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-hydroxyethylamino] -2-methyla Niline sulfate 4.5 5.5 Add water 1.0L 1.0L pH 10.05 10.10 (Bleaching solution) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid sodium ferric sodium trihydrate 100.0 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 10.0 Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 Ammonia Water (27%) 6.5 mL 4.0 mL Add water 1.0 L 1.0 L pH 6.0 5.7 (Fixing solution) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid disodium salt 0. 5 0.7 Sodium sulfite 7.0 8.0 Sodium bisulfite 5.0 5.5 Ammonium thiosulfate aqueous solution (70%) 170.0 mL 200.0 mL Add water 1.0 L 1.0 L pH 6.7 6. 6 (Stabilizing solution) Mother liquor (g) Replenisher (g) Formalin (37%) 2.0 mL 3.0 mL Polyoxyethylene-p-monononyl phenyl ether (average degree of polymerization 10) 0.3 0.45 Ethylenediaminetetraacetic acid Sodium salt 0.05 0.08 Add water 1.0 L 1.0 L pH 5.0-8.0 5.0-8.0 As is clear from Table 1, the sample using the compound of the present invention.
105 to 107 and 109 to 112 are comparative samples 10
As compared with Nos. 1 to 103, the color reproducibility represented by the degree of color turbidity and the desilvering property were excellent, and the sensitivity fluctuation during the storage period from the exposure to the development was small, indicating the effectiveness of the present invention.

[0121]

[Table 1] Example 2 Cpd-1 added to the fifth layer of sample 105 described in JP-A-2-285346 was replaced with the compound (10) of the present invention and the compound (16) of the reference example in equimolar amounts. Samples 201 and 202 were prepared. The compound (1) of the present invention was added to the fourth layer of the patent sample 105.
0), Reference Example Compound (16) and Comparative Compound R-
1, Samples 203 to 203 were added by adding 0.015 g / m ^{2 of} R-2.
206 were produced.

When these samples were tested in the same manner as in Example 1, Samples 201 and 203 were superior to Sample 105 and Comparative Samples 205 and 206 of the patent in color reproducibility, desilvering, and storage stability. It was confirmed that. Table 2 shows the desilvering data.

The above sample was treated in the same manner as in Example 1 except that the bleaching step was performed for 6 minutes and 30 seconds.
When the desilvering property was evaluated, the results shown in Table 2 were obtained.

[0124]

[Table 2] As can be seen from Table 2, the samples using the compounds of the present invention can be efficiently desilvered to a practically acceptable level with a short bleaching time of 3 minutes or less.

Example 3 Compounds (13) and (19) of the present invention were prepared in the same manner as in Samples 3 to 3 of Table 3 in Example 3 except that Sample 301 described in Example 3 of JP-A-2-93454 was used. Samples 321 and 322 to which was added.

When the amount of residual silver of these samples was measured in the same manner as in this example, it was confirmed that samples 321 and 322 had a smaller amount of residual silver than samples 306 to 310 of the patent.

The compounds and emulsions used in the examples are shown below.

[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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[0141]

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[0142]

[Table 3]

Conventionally, a photographic material using a redox-type bleaching accelerator releasing compound has a drawback that the desilvering property is not sufficient and the storage stability is deteriorated. It has become possible to obtain photographic materials overcoming the disadvantages.

Claims (2)

(57) [Claims] 1. A silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, characterized by containing a compound represented by the following formula (II) or (III). Silver halide photographic light-sensitive material. Embedded image Wherein R ₄ is at least one carboxyl group, sulfo
An alkyl group having a group or a hydroxyl group, an aryl group or
Represents a heterocyclic group, wherein R ₅ and R ₆ are each independently
Represents an alkyl group or an aryl group having a prime number of 12 or more. 2. The silver halide according to claim 1, wherein the compound represented by the formula (I) or (II) is contained in a non-light-sensitive layer adjacent to the light-sensitive silver halide emulsion layer. Photosensitive material.