JP2893101B2 - Processing method of silver halide photographic light-sensitive material and photographic fixing function composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide light-sensitive material, and more particularly to a bath containing a fixing agent which is excellent in fixability and can be used even at a low replenishment rate, and the liquid stability of the bath thereafter. The present invention relates to a method for processing a silver halide light-sensitive material having excellent heat resistance.

[0002]

2. Description of the Related Art Generally, processing of a silver halide color photographic light-sensitive material comprises a color developing process and a silver removing process. Silver generated by development is oxidized by a bleaching agent and then dissolved by a fixing agent. Ferric (III) ion complex salts (eg, aminopolycarboxylic acid-iron (III) complex salts) are mainly used as bleaching agents, and thiosulfates are generally used as fixing agents. The processing of the black-and-white photographic light-sensitive material comprises a developing step and a step of removing unexposed silver halide, and unlike the processing of a color photographic light-sensitive material, fixing processing is performed without a bleaching step after development. Also in this case, thiosulfate is usually used as a fixing agent.

In recent years, as the replenishment rate has been reduced, a more stable liquid composition has been desired for each treatment bath. Regarding the fixing bath, thiosulfate, which is usually used, undergoes oxidative deterioration and is sulfurized to form a precipitate. Therefore, in most cases, sulfite is added as a preservative for preventing oxidation. However, as the replenishment further progresses, the improvement of the liquid stability is further desired.However, it is possible to solve the problem by increasing the amount of added sulfite because of the solubility problem and the precipitation of sodium sulfate when the sulfite is oxidized. It's gone.

On the other hand, from the viewpoint of speeding up, there is a demand for a compound having better fixability than thiosulfate. For these reasons, it has been desired to develop a fixing agent that replaces thiosulfate, which is excellent in oxidative stability and fixing property, but no good alternative compound has been found up to the present.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a fixing method having excellent fixing properties. Another object of the present invention is to provide a bath containing a fixing agent even when the replenishment amount is low, and a method for processing a silver halide light-sensitive material having improved bath stability.

[0006]

The above object has been achieved by the following processing method and processing composition. (1) After exposure of a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, a bath having a fixing ability in a processing method of developing does not substantially contain thiosulfate ions. And at least one compound represented by the following general formula (I) as a fixing agent. General formula (I)

[0007]

Embedded image

In the formula, Q represents a group of atoms necessary to form a 5- or 6-membered heterocyclic ring. This heterocyclic ring may be condensed with a carbon aromatic ring or a heteroaromatic ring. R represents a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, an alkyl group substituted with at least one of an amino group or an ammonium group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, Represents a bond. Here, the single bond means a case where a carboxylic acid, a sulfonic acid, a phosphonic acid or a salt thereof, an amino group or an ammonium group is directly bonded to the hetero ring composed of Q. n represents an integer of 1 to 3, and M represents a cationic group.

(2) A photographic fixing power composition substantially free of thiosulfate ions and containing at least one compound represented by the above general formula (I).

Next, the general formula (I) will be described in detail.
In the general formula (I), Q is preferably an atom group necessary for forming a 5- or 6-membered heterocyclic ring composed of at least one atom of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom. Represents The heterocyclic ring may be fused with a carbon aromatic ring or a heteroaromatic ring. As the heterocycle, for example, tetrazole, triazole, imidazole, thiadiazole, oxadiazole, selenadiazole, oxazole, thiazole, benzoxazole, benzothiazole, benzimidazole, pyrimidine, triazain Dens, tetraazaindenes, pentaazaindenes and the like.

R represents a carboxylic acid or a salt thereof (eg, sodium salt, potassium salt, ammonium salt, calcium salt), a sulfonic acid or a salt thereof (eg, sodium salt,
Potassium salts, ammonium salts, magnesium salts, calcium salts), phosphonic acids or salts thereof (eg, sodium salts, potassium salts, ammonium salts), substituted or unsubstituted amino groups having 1 to 10 carbon atoms (eg, unsubstituted amino groups, At least one selected from a dimethylamino group, a diethylamino group, a methylamino group, a bismethoxyethylamino group) and a substituted or unsubstituted ammonium group having 3 to 12 carbon atoms (eg, trimethylammonium group, triethylammonium group, dimethylbenzylammonium group) An alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, isopropyl group, 2-hydroxypropyl group, hexyl group, octyl group), Alkenyl group (for example, vinyl group, propenyl group Butenyl group), an aralkyl group having 7 to 12 carbon atoms (eg, benzyl group, phenethyl group), an aryl group having 6 to 12 carbon atoms (eg, phenyl group, 2-chlorophenyl group, 3-methoxyphenyl group, naphthyl group), carbon atom Represents a heterocyclic group represented by Formulas 1 to 10 (for example, a pyridyl group, a thienyl group, a furyl group, a triazolyl group, an imidazolyl group) or a single bond. R may be a group obtained by arbitrarily combining the above-mentioned alkyl group, alkenyl group, aralkyl group, aryl group and heterocyclic group (for example, a heterocyclic-substituted alkyl group, benzyl group, phenethyl group, styryl group). , -CO-, -CS-, -SO
_{2 -, - NR 1 -,} - O- or -S- any combination linking group (e.g. _{-COO-, -OCO-, -CON (R 1} ) -, -N (R 1)
CO-, -SO _3- , -SO ₂ N (R ₁ )-, -N (R ₁ ) SO _2- , -N (R ₁ ) CON (R ₁ )-, -N
(R ₁ ) CSN (R ₁ )-) may be included. Here, R ₁ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, butyl group, hexyl group), an aralkyl group having 7 to 10 carbon atoms (eg, benzyl group, phenethyl group), Represents 6 to 10 aryl groups (for example, a phenyl group and a 4-methylphenyl group).

M is a cationic group (eg, an alkali metal atom such as a hydrogen atom, a sodium atom or a potassium atom, an alkaline earth metal atom such as a magnesium atom or a calcium atom, an ammonium group such as an ammonium group or a triethylammonium group). Represents

The heterocyclic ring represented by the general formula (I) and R are a nitro group, a halogen atom (eg, a chlorine atom or a bromine atom), a mercapto group, a cyano group, a substituted or unsubstituted alkyl group (eg, a methyl group) , Ethyl group, propyl group, t-butyl group, cyanoethyl group), aryl group (for example, phenyl group, 4-methanesulfonamidophenyl group, 4-methylphenyl group, 3,4-dichlorophenyl group, naphthyl group), Alkenyl (eg, allyl), aralkyl (eg, benzyl, 4-methylbenzyl, phenethyl), sulfonyl (eg, methanesulfonyl, ethanesulfonyl, p-toluenesulfonyl), carbamoyl (eg, unsubstituted) Carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group), sulfamoyl Groups (for example, unsubstituted sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group), carbonamide group (for example, acetamido group, benzamide group), and sulfonamide group (for example, methanesulfonamide group, benzenesulfonamide group, p- Toluenesulfonamide group), acyloxy group (eg, acetyloxy group, benzoyloxy group), sulfonyloxy group (eg, methanesulfonyloxy group), ureido group (eg, unsubstituted ureido group, methylureido group, ethylureido group, phenylureido group) ), Thioureido groups (eg unsubstituted thioureido groups, methylthioureido groups),
Acyl groups (eg, acetyl group, benzoyl group), oxycarbonyl groups (eg, methoxycarbonyl group, phenoxycarbonyl group), oxycarbonylamino groups (eg, methoxycarbonylamino group, phenoxycarbonylamino group, 2-ethylhexyloxycarbonylamino group), It may be substituted with a hydroxyl group or the like.

N represents an integer of 1 to 3, but when n represents 2 or 3, each R may be the same or different.

In the general formula (I), preferably Q is tetrazole, triazole, imidazole, oxadiazole, triazaindene, tetraazaindene,
Pentaazaindenes; R represents an alkyl group having 1 to 6 carbon atoms substituted with one or two of a group selected from a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, and n represents 1 or 2 Represents In the general formula (I), a more preferable compound is the general formula (II). General formula (II)

[0016]

Embedded image

In the formula, M and R have the same meanings as in each of the general formula (I). T and U are CR 'or N
And R 'represents a hydrogen atom, a halogen atom, a hydroxy group, a nitro group, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a carbonamido group, a sulfonamido group, a ureido group, a thioureido group or R. However, when R ′ represents R, it may be the same as or different from R in the general formula (II).

Next, the general formula (II) will be described in detail.
T and U represent C-R 'or N, and R' is a hydrogen atom, a halogen atom (eg, a chlorine atom, a bromine atom, etc.),
A hydroxy group, a nitro group, an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a methoxyethyl group, an n-
Butyl group, 2-ethylhexyl group, etc.), having 2 to 1 carbon atoms
0 alkenyl group (for example, allyl group, etc.), having 7 to 7 carbon atoms
15 aralkyl groups (for example, benzyl group, 4-methylbenzyl group, phenethyl group, 4-methoxybenzyl group,
Etc.), an aryl group having 6 to 15 carbon atoms (e.g., phenyl group, naphthyl group, 4-methanesulfonamidophenyl group, 4-methylphenyl group, etc.), a carbonamido group having 1 to 10 carbon atoms (e.g., acetyl An amino group, a benzoylamino group, a methoxypropionylamino group, etc.), a sulfonamide group having 0 to 10 carbon atoms (for example, a methanesulfonamide group, a benzenesulfonamide group, a p-toluenesulfonamide group, etc.), a carbon number of 1 To 10 ureido groups (eg, unsubstituted ureido groups, methylureido groups,
A phenylureido group, etc.), a thioureido group having 1 to 10 carbon atoms (eg, an unsubstituted thioureido group, a methylthioureido group, a methoxyethylthioureido group, a phenylthioureido group, etc.)

Or R. However, when R ′ represents R, it may be the same as or different from R in general formula (II). In the general formula (II), preferably T = U = N or T
= U = C-R ', wherein R' is a hydrogen atom and has 1 to 1 carbon atoms.
And R represents a C1 to C4 alkyl group substituted by one or two of a group selected from carboxylic acid or a salt thereof, sulfonic acid or a salt thereof. Hereinafter, specific examples of the compound of the present invention are shown, but the present invention is not limited thereto.

[0020]

Embedded image

[0021]

Embedded image

[0022]

Embedded image

[0023]

Embedded image

[0024]

Embedded image

[0025]

Embedded image

[0026]

Embedded image

[0027]

Embedded image

[0028]

Embedded image

[0029]

Embedded image

[0030]

Embedded image

[0031]

Embedded image

[0032]

Embedded image

The compound used in the present invention is
Berichte der Deutschen Chemischen Gesellschaft
28, 77 (1895), JP-A-50-37436,
No. 51-3231, U.S. Patent No. 3,295,976,
U.S. Pat. No. 3,376,310, Berichte der Germany, Chen Hemitschen Geselshaft
er Deutschen Chemischen Gesellschaft) 22, 568
(1889), 29, 2483 (1896), Journal of Chemical Society (J. Chem. Soc.)
1932, 1806, Journal of the American Chemical Society (J. Am. Chem. Soc.)
71, 4000 (1949); U.S. Pat.
Nos. 88 and 2,541,924, Advances in Heterocyclic Chemistry (Advances in
Heterocyclic Chemistry) 9, 165 (1968), Organic Synthesis IV, 56
9 (1963), Journal of the American
Chemical Society (J. Am. Chem. Soc.) 4
5, 2390 (1923), Chemish Berichte (Chem)
ische Berichte) 9, 465 (1876)
-28496, JP-A-50-89034, U.S. Pat. Nos. 3,106,467, 3,420,670, 2,271,229, 3,137,578, and 3,148, 066, 3,511,663, 3,060,028, 3,271,154, 3,251,691, 3,598,599, 3,148,066 JP-B-43-4135, U.S. Pat. Nos. 3,615,616 and 3,420,664,
Nos. 3,071,465, 2,444,605, 2,444,606, 2,444,607, 2,935,404, etc. It can be synthesized according to the typical synthesis examples described above.

Synthesis Example 1 (Synthesis of Exemplified Compound 1) 2-Sulfoethylisothiocyanate sodium salt 5
100 ml of water was added to 6.8 g and 21.7 g of sodium azide, and the mixture was heated and stirred at 70 ° C. for 4 hours. After the reaction, insolubles were removed by filtration, and the solid obtained by drying under reduced pressure was recrystallized from 400 ml of methyl alcohol to obtain 45.1 g of the desired product (yield 64.
7 g) were obtained. Compounds having a melting point of 300 ° C. or higher are NM
The product was confirmed to be the target product by R, mass spectrum and elemental analysis.

Synthesis Example 2 (Synthesis of Exemplified Compound 13) 2-Sulfoethylisothiocyanate sodium salt 3
230 ml of water was added to 0.0 g and 9.6 g of formylhydrazine, and the mixture was stirred at room temperature for 2 hours. Next, sodium hydroxide 6.
After adding 3 g and heating under reflux for 2 hours, concentrated hydrochloric acid 13.6 was added under ice cooling.
The solid obtained by drying under reduced pressure was recrystallized from 50 ml of water to obtain 17.6 g (yield: 48.2%) of the desired product. Melting point: 269 ° C. (decomposition) The obtained compound was confirmed to be the target compound by NMR, mass spectrum and elemental analysis.

Synthesis Example 3 (Synthesis of Exemplified Compound 18) 2-Sulfoethylisothiocyanate sodium salt 3
100 ml of water was added to 8.0 g, and 26.8 g of aminoacetaldehyde diethyl acetal was added dropwise under ice cooling. After the dropwise addition, the mixture was heated and stirred at 60 ° C. for 3 hours, and then 40 ml of acetic acid was added.
Heated to reflux for an hour. After the reaction, the reaction solution was evaporated to dryness under reduced pressure, and recrystallized from 200 ml of a 3: 1 mixture of methyl alcohol and water to obtain 19.0 g (yield: 41.2%) of the desired product. Melting point: 274 to 275 ° C The obtained compound was confirmed to be the target compound by NMR, mass spectrum and elemental analysis.

The "bath having a fixing ability" in the present invention includes, for example, a fixing bath, a bleach-fixing bath and the like. Examples of the photographic fixing ability composition in the present invention include those used in a fixing bath such as a fixing solution and those used in a bleach-fixing bath such as a bleach-fixing solution.

The amount of the compound of the present invention used in the fixing bath is preferably 1 × 10 ⁻⁴ to 10 mol / l, more preferably 1 × 10 ^{−2 to} 3 mol / l, and particularly preferably ² × 10 ^{−2 to} 3 mol / l. It is 10 ^{-1 to} 3 mol / l. Alternatively, the amount used in the bleach-fix bath is 2 × 10 ^-2 to 10 mol /
Liter is appropriate, and preferably 2 × 10 ^{-1 to} 3 mol / l. Here, when the halogen composition of the silver halide emulsion in the light-sensitive material to be processed is AgBrI (for example, I ≧ 2 mol% or more, preferably 3 to 15 mol%), 0.5
It is preferably used in an amount of from 2 to 2 mol / l, more preferably from 1.2 to 2 mol / l. When the halogen composition is AgBr, AgBrCl or high silver chloride (for example, A
(gCl ≧ 80 mol%, preferably 90 to 100 mol%, more preferably 95 to 99.5 mol%), especially in the case of high silver chloride, use 2 × 10 ⁻¹ to 1 mol / l. Is preferred.

The phrase "the fixing ability composition used in the present invention does not substantially contain thiosulfate ions" specifically means thiosulfate ions (for example, ammonium thiosulfate)
0.1 mol / liter or less, more preferably 0.05
It means that it is at most mol / l, particularly preferably at most 0.01 mol / l. Thus, the compound of the present invention can be used as an effective fixing agent by using at least a relatively large amount of the compound or only the compound of the present invention. In recent years, with the progress of low replenishment, improvement in liquid stability of each processing bath is desired. A problem with the stability of the fixing bath (or bleach-fixing bath) and the subsequent rinsing bath is the precipitation of sulfides resulting from the oxidative degradation of the thiosulfate used as the fixing agent. The problem also occurs in the washing bath because the fixing solution (or bleach-fixing solution) is brought into the washing bath during processing. In order to prevent this precipitation, sulfite is usually used as an antioxidant, but in the case of low replenishment, increasing the usage of sulfite no longer causes solubility problems and oxidization of sulfite It cannot be solved due to problems such as formation of sodium sulfate.

The present inventors have studied various fixing agents having excellent oxidation stability in place of thiosulfate. As a result, the compound of the present invention has a fixing ability, is stable against oxidation and can be precipitated even at a low replenishing amount. Found no generation. On the other hand, in the bleach-fixing bath, since the oxidizing property of the solution itself is considerably higher than that of the fixing bath, when thiosulfate coexists, precipitation was observed in the bleach-fixing bath and the post-washing bath at low replenishment. Was used only for the compound of the present invention, and good liquid stability was obtained without precipitation. The addition of the compound of the present invention to a washing bath or a stabilizing bath is also effective and effective for preventing precipitation of the washing bath. Here, the concentration in these baths is preferably 10 ^{−3 to} 0.5 times the fixing agent concentration in the previous bath.

Next, a silver halide color photographic light-sensitive material and a processing method using the same will be described in detail. The silver halide color photographic 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. The number and order of the silver halide emulsion layers and the non-photosensitive layers are not particularly limited. 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. Wherein 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 light-sensitive material,
In general, the arrangement of the unit photosensitive layers is, in order from the support, a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. 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-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 is described in JP-A-61-43748,
Nos. 9-113438, 59-113440, 61
Couplers, DIR compounds and the like described in JP-A-20037 and JP-A-61-20038, and may contain a color mixture inhibitor 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 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, JP-A-62-200350 and JP-A-6-200350
A low-speed emulsion layer on the side away from the support as described in JP-A-2-206541 and JP-A-62-206543;
A high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support,
Low-sensitivity blue-sensitive layer (BL) / High-sensitivity blue-sensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
And so on. In addition, Japanese Patent Publication No. 55-34
As described in Japanese Patent No. 932, it is also possible to arrange in the order of blue-sensitive layer / GH / RH / GL / RL from the farthest side from the support. Japanese Patent Application Laid-Open No. 56-25738
And the blue-sensitive layer / GL / RL from the side farthest from the support as described in JP-A-62-63936.
The sequence may be arranged in the order of / GH / RH.

As described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. Further, an arrangement is also possible in which a silver halide emulsion layer having a lower sensitivity is further disposed, and an arrangement is formed of three layers having different sensitivities in which the sensitivities are successively decreased toward the support. Even in the case of three layers having different sensitivities, as described in JP-A-59-202264, a medium-sensitivity emulsion from the side farther from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers. As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material. When the silver halide color photographic material is a color negative film or a color reversal film, preferred silver halide contained in the photographic emulsion layer is silver iodobromide containing about 30 mol% or less of silver iodide, It is silver iodochloride or silver iodochlorobromide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 25 mol% of silver iodide.

When the silver halide color photographic light-sensitive material is color photographic paper, the silver halide contained in the photographic emulsion layer may be silver chlorobromide or silver chloride containing substantially no silver iodide. Can be preferably used. Here, "contains substantially no silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide / silver chloride emulsion can be used. Although this ratio can take a wide range depending on the purpose, a silver chloride ratio of 2 mol% or more can be preferably used. A so-called high silver chloride emulsion having a high silver chloride content is preferably used as a light-sensitive material suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably at least 90 mol%, more preferably at least 95 mol%. For the purpose of reducing the replenishment amount of the developing solution, the silver chloride content is 98 to 99.9.
Emulsions of almost pure silver chloride, such as mol%, are also preferably used.

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 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 that can be used in the present invention is, for example, Research Disclosure (hereinafter referred to as RD).
No. 17643 (December 1978), pp. 22-23,
"I. Emulsion preparation and type
s) ", and No. 18716 (November 1979), 6
It can be prepared using the method described on page 48 and the like. U.S. Pat. Nos. 3,574,628 and 3,653
Monodisperse emulsions described in US Pat. No. 5,394 and British Patent No. 1,413,748 are also preferable.

Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineering (Gutoff, Photographic Science and E
ngineering), Vol. 14, pp. 248-257 (1970)
U.S. Pat. Nos. 4,434,226 and 4,41.
No. 4,310, No. 4,433,048, No. 4,43
No. 9,520 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 sensitization and spectral sensitization are used. In the process of physical ripening, various polyvalent metal ion impurities (such as salts or complex salts of cadmium, zinc, lead, copper, thallium, iron, ruthenium, rhodium, palladium, osmium, iridium, platinum, etc.) can also be introduced. . Compounds used for chemical sensitization are described in JP-A-62-21.
No. 5,272, page 18, lower right column to page 22, upper right column. The additives used in such a process are RD No. 17643 and RD No. 187.
16 and the corresponding locations are summarized in the table below. Known photographic additives which can be used in the present invention are also described in the above two RDs, and the relevant portions are shown in the following table.

Additive type RD17643 RD18716 1 Chemical sensitizer page 23, page 648, right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, page 23-24, page 648 right column to supersensitizer 649, right column 4 Brightener page 24 5 Antifoggant page 24-25 page 649 right column and stabilizer 6 Light absorber, f 25-26 page 649 right column filter dye, page 650 left column UV absorber 7 Stain inhibitor Page 25 right column 650 page left to right column 8 Dye image stabilizer 25 page 9 Hardener 26 page 651 left column 10 Binder 26 same as above 11 Plasticizer, lubricant 27 page 650 right column 12 Coating aid, Page 26 to 27 Page 650 Right column Surfactant 13 Antistatic agent Page 27 Same as above

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat.
It is preferable to add a compound that can be fixed by reacting with formaldehyde described in JP-A Nos. 7 and 4,435,503 to the photosensitive material. Various color couplers can be used in the present invention, and specific examples thereof are described in RD No.
17643, VII-CG.

As the yellow coupler, for example, US Pat. Nos. 3,933,501 and 4,022,620;
Nos. 4,326,024, 4,401,752, 4,248,961, JP-B-58-10739, British Patent Nos. 1,425,020, and 1,476,760.
No. 3,973,968, U.S. Pat.
Nos. 023 and 4,511,649, European Patent No. 24
What is described in 9,473A etc. is preferable.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897,
European Patent No. 73,636, US Patent No. 3,061,4
No. 32, No. 3,725,064, RD No. 24220
(June 1984), JP-A-60-33552, RD
No. 24230 (June 1984), JP-A-60-43
No. 659, No. 61-72238, No. 60-35730
No. 55-118034, No. 60-185951
No. 4,500,630, U.S. Pat.
654, 4,556,630, WO (PCT) 8
What is described in 8/04795 etc. is especially preferable.

Examples of the cyan coupler include phenol-based and naphthol-based couplers.
52,212, 4,146,396, 4,22
8,233, 4,296,200, 2,36
9,929, 2,801,171, 2,77
2,162, 2,895,826, 3,77
2,002, 3,758,308, 4,33
4,011, 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A.
No. 249,453A, U.S. Pat.
No. 22, 4,333, 999, 4, 753, 87
No. 1, No. 4,451,559, No. 4,427,767
Nos. 4,690,889 and 4,254,212
No. 4,296,199, JP-A-61-42658.
And the like are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are described in RD No. 17643, Sections VII-G,
U.S. Pat. No. 4,163,670, JP-B-57-394.
No. 13, U.S. Pat. Nos. 4,004,929 and 4,13
8,258 and British Patent No. 1,146,368 are preferred. No. 4,774,18.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in No. 1, or a dye precursor capable of forming a dye by reacting with a developing agent described in U.S. Pat. No. 4,777,120. It is preferable to use a coupler having a group as a leaving group.

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. Typical examples of polymerized dye-forming couplers are described in U.S. Pat.
0,211, 4,367,282, 4,40
9,320, 4,576,910, British Patent 2,
102, 173 and the like.

Couplers 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
D17643, Patents described in VII to F, JP-A-5
Nos. 7-151944, 57-154234, 60
Nos. 184248, 63-37346, U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred. Examples of couplers which release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,131,188, JP-A-59-157538 and JP-A-59-170840. Are preferred.

Other couplers usable in the light-sensitive material of the present invention include those described in US Pat. No. 4,130,42.
No. 7,283, etc .; U.S. Pat.
No. 472, No. 4,338,393, No. 4,310,6
No. 18, etc .;
No. 950, DIR described in JP-A-62-24252 and the like.
Redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 1
No. 73,302A, couplers capable of releasing dyes that recolor after release, RD Nos. 11449 and 24241, bleaching accelerator releasing couplers described in JP-A-61-201247, and the like, U.S. Pat. No. 4,553,477. And the couplers releasing leuco dyes described in JP-A-63-75747, U.S. Pat.
No. 4,181, for example, couplers that release a fluorescent dye.

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 used in the oil-in-water dispersion method are described in US Pat.
No. 027 and the like. Specific examples of the high boiling organic solvent having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, 2-ethylhexyl phthalate, decyl phthalate, bis (2,4-
Di-t-amylphenyl) phthalate, bis (2,4-
Di-t-amylphenyl) isophthalate, bis (1,
Esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxy) Ethyl phosphate,
Trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate, etc.), benzoic esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecaneamide, N , N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-
Amyl phenols, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2) -Butoxy-5-t
tert-octylaniline), and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). 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.
Butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
No. 63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230.
Further, these couplers are impregnated with a loadable latex polymer (for example, U.S. Pat. No. 4,203,716) in the presence or absence of the high-boiling organic solvent,
Alternatively, it can be dissolved in a water-insoluble and organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution. Preferably, homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO88 / 00723 are used. In particular, use of an acrylamide-based polymer is preferred for stabilizing a color image.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, direct positive color light-sensitive materials, color positive films and color reversal papers. Suitable supports that can be used in the present invention are described in, for example, RD. No. 17643, page 28,
No. 18716, from the right column on page 647 to the left column on page 648.

In the light-sensitive material of the present invention, the total thickness of the hydrophilic colloid layers on the side having the emulsion layer is 25 μm, preferably 20 μm or less, and the film swelling speed T _1/2 is 3 μm or less.
It is preferably 0 seconds or less (preferably 15 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 rate T _1/2 can be measured according to a method known in the art. For example,
Photographic Science and Engineering (Photogr.Sc) by A. Green et al.
i.Eng.), 19 vol., No. 2, can be measured by using the type of Swellometer described (swelling meter) pp 124-129, T _1/2 is 30 ° C. in a color developing solution, 3 minutes 90% of the maximum swelling film thickness reached after the treatment for 15 seconds is defined as the saturated film thickness, and defined as the time required to reach half the film thickness. The film swelling speed T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. In addition, the swelling ratio is 150 ~
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 above-mentioned color photographic light-sensitive material is made of the above-mentioned RD
No. 17643, pp. 28-29, and No. 18716
615 can be developed by the usual method described in the left column to the right column. The color developing solution used for developing the photosensitive material is preferably an alkaline aqueous solution mainly containing an aromatic primary amine-based color developing agent. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3-methylaniline. -4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-
N-ethyl-β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof are exemplified. These compounds can be used in combination of two or more depending on the purpose.

The color developing solution may be a pH buffer such as a carbonate, borate or phosphate of an alkali metal, a development inhibitor such as a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. It generally contains an agent or an antifoggant. If necessary, such as hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazide, triethanolamine, catecholsulfonic acid, and triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts and amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride , An auxiliary developing agent such as 1-phenyl-3-pyrazolidone, a viscosity-imparting agent, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid (for example, Ethylenediamine tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexane diamine tetraacetic 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), 4,4'-diamino-2 Fluorescent brighteners such as 2,2'-disulfostyrenebenne compounds, alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids,
Various surfactants such as aromatic carboxylic acids may be added.

However, it is preferable that benzyl alcohol is not substantially contained in terms of pollution, liquid preparation and prevention of color contamination. Here, "substantially" means 2 ml or less (more preferably not containing at all) per liter of color developing solution. When the reversal process is performed, color development is usually performed after black and white development. The black-and-white developer includes dihydroxybenzenes such as hydroquinone, 1-phenyl-3
Known black-and-white developing agents such as 3-pyrazolidones such as -pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The pH of the color developing solution and the black and white developing solution
Is generally 9 to 12. The replenishing 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 can be reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also. In particular,
When a so-called high silver chloride light-sensitive material is used, by lowering bromine ions in the color developing solution and relatively increasing chloride ions, photographic properties and processing properties are excellent, and fluctuations in photographic properties can be suppressed. This is particularly preferred. In such a case, the replenishing amount can be reduced to about 20 ml per square meter of the light-sensitive material, in which overflow in the color developing bath is substantially eliminated. When the replenishment rate 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. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The processing temperature of the color developing solution of the present invention is from 20 to
At 50 ° C, preferably 30 to 45 ° C. Processing time is
The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of a 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 successive bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. The processing temperature of the bleaching solution and the bleach-fixing solution of the present invention is 20 to 50C, preferably 30 to 45C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 4 minutes. Examples of the bleaching agent include iron (III), cobalt (II
Compounds of polyvalent metals such as I), chromium (IV) and copper (II), peracids, quinones, nitro compounds and the like are used. Representative bleaches include ferricyanide; dichromate; iron (II
Organic complex salts of I) or cobalt (III), for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Use of aminopolycarboxylic acids such as diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid; persulfates; bromates; permanganates; it can. Among these, iron (III) aminopolycarboxylates including iron (III) complex salts of ethylenediaminetetraacetate
The complex salt is preferably a persulfate from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. In particular, the bleaching solution for negative photosensitive materials for photography includes 1,3-
Iron (III) complex diaminopropanetetraacetate is preferred from the viewpoint of bleaching ability. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5.
-8, but the treatment can be carried out at a lower pH to speed up the treatment. The bleaching agent is preferably used in an amount of 0.05 to 1 mol per liter of the processing solution.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators are described in the following specification. U.S. Pat. No. 3,893,858, West German Patent Nos. 1,290,812, 2,059,988, JP-A-53-32736, JP-A-53-57831, and JP-A-53-57831.
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, RD No. 17129 (1
A compound having a mercapto group or a disulfide group described in, for example, Japanese Patent Application Laid-Open No. Sho 50-140129; Japanese Patent Publication No. 45-8506.
JP-A-52-20832 and JP-A-53-32735.
Thiourea derivatives described in U.S. Patent No. 3,706,561; West German Patent No. 1,127,715;
Iodide salts described in US Pat. No. 16,235; West German Patent No. 96
Polyoxyethylene compounds described in JP-A-6-410 and JP-A-2,748,430; polyamine compounds described in JP-B No. 45-8836;
Nos. 49-59644, 53-94927, 54
No. 35727, No. 55-26506, No. 58-16
Compounds described in No. 3940; 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. 3,893,858 and West German Patent 1,290,
No. 812 and compounds described in JP-A-53-95630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferred. The amount of the bleaching accelerator used in the bleaching solution and the bleach-fixing solution is 1 × 10 ^-4 to 1 × per liter.
It is preferably 10 ^-2 mol, preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻³ mol. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

Known additives such as rehalogenating agents such as ammonium bromide and ammonium chloride, pH buffering agents such as ammonium nitrate, and metal corrosion inhibitors such as ammonium sulfate can be added to the bleach-fixing solution of the present invention. . In the fixing bath of the present invention, a known fixing agent other than the thiosulfate ion may be used in addition to the compound of the present invention. For example, examples of the fixing agent include thiocyanates, thioether compounds, thioureas, and a large amount of iodide. The amount of the fixing agent to be used in combination is approximately the same as that of the compound of the formula (I) of the present invention, and may be mixed with the compound of the formula (I) at an arbitrary ratio. As a preservative of the bleach-fix solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct, and a sulfinic acid compound are preferable. In order to improve the stability of the fixing solution, amino fixing agents such as aminopolycarboxylic acids and organic phosphonic acid chelating agents (preferably 1-hydroxyethylidene-1,1-diphosphonic acid and N, N, N ',
(N'-ethylenediaminetetraphosphonic acid).

The processing temperature of the fixing solution of the present invention is 20 to 50 ° C.
And preferably 30 to 45 ° C. Processing time is 20 seconds ~
5 minutes, preferably 30 seconds to 4 minutes. The fixing solution may further contain various fluorescent whitening agents, antifoaming agents, surfactants, polyvinylpyrrolidone, methanol, and the like. It is preferable that the stirring of each processing solution in the desilvering step is strengthened as much as possible from the viewpoint of shortening the desilvering processing time. Examples of the stirring means include the methods described in JP-A-62-183460 and JP-A-62-183461. In the case of the means for impinging the jet, the time until the collision is such that the photosensitive material is treated with the processing liquid. Preferably, it is performed within 15 seconds after the introduction.

In the present invention, the crossover time from the color developing solution to the bleaching solution (the air time from the time when the photosensitive material leaves the color developing solution to the time when entering the bleaching solution) is improved in terms of bleaching fog and adhesion of dirt on the surface of the photosensitive material. The time is preferably within 10 seconds. Further, the crossover time from the bleaching solution of the invention to the processing solution having fixing ability is preferably within 10 seconds from the viewpoint of improving the poor recoloring of the cyan dye. According to the method of the present invention, the amount of replenishment can be reduced. Here, the replenishment amount of the fixing solution is preferably 300 to 800 ml / m ^{2 in} the case of a color photographic material for photography (for example, a coated silver amount of 4 to 12 g / m ² ). 20-50ml
/ M ² is preferred.

The silver halide color photographic light-sensitive material used in the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (number of stages), countercurrent,
It can be set in a wide range according to a replenishment method such as a forward flow and other various conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the Society
on Picture and Television Engineers Vol. 64,
P. 248-253 (May, 1955). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing Ca ions and Mg ions described in JP-A-62-288838 can be used very effectively. Also, Japanese Patent Application Laid-Open No. 57-85
No. 42, isothiazolone compounds, thiabendazoles, chlorinated bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Sterilization, sterilization,
Fungicides described in "Antifungal Technology", "Encyclopedia of Antifungal Agents" edited by the Japan Society of Antifungals and Fungi.

The pH of the washing water in the processing of the light-sensitive material of the present invention is from 4 to 9, preferably from 5 to 8. The washing temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the use, etc., but are generally at 15 to 45 ° C. for 20 seconds to 10 minutes,
Preferably, a range of 30 seconds to 5 minutes at 25 to 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 stabilizing process, JP-A-57-8543 and JP-A-58-8543 are used.
All known methods described in JP-A-14834 and JP-A-60-220345 can be used.

In some cases, a stabilization treatment may be performed after the water washing treatment. For example, for example, formalin, hexamethylenetetramine, hexahydrotriazine, N-hydrogenazine or the like, which is used as a final bath of a color light-sensitive material for photography, may be used. A stabilizing bath containing a dye stabilizer represented by a methylol compound can be used. If necessary, a metal compound such as an ammonium compound, Bi, or Al, a fluorescent brightener, various chelating agents, a film pH regulator, a hardening agent, a bactericide, an antifungal agent, an alkanolamine, or a surfactant may be used in this stabilizing bath. An agent (preferably a silicon-based agent) can also be added. The water used in the washing step or the stabilization step includes tap water, water deionized to a Ca ion and Mg ion concentration of 5 mg / l or less by ion exchange resin, halogen, and water sterilized by an ultraviolet germicidal lamp or the like. It is preferred to use

The replenishment amount of the above-mentioned washing and / or stabilizing solution may be 1 to 50 of the amount brought in from the previous bath per unit area of the light-sensitive material.
Times, preferably 2 to 30 times, more preferably 2 to 15 times. The overflow solution accompanying this replenishment can be reused in the desilvering step and other steps. 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 US Pat. No. 3,342,597, US Pat. No. 3,342,599, RD
Nos. 14,850 and 15,159, Schiff base type compounds, aldol compounds, described in US Pat. No. 13,924, metal salt complexes described in U.S. Pat. No. 3,719,492, JP-A-53-135628 The urethane-based compounds described in (1) can be cited. The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development. Typical compounds are described in JP-A-56-64339.
Nos. 57-1444547 and 58-11543
No. 8, etc.

The various processing solutions used in the present invention are in the range of 10 ° C. to 50
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.

As one example of a silver halide color light-sensitive material, there is one using direct positive silver halide. The processing using this photosensitive material will be described below. A surface developer having a pH of 11.5 or less containing an aromatic primary amine color developer after imagewise exposure of a silver halide color photographic light-sensitive material, or after or while performing fog treatment with light or a nucleating agent. It is also preferable to form a positive color image directly by color development, bleaching and fixing. The pH of the developer is more preferably in the range of 11.0 to 10.0. The fogging treatment in the present invention includes a method of applying a second exposure to the entire surface of a photosensitive layer called a so-called "light fogging method" and a method of developing in the presence of a nucleating agent called a "chemical fogging method". Either one may be used. Development processing may be performed in the presence of a nucleating agent and fog light. Further, fog exposure may be performed on a photosensitive material containing a nucleating agent.

Regarding the light fogging method, see the aforementioned Japanese Patent Application No.
No. 253716, page 47, line 4 to page 49, line 5; nucleating agents that can be used in the present invention are described in page 49, line 6 to page 67, line 2; In particular, use of the compounds represented by the general formulas [N-1] and [N-2] is preferred. Specific examples of these are described in the fifth specification of the same specification.
[NI-1] to [NI-10] described on pages 6 to 58
And [N-II-1] on pages 63 to 66 of the same specification.
The use of [N-II-12] is preferred. With respect to the nucleation promoter that can be used in the present invention, the same specification, page 68, line 11 to 71
It is described on page 3, line 3, and as this specific example, the use of (A-1) to (A-13) described on pages 69 to 70 is particularly preferable.

Next, a silver halide black-and-white photographic light-sensitive material and processing using the same will be described in detail. The halogen composition of the silver halide emulsion used is not particularly limited, and may be any composition such as silver chloride, silver chlorobromide, silver iodobromide, silver bromide, silver iodobromochloride, etc. The silver halide content is preferably at most 10 mol%, particularly preferably at most 5 mol%. When used for forming a high-contrast negative image, the silver halide used has an average grain size of fine grains (for example, 0.7 grains).
μ) or less, more preferably 0.5 μ or less. The particle size distribution is basically not limited, but is preferably monodispersed. The monodispersion as used herein means that at least 95% of the weight or the number of particles is ±± of the average particle size.
It means that it is composed of a particle group having a size within 40%. Silver halide grains in photographic emulsions are regular, such as cubic, octahedral, rhombodecahedral, and tetradecahedral.
It may be one having an irregular crystal, one having an irregular (spherical, flat, etc.) crystal, or one having a complex of these crystal forms.

Regarding the other points of the photographic emulsion, the above-mentioned photographic emulsion can be basically used. In the present invention, the silver halide emulsion layer contains two types of monodisperse emulsions having different average grain sizes as disclosed in Japanese Patent Application Nos. 60-64199 and 602322086, whereby the maximum density (Dmax) is increased. In view of this, the small-sized single-particulate particles are preferably chemically sensitized, and the method of chemical sensitization is most preferably sulfur sensitization. The large-size monodisperse emulsion may not be chemically sensitized, but may be chemically sensitized. Generally, large-sized monodispersed particles are not subjected to chemical sensitization because black spots are easily generated. However, when chemically sensitized, it is particularly preferable to apply the light as shallow as not to generate black spots.
Here, "shallow application" refers to shortening the time for chemical sensitization, lowering the temperature, or reducing the amount of chemical sensitizer added as compared with the chemical sensitization of small-sized grains.
The difference in sensitivity between the large-sized monodispersed emulsion and the small-sized monodispersed emulsion is not particularly limited, but ΔlogE is 0.1 to 1.0, more preferably 0.2 to 0.7. Is preferably higher. The average grain size of the small-sized monodispersed grains is 90% or less, preferably 80% or less, of the average size of the large-sized silver halide monodispersed grains.

The photographic light-sensitive material used in the present invention may contain a known nucleating agent in a photographic emulsion layer or another hydrophilic colloid layer to form a super-high contrast image. As the nucleating agent used in the present invention, for example, RESEARCH DISC
LOSURE Item 23516 (November 1983, p.
346) and the references cited therein. Examples of development accelerators suitable for use in the present invention or accelerators for nucleation and infectious development include JP-A-53-77616.
No. 54-37732, No. 53-137133,
In addition to the compounds disclosed in JP-A-60-140340 and JP-A-60-14959, various compounds containing an N or S atom are effective.

The direct-positive light-sensitive material used in the present invention may contain a desensitizer in the photographic emulsion layer and other hydrophilic colloid layers. The organic desensitizer is defined by its polarographic half-wave potential, that is, the oxidation-reduction potential determined by polarography, and the sum of the polaro anodic potential and the cathodic potential becomes positive. As an organic desensitizer, Japanese Patent Application No. 61-
Those represented by the general formulas (III) to (V) described on pages 55 to 72 of 280998 are preferably used.

The developer for developing the black-and-white silver halide light-sensitive material of the present invention contains commonly used additives (for example, a developing agent, an alkaline agent, a pH buffer, a preservative, and a chelating agent). be able to. In the process of the present invention,
Any of the known methods can be used, and a known processing solution can be used. The processing temperature is usually selected between 18 ° C and 50 ° C, but may be lower than 18 ° C or higher than 50 ° C. The processing time is 10 seconds to 3 minutes, preferably 10 seconds to 1 minute. Known developing agents such as dihydroxybenzenes (for example, hydroquinone), 1-phenyl-3-pyrazolidones, and aminophenols (for example, N-methyl-p-aminophenol) are used alone or in combination in the black-and-white developer. Can be used.

The dihydroxybenzene-based developing agent is preferably used usually in an amount of 0.05 mol / l to 0.8 mol / l. Also, dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-amino-
When the combination with phenols is used, the former is 0.0
5 mol / l to 0.5 mol / l, the latter being 0.1 mol / l.
It is preferably used in an amount of not more than 06 mol / liter. Examples of the sulfite preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. Sulfite is used in a black-and-white developer, particularly in a graphic arts developer, in an amount of 0.3 mol / l or more. However, if an excessively large amount is added, it precipitates in the developer and causes liquid contamination, so the upper limit is 1.2 mol / l. It is preferred that

The alkaline agent used in the developer of the present invention may be a pH such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium tertiary phosphate, potassium tertiary phosphate, sodium silicate or potassium silicate. Contains regulators and buffers. As additives used in addition to the above components, boric acid, compounds such as borax, sodium bromide,
Development inhibitors such as potassium bromide and potassium iodide: ethylene glycol, diethylene glycol, toluene glycol, dimethylformamide, methyl cellosolve,
Organic solvents such as hexylene glycol, ethanol and methanol: mercapto compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, indazole compounds such as 5-nitroindazole, 5 An antifoggant such as a benztriazole-based compound such as methylbenztriazole or a black pepper inhibitor, and further, if necessary, a color tone agent, a surfactant, an antifoaming agent, a water softener, Hardeners and the like may be included. Compounds described in JP-A-56-24347 are used as silver stain inhibitors, and JP-A-62-21265 are used as development unevenness preventing agents.
Compounds described in No. 1 as dissolution aids
The compounds described in No. 9743 can be used.

In the developer used in the present invention, boric acid described in Japanese Patent Application No. 61-28708, saccharides (for example, saccharose) and oximes (for example, Oximes), phenols (for example, 5-sulfosalicylic acid), and tertiary phosphates (for example, sodium salts and potassium salts). The fixing solution is an aqueous solution containing a hardener (for example, a water-soluble aluminum compound), acetic acid, and a dibasic acid (for example, tartaric acid, citric acid, or a salt thereof), if necessary, in addition to the fixing agent. 8 or more, more preferably 4.
0-7.5. In the fixing bath of the present invention, a known fixing agent other than the thiosulfate ion may be used in addition to the compound of the present invention. For example, examples of the fixing agent include thiocyanates, thioether compounds, thioureas, and a large amount of iodide. The amount of the fixing agent to be used in combination is the same as that of the compound of the formula (I) of the present invention, and may be mixed with the compound of the formula (I) at an arbitrary ratio. A water-soluble aluminum salt mainly used as a hardener in a fixing solution is a compound generally known as a hardening agent for an acidic hardening fixer,
For example, there are aluminum chloride, aluminum sulfate, potassium alum and the like. As the above-mentioned dibasic acid, tartaric acid or a derivative thereof, citric acid or a derivative thereof can be used alone or in combination of two or more. It is effective that these compounds contain 0.005 mol or more per liter of the fixing solution, and particularly 0.01 to 0.03 mol / l is particularly effective. Specifically, tartaric acid,
Potassium tartrate, sodium tartrate, potassium sodium tartrate, ammonium tartrate, potassium ammonium tartrate, and the like.

The fixing solution may further contain a preservative (for example, sulfite or bisulfite), a pH buffer (for example, acetic acid or boric acid), a pH adjuster (for example, ammonia or sulfuric acid), or an image preserving agent, if desired. Agents (eg, potassium iodide) and chelating agents. Here, the pH buffer is used in an amount of 10 to 40 g / liter, more preferably about 18 to 25 g / liter, because the pH of the developer is high. The fixing temperature and time are the same as in the case of the development.
0 seconds to 1 minute is preferred. Here, the replenishment rate of the fixing solution is preferably 50 to 300 ml / m ² or less.

As the washing water, those described above can be used. Further, a stabilizer may be used in place of the washing water. The roller transport type automatic developing machine is described in U.S. Pat. Nos. 3,025,779 and 3,545,971 and the like, and is simply referred to as a roller transport type processor in this specification. The roller transport type processor has four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stop step), but most preferably follows these four steps. . Here, in the rinsing step, water can be saved by using two to three stages of countercurrent rinsing. Examples of the black-and-white photographic light-sensitive material according to the present invention include ordinary black-and-white silver halide photographic light-sensitive materials (for example, black-and-white light-sensitive materials for photography, X-ray black-and-white light-sensitive materials, black-and-white light-sensitive materials for printing), and infrared light for laser scanners Sensitive materials.

[0089]

The use of the compound of the present invention can improve the stability (especially, no sulfuration or the like) of a fixing solution or a fixing solution having a bleaching ability (for example, a bleach-fixing solution) and improve the fixing ability. Can be obtained. When the compound of the present invention is used, stable processing can be performed even when the replenishment amount of the fixing solution or the bleach-fixing solution is greatly reduced.

[0090]

EXAMPLES Examples of the present invention will be specifically described below, but the present invention is not limited thereto. Example 1 On an undercoated cellulose triacetate film support,
Sample 101, which is a multilayer color photographic material composed of each layer having the following composition, was prepared. The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dyes are shown in terms of moles per mole of silver halide in the same layer.

First layer (antihalation layer) Black colloidal silver 0.15 Gelatin 1.5 ExM-8 0.08 UV-1 0.03 UV-2 0.06 Solv -2 0.08 UV-3 0.07 Cpd-5 6 × 10 ^-4 Second layer (intermediate layer) Gelatin 1.5 UV-1 0.03 UV-2 0.06 UV-3 0.07 ExF-1 0.004 Solv-2 0.07 Cpd-5 6 × 10 ^-4

Third Layer (First Red-Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type, sphere equivalent diameter 0.3 μm, sphere equivalent diameter variation coefficient 29%, normal crystal, twin crystal Crystal mixed particles, diameter / thickness ratio 2.5) Silver coating amount 0.5 Gelatin 0.8 ExS-1 1.0 x ^10-4 ExS-2 3.0 x ^10-4 ExS-3 1 × 10 ^-5 ExC-3 0.22 ExC-4 0.02 Cpd-5 3 × 10 ^-4 Fourth layer (second red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal height AgI type, equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 20%, normal crystal, twin mixed particles, diameter / thickness ratio 1) coated silver amount 0.7 gelatin 1.26 ExS-1 1 × 10 ^-4 ExS-2 3 × 10 ^-4 ExS-3 1 × 10 ^-5 ExC-3 0.33 Ex C-4 ... 0.01 ExY-16 ... 0.01 ExC-7 ... 0.04 ExC-2 ... 0.08 Solv-1 ... 0.03 Cpd-5 ... 5 x ^10-4

Fifth Layer (Third Red Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, sphere equivalent diameter 0.7 μm, sphere equivalent diameter variation coefficient 30%, normal crystal Twin mixed particles, diameter / thickness ratio 2) Coating silver amount 0.7 Gelatin 0.8 ExS-1 1 × 10 ^-4 ExS-2 3 × 10 ^-4 ExS-3 1 × 10 ^-5 ExC-5 0.05 ExC-6 0.06 Solv-1 0.15 Solv-2 0.08 Cpd-5 3 × 10 ^-5 6th layer (Intermediate layer) Gelatin 1.0 Cpd-5 4 × 10 ^-4 Cpd-1 0.10 Cpd-4 1.23 Solv-1 0.05 Cpd-3 0 .25

Seventh Layer (First Green Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type, sphere equivalent diameter 0.3 μm, sphere equivalent diameter variation coefficient 28%, normal crystal, twin crystal Crystal mixture particles, diameter / thickness ratio 2.5) Silver coating amount 0.30 Gelatin 0.4 ExS-4 5 × 10 ^-4 ExS-6 0.3 × 10 ^-4 ExS-5 ... 2 × 10 ^-4 ExM-9 0.2 ExY-14 0.03 ExM-8 0.03 Solv-1 0.2 Cpd-5 2 × 10 ^-4 Eighth Layer (second green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type, equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 20%, normal crystal, twin mixed grains, diameter / thickness ratio 4) coating silver amount ...... 0.6 gelatin ...... 0.8 ExS-4 ...... 5 × 10 -4 ExS-5 ...... 2 × 10 -4 Ex ^{-6 ...... 0.3 × 10 -4 ExM-} 9 ...... 0.25 ExM-8 ...... 0.03 ExM-10 ...... 0.015 ExY-14 ...... 0.04 Solv-1 ...... 0.2 Cpd -5 ... 3 × 10 ^-4

Ninth Layer (Third Green Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, sphere equivalent diameter 0.7 μm, sphere equivalent diameter variation coefficient 30%, normal crystal Twin mixed grains, diameter / thickness ratio 2.0) Silver coating amount 0.85 Gelatin 1.0 ExS-4 2.0 × 10 ^-4 ExS-5 2.0 × 10 ^-4 ExS-6 0.2 × 10 ^-4 ExS-7 3.0 × 10 ^-4 ExM-12 0.06 ExM-13 0.02 ExM-8 0.02 Solv-1 0.20 Solv -2 0.05 Cpd-5 4 × 10 ^-4

10th layer (yellow filter layer) Gelatin 0.9 0.9 yellow colloidal silver 0.05 Cpd-1 0.2 Solv-1 0.15 Cpd-5 4 × 10 ^{− 4th} layer (first blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type, equivalent sphere diameter 0.5 μm, coefficient of variation of equivalent sphere diameter 15%, octahedral grain) coated silver Amount 0.4 Gelatin 1.0 ExS-8 2 × 10 ^-4 ExY-16 0.9 ExY-14 0.09 Solv-1 0.3 Cpd-5 … 4 × 10 ^-4

Twelfth Layer (Second Blue Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, sphere equivalent diameter 1.3 μm, sphere equivalent diameter variation coefficient 25%, normal crystal Twin mixed particles, diameter / thickness ratio 4.5) Silver coating amount 0.5 Gelatin 0.6 ExS-8 1 × 10 ^-4 ExY-16 0.12 Solv-1 0.04 Cpd-5... 2 × 10 ^-4 th thirteenth layer (first protective layer) fine grain silver iodobromide (average particle size 0.07 μm, AgI 1 mol%) 0.2 gelatin. 8 UV-3 ... 0.1 UV-4 ... 0.1 UV-5 ... 0.2 Solv-3 ... 0.04 Cpd-5 ... 3 x ^10-4

Fourteenth layer (second protective layer) Gelatin 0.9 polymethyl methacrylate particles (1.5 μm in diameter) 0.2 Cpd-5 4 × 10 ^-4 H-1 0. 4 In each layer, in addition to the above components, a surfactant was added as a coating aid. The sample prepared as described above was used for sample 10
It was set to 1. Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below.

[0099]

Embedded image

[0100]

Embedded image

[0101]

Embedded image

[0102]

Embedded image

[0103]

Embedded image

[0104]

Embedded image

[0105]

Embedded image

[0106]

Embedded image

[0107]

Embedded image

[0108]

Embedded image

[0109]

Embedded image

[0110]

Embedded image

The dried film thickness of the coating layer excluding the undercoat layer of the support and the support of the sample 101 manufactured at this time was 17.6 μm.
And the swelling rate (T _1/2 ) was 8 seconds. The prepared sample was cut and processed into a width of 35 mm, and after exposure, a running process was performed using an automatic developing machine according to the processing recipe shown below until the cumulative replenishment amount of the fixing solution became three times the mother liquor tank capacity.

Processing Step Processing Time Processing Time Processing Temperature Replenishment Amount Tank Capacity Color Developing 3 min 15 sec 38 ° C 15 ml 20 liter Bleaching 4 min 30 sec 38 ° C 10 ml 40 liter Washing 2 min 10 sec 35 ° C 10 ml 20 liter 4 minutes 20 seconds 38 ° C 30 ml 30 liters or 15 ml water wash (1) 1 minute 05 seconds 35 ° C 10 liters from (2) to (1) Counterflow piping system. Washing with water (2) 1 minute 00 seconds 35 ° C 20ml 10 liters Stabilization 1 minute 05 seconds 38 ° C 10ml 10 liters Drying 4 minutes 20 seconds 55 ° C

Next, the composition of the processing solution will be 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 4.9 Potassium carbonate 30.0 30.0 Potassium bromide 1.4-Potassium iodide 1.5 mg -Hydroxyamine sulfate 2.4 3.6 4- (N-ethyl-N-β-hydroxyethylamino) 4.5 7.2-2-Methylaniline sulfate 1.0 liter 1.0 liter with addition of water pH 10.05 10.10

(Bleaching solution) Mother liquor (g) Replenishing solution (g) Ferric ammonium 1,3-propylenediaminetetraacetate 144.0 206.0 ammonium monobromide 84.0 120.0 ammonium nitrate 30.0 41.7 acetic acid (98%) 28.0 40.0 hydroxy Acetic acid 63.0 90.0 Add water 1.0 liter 1.0 liter pH (adjusted with aqueous ammonia (27%) 3.0 2.8

(Fixing solution) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid disodium salt 0.5 1.0 Sodium sulfite 7.0 12.0 Sodium bisulfite 5.0 9.5 Fixing agent; aqueous solution of ammonium thiosulfate (70 wt%) 170.0 ml 240.0 ml or Table 1 0.8 mol 1.1 mol Add water and add 1.0 liter 1.0 liter pH 6.7 6.7

(Washing solution) Common tap water is treated with tap water of H type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite IR-400). Water was passed through the packed mixed-bed column to reduce the calcium and magnesium ion concentrations to 3 mg / l or less, and then 20 mg / l of sodium diisocyanurate and 0.15 g / l of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) Mother liquor (g) Replenisher (g) Formalin (37%) 2.0 ml 3.0 ml polyoxyethylene-p-monononylphenyl ate 0.3 0.45 ter ((average degree of polymerization: 10) disodium ethylenediaminetetraacetate Salt 0.05 0.08 Water was added and 1.0 liter 1.0 liter pH 5.0-8.0 5.0-8.0 After the running process was completed, the fixing time was shortened to 2 minutes and 3 minutes using the same sample as the running process sample. The amount of silver remaining in the unexposed area of the sample after the treatment was measured using a fluorescent X-ray analyzer, and the presence or absence of a precipitate in the fixing bath and the washing bath (1) was visually examined.
Table 1 shows the results.

[0118]

[Table 1]

Table 1 shows that when the compound of the present invention was used,
It can be seen that no precipitation occurs during the running process, the liquid stability is good, and desilvering is possible with a fixing time of 3 minutes, which is clearly superior to thiosulfate.
This effect is particularly remarkable when the replenishment is reduced.

Example 2 Compound 1 of Example 1 was replaced with Compounds 2, 3, 9, 12, 1
The same tests as in Example 1 were performed in place of 3, 14, 20, 23, 25, 26, or 32, respectively. As a result, a good result was obtained in which the fixing ability was high as in Example 1, and no precipitation occurred during the running process. This effect was particularly remarkable when the replenishment was reduced.

Example 3 A multilayer color printing paper having the following layer constitution was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows. Preparation of First Layer Coating Solution 19.1 g of yellow coupler (exY), 4.4 g of color image stabilizer (cpd-1) and color image stabilizer (cpd-)
7) 27.2 cc of ethyl acetate and solvent (so
lv-1) 8.2 g was added and dissolved, and the solution was added to 10% sodium dodecylbenzenesulfonate containing 8 cc of 10%
It was emulsified and dispersed in 185 cc of an aqueous gelatin solution. On the other hand, a silver chlorobromide emulsion (cubic, a 3: 7 mixture (silver molar ratio) of an average grain size of 0.88 μm and an average grain size of 0.70 μm) has a variation coefficient of grain size distribution of 0.08 and 0.10, Each emulsion contains 0.2 mol% of silver bromide localized on the grain surface) and the following blue-sensitizing sensitizing dye is 2.0 × 10 ⁻⁴ mol per mol of silver per mol of silver emulsion. In addition, small-size emulsions were prepared by adding 2.5 × 10 ^-4 mol of each and then sensitizing with sulfur. The above-mentioned emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the following composition. Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. The following were used as spectral sensitizing dyes for each layer. Blue-sensitive emulsion layer

[0122]

Embedded image

(Per mol of silver halide: 2.0 × 10 ⁻⁴ mol for large-size emulsion and 2.5 × 10 ⁻⁴ mol for small-size emulsion, respectively) Green-sensitive emulsion layer

[0124]

Embedded image

(4.0 × 10 ^-4 mol for a large-size emulsion and 5.6 × 10 ^-4 mol for a small-size emulsion) per mol of silver halide

[0126]

Embedded image

(Per mol of silver halide: 7.0 × 10 ⁻⁵ mol for large-size emulsion, and 1.0 × 10 ⁻⁵ mol for small-size emulsion) Red-sensitive emulsion layer

[0128]

Embedded image

(Per mol of silver halide: 0.9 × 10 ^-4 mol for large-size emulsion, and 1.1 × 10 ^-4 mol for small-size emulsion) For red-sensitive emulsion layer The following compound silver halide 1
2.6 × 10 ^-3 mol was added per mol.

[0130]

Embedded image

The blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer were added to 1- (5-methylureidophenyl)-
5-mercaptotetrazole was replaced by silver halide 1
8.5 × 10 ⁻⁵ mol, 7.7 × 10 ⁻⁴ mol per mol,
2.5 × 10 ^-4 mol was added. In addition, 4-hydroxy-6-methyl-1, 4-hydroxy-6-methyl-1,
3,3a, 7-Tetrazaindene was added in an amount of 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide, respectively. The following dyes were added to the emulsion layer to prevent irradiation.

[0132]

Embedded image

[0133]

Embedded image

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. Support Polyethylene laminated paper [The first layer side polyethylene contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (exY) 0.82 Color image stabilizer (cpd-1) 0.19 Solvent (solv-1) 0.35 Color image stabilizer (cpd-7) 0.06 Second layer (color mixture prevention layer) Gelatin 0.99 color mixing inhibitor (cpd-5) 0.08 solvent (solv-1) 0.16 〃 (solv-4) 0.08

Third Layer (Green Sensitive Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture (Ag mole ratio) of 0.55 μm and 0.39 μm in average grain size) Particle size distribution Are 0.10 and 0.08, and each emulsion contains 0.8 mol% of AgBr locally on the surface of the grains.) 0.12 Gelatin 1.24 Magenta coupler (exM) 0.20 Color image stabilizer ( cpd-2) 0.03 Color image stabilizer (cpd-3) 0.15 Color image stabilizer (cpd-4) 0.02 Color image stabilizer (cpd-9) 0.02 Solvent (solv-2) 0 .40 fourth layer (ultraviolet ray absorbing layer) gelatin 1.58 ultraviolet ray absorbent (uv-1) 0.47 color mixture inhibitor (cpd-5) 0.05 solvent (solv-5) 0.24

Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cube, 1: 4 mixture of 0.58 μm and 0.45 μm average grains, Ag mole ratio), grain size distribution The coefficient of variation was 0.09 and 0.11, and each emulsion contained 0.6 mol% of AgBr locally on a part of the grain surface.) 0.23 Gelatin 1.34 Cyan coupler (exC) 0.32 Color image Stabilizer (cpd-6) 0.17 Color image stabilizer (cpd-7) 0.40 Color image stabilizer (cpd-8) 0.04 Solvent (solv-6) 0.15 Sixth layer (ultraviolet absorbing layer) ) Gelatin 0.53 UV absorber (uv-1) 0.16 Color mixing inhibitor (cpd-5) 0.02 Solvent (solv-5) 0.08

Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03

[0138]

Embedded image

[0139]

Embedded image

[0140]

Embedded image

[0141]

Embedded image

[0142]

Embedded image

[0143]

Embedded image

[0144]

Embedded image

[0145]

Embedded image

After exposing the above photosensitive material, continuous processing (running test) was performed using a paper processor until the replenishment of the bleach-fix tank capacity was twice as much in the following processing steps. Testing). Processing temperature Temperature Replenishment amount Tank capacity Color development 35 ° C 45 seconds 109 ml 17 liter Bleaching and fixing 35 ° C 45 seconds 61ml 17 liter or 30ml 10 liter Rinse 35 ° C 30 seconds-10 liter Rinse 35 ° C 30 seconds-10 liter Rinse 35 ° C. 30 seconds 300 ml 10 liters drying 80 ° C. 60 seconds ※ replenishment rate photosensitive material 1 m ² per ※ blix solution bleach-fixing replenisher and rinsing solution (12
1 ml) is replenished. * (Rinse → 3 tank countercurrent method)

The composition of each processing solution is as follows. Color developer tank liquid Replenisher water 800 ml 800 ml ethylenediamine-N, N, N, N-tetramethylenephosphonic acid 3.0 g 3.0 g triethanolamine 5.0 g 5.0 g potassium chloride 3.1 g-potassium bromide 0.015 g -Potassium carbonate 25 g 25 g Hydrazinodiacetic acid 5.0 g 7.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 9.5 g Fluorescent brightener (WHITEX-4 manufactured by Sumitomo Chemical Co., Ltd.) 1.0 g 2.5 g Add water 1000 ml 1000 ml pH (add potassium hydroxide) 10.05 10.60

Bleach-fix solution Tank solution Replenisher Replenisher Water 600 ml 150 ml 150 ml Ammonium thiosulfate (70 wt%) 100 ml 245 ml 245 ml or compound of the present invention 0.4 mol 1.0 mol 1.0 mol ammonium sulfite 45 g 105 g 105 g Iron (III) acetate 55 g 135 g 135 g Monium Ethylenediaminetetraacetic acid 3.0 g 8.0 g 8.0 g Ammonium bromide 30 g 75 g 150 g Nitric acid (67%) 27 g 68 g 100 g Add water 1 liter 1 liter 1 liter pH 5.80 5.60 5.40

Rinse solution (the tank solution and the replenisher are the same) Deionized water (3 ppm or less for each of calcium and magnesium) After the completion of the running treatment, the presence or absence of a precipitate in the bleach-fix bath and the rinse bath was visually examined. Table 2 shows that when the compound of the present invention was used as a fixing agent in place of thiosulfate, no precipitate was formed even during the running treatment, and the liquid stability was excellent. This effect is particularly remarkable when the replenishment is reduced.

[0150]

[Table 2]

Example 4 Compound 1 of Example 3 was replaced with Compounds 3, 7, 9, 14, 2
Example 3 in place of 0, 26, 29 or 32, respectively
The same test was performed. As a result, as in Example 3, good results were obtained in which no precipitate was formed during the running treatment. This effect was particularly remarkable when the replenishment was reduced.

Example 5 Preparation of Emulsion 30 g of gelatin and 6 g of potassium bromide were added to 1 liter of water, and an aqueous silver nitrate solution (5 g as silver nitrate) and 0.15 g of potassium iodide were added to a container kept at 60 ° C. while stirring. The aqueous potassium bromide solution was added by the double jet method over 1 minute. Further, an aqueous solution of silver nitrate (145 g as silver nitrate) and an aqueous solution of potassium bromide containing 4.2 g of potassium iodide were added by a double jet method. At this time, the flow rate was accelerated so that the flow rate at the end of the addition was five times that at the start of the addition. After completion of the addition, the soluble salts were removed at 35 ° C. by sedimentation, and the temperature was raised to 40 ° C., and 75 g of gelatin was added.
Was adjusted to 6.7. The resulting emulsion was tabular grains having a projected area diameter of 0.98 μm and an average thickness of 0.138 μm, and the silver iodide content was 3 mol%. This emulsion contains gold,
Chemical sensitization was performed in combination with sulfur sensitization.

Preparation of photographic material In addition to gelatin, an average molecular weight of 8000 was used as a surface protective layer.
A gelatin aqueous solution containing polyacrylamide, sodium polystyrene sulfonate, polymethyl methacrylate fine particles (average particle size: 3.0 μm), polyethylene oxide, and a hardener was used. Anhydro-5,5'-dichloro-9-ethyl-3,3'-di (3-sulfopropyl) oxacarbocyanine hydroxide sodium salt was added to the above emulsion as a sensitizing dye in 500 parts.
200 mg / 1 mole of potassium iodide at a rate of mg / 1 mole Ag
Ag was added at the rate. Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine and nitrone as stabilizers, and dry fog prevention A photographic material was prepared by adding trimethylolpropane, a coating aid, and a hardening agent as an agent to form a coating solution, and coating and drying the both sides of the polyethylene terephthalate support simultaneously with the surface protective layer. The coated silver amount of this photographic material is 2 g / m ² per one side. The swelling ratio according to the above definition was 180%.

The photographic material was exposed to X-rays by 50% and processed with the following formulas of a developing solution, a fixing solution and a washing solution. Processing process Step Processing time Processing temperature Replenishment tank capacity Developing 13.7 seconds 35 ° C 20 ml (+ diluent 10 ml) 15 liters Fixing 12.5 seconds 32 ° C 10 ml (+ diluent 30 ml) 15 liters 5 ml (+ diluent) (Water 15ml) Water washing 6.2 seconds 20 ℃ 500ml 10l squeeze roller washing tank 200ml ※ Replenishment amount: Quantity per photosensitive material 4 size (10 inch x 12 inch)

(Developer) Mother liquor (g) Replenisher (g) Potassium hydroxide 24 60 Sodium sulfite 40 100 Potassium sulfite 50 125 Diethylenetriaminepentaacetic acid 2.46 Boric acid 1025 Hydroquinone 35 87.5 Diethylin glycol 11. 228 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 2.5 6.25 5-methylbenzotriazole 0.06 0.15 pH 10.05 11.00

(Fixing solution) or Fixing agent Mother liquor (g) Replenishing solution (g) Replenishing solution (g) Ammonium thiosulfate 140 560 560 or compound of the present invention 1 mol 4 mol 4 mol sodium sulfite 15 60 60 disodium ethylenediaminetetraacetate 0.025 0.1 0.1 ・ Dihydrate sodium hydroxide 6 24 48 pH 5.5 5.10 4.70

(Washing solution) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetate disodium / 0.5 0.5 dihydrate 50 pieces per day (development rate of one film: 40
%) Was continued until the cumulative replenishment amount of the fixing solution became three times the mother liquor tank capacity.

When the photosensitive material was subjected to the development processing, the amount of the circulating stirring liquid of the developer was set to 20 liters / minute, and to 6 liters / minute during the standby time when the development processing was not performed. After the completion of the running process, the same sample as the running process was used, and the fixing time was reduced to 10.5 seconds and 11.5, and the process was performed. Then, the amount of silver remaining in the unexposed portion of the sample after the treatment was measured using a fluorescent X-ray analyzer. The presence or absence of a precipitate in the fixing bath was visually inspected. Table 3 shows the results.

[0159]

[Table 3]

Table 3 shows that when the compound of the present invention was used,
It can be seen that no precipitation occurs during the running process, the solution stability is good, and desilvering is possible with a fixing time of 11.5 seconds, which is clearly superior to thiosulfate. This effect is particularly remarkable when the replenishment is reduced.

Example 6 Compound-1 of Example 5 was replaced with Compounds-3, 5, 10, 12,
A test similar to that of Example 5 was performed in place of 14, 19, 26, or 32, respectively. As a result, as in Example 5, good results were obtained in which the fixing ability was high and no precipitation occurred during the running process. This effect is particularly remarkable when the amount of replenishment is low.

Example 7 (Preparation of photosensitive emulsion) 4 × 10 ⁻⁷ mol of iridium (III) hexachloride per mol of silver was added to an aqueous gelatin solution kept at 50 ° C.
In the presence of potassium and ammonia, an aqueous solution of silver nitrate and an aqueous solution of potassium iodide are simultaneously added over 60 minutes, and the pAg between them is kept at 7.8, so that the average particle size is 0.28 μm and the average silver iodide content is A cubic monodisperse emulsion of 0.3 mol% was prepared. The emulsion was desalted by flocculation, and then 4 mol / mol of silver.
After adding 0 g of inert gelatin, the mixture was kept at 50 ° C., and 5,5′-dichloro-9-ethyl-3,3′-bis (3-sulfopropyl) oxacarbocyanine was used as a sensitizing dye.
The solution was added to a KI solution of 10 ⁻³ mol per mol of silver, allowed to stand for 15 minutes, and then cooled. (Coating of photosensitive emulsion layer) This emulsion was redissolved, and the following hydrazine derivative was added at 40 ° C.

[0163]

Embedded image

Further, 5-methylbenztriazole, 4-
30 wt% for hydroxy-1,3,3a, 7-tetrazaindene, the following compounds (a), (b) and gelatin
% Polyethyl acrylate and the following compound (c) as a gelatin hardener were added, and a silver amount of 3.4 g / g on a polyethylene terephthalate film (150 μ) having an undercoat layer (0.5 μ) of a vinylidene chloride copolymer. It was applied as a m ^2.

[0165]

Embedded image

(Application of protective layer)
Gelatin 1.5 g / m ² , polymethyl methacrylate particles (average particle size 2.5 μ) 0.3 g / m ² , and AgCl fine particles (0.08 μ) so that the amount of Ag becomes 0.3 g / m ² .
Coating was performed using the following surfactants.

[0167]

Embedded image

These samples were prepared in a large size (50.8 cm ×
61.0cm) and 5 with 3200 ° K tungsten light
After 0% blackening exposure, 200 sheets were processed according to the following processing recipe. Processing Engineering as engineering more processing time processing temperature Replenishment rate current image 30 seconds 34 ° C. 240 ml Fixing 30 sec 34 ° C. 390 ml 250 ml water wash 30 seconds 20 ° C. 2 liters replenishment rate here shown as the amount per photographic material 1 m ² .

(Developer) Mother liquor = replenisher hydroquinone 50.0 g N-methyl-p-aminophenol 0.3 g sodium hydroxide 18.0 g boric acid 20.0 g potassium sulfite 110.0 g disodium ethylenediaminetetraacetate 1.0 g Potassium bromide 10.0 g 5-Methylbenzotriazole 0.4 g 5-mercaptobenzimidazole-5-sulfonic acid 0.3 g 3- (5-mercaptotetrazole) benzenesulfo 0.2 g Sodium acid 6-dimethylamino-1- Hexanol 4.0 g Sodium p-toluenesulfonate 15.0 g 5-Sulfosalicylic acid 30.0 g Add water, add 1 liter, add potassium hydroxide to adjust pH to 11.7.

(Fixing solution) Mother solution = replenisher solution 190.0 g of ammonium thiosulfate or 1 mol of the compound of the present invention 22.0 g of sodium sulfite 0.1 g of disodium ethylenediaminetetraacetate 0.1 g of tartaric acid 3.0 g of ammonia water (27%) 10.0 g of acetic acid (90%) 30.0 g Aluminum sulfate (27%) 35.0 g Add 1 liter of water and adjust to pH 4.8 by adding sodium hydroxide.

After this series of continuous processing, the presence or absence of a precipitate in the fixing solution was visually examined. Further, the amount of silver remaining in the unexposed portion of the processed sample immediately before the end of the series of processes was examined by a fluorescent X-ray analyzer. Table 4 shows that when the compound of the present invention was used, the fixing ability was excellent, and no precipitate was formed even in a large amount of processing, and the liquid stability was excellent. This effect is particularly noticeable when the replenishment rate is reduced.

[0172]

[Table 4]

Example 8 The compound-1 of Example 7 was replaced with the compound 9, 13, 20, or 2
A test similar to that of Example 7 was performed in place of Sample No. 5.
As a result, as in Example 7, good results were obtained in which the fixing ability was high and no precipitation occurred during the running process. This effect was particularly remarkable when the replenishment was reduced.

Example 9 Silver halide grains were precipitated by a double jet method.
After physical ripening and desalting, it is further chemically ripened and silver chloroiodobromide (bromine content: 30 mol%, iodine content: 0.1 mol%)
An emulsion was obtained. The average diameter of silver halide grains contained in this emulsion was 0.3 μm. 0.6 kg of silver halide was contained in 1 kg of this emulsion. This emulsion is
After weighing each kg and dissolving by heating at 40 ° C, the following sensitizing dye ^{* 1}
Was added, and a predetermined amount of an aqueous solution of sodium bromide was added. Next, 25 ml of a 1.0% by weight methanol solution of the following dye ^{* 2} was
In addition, 30 ml of a 1% by weight aqueous solution of 1-hydroxy-3,5-dichlorotriazine sodium salt was further added, and 40 ml of a 1.0% by weight aqueous solution of dodecylbenzenesulfonic acid sodium salt was further added, followed by stirring. This finished emulsion was coated on a cellulose triacetate film base so as to have a dry film thickness of 5 μm and dried to obtain a sample of a light-sensitive material. These samples were cut and exposed to 50% blackening using a sensitometer having a light source having a color temperature of 2666 ° K.

[0175]

Embedded image

A running process was performed according to the following processing recipe until the cumulative replenishment amount of the fixing solution became three times the capacity of the mother liquor tank. Processing step Processing time Processing time Processing temperature Replenishment amount Tank capacity Current image 20 seconds 38 ° C 320ml 18 liters Fixation 20 seconds 38 ° C 320ml 18 liters 220ml Rinse 20 seconds 20 ° C 2 liters 18 liters * Replenishment amount: photosensitive material 1m Quantity per ²

(Developer) Mother liquor = replenisher Methol 0.31 g Anhydrous sodium sulfite 39.6 g Hydroquinone 6.0 g Anhydrous sodium carbonate 18.7 g Potassium bromide 0.86 g Citric acid 0.68 g Potassium metabisulfite 1 1.5 g 1 liter with water

(Fixing solution) Mother liquor = replenisher 200 ml of ammonium thiosulfate or 1 mol of the compound of the present invention 12.0 g of sodium bisulfite 0.1 g of disodium ethylenediaminetetraacetate 0.1 g of tartaric acid 3.0 g of aqueous ammonia (27%) 0 g Acetic acid (90%) 20.0 g Aluminum sulfate (27%) 35.0 g Add 1 liter with water, add sodium hydroxide to adjust the pH of the fixer to pH 4.2, and adjust the pH of the fixer to pH 4.0. Was. The presence or absence of a precipitate in the fixing solution after the running process was visually inspected. Further, the amount of silver remaining in the unexposed portion of the processed sample immediately before the end of the running process was examined using a fluorescent X-ray analyzer.

[0179]

[Table 5]

From Table 5, it can be seen that when the compound of the present invention was used, the fixing ability was high, and the liquid stability was excellent in that no precipitate was formed even in the case of large-scale processing. Also, this effect is remarkably observed at a low replenishment rate.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-59-201056 (JP, A) JP-A-61-182037 (JP, A) JP-A 64-4739 (JP, A) JP-A-1- 201659 (JP, A) JP-A-58-122535 (JP, A) European publication 54415 (EP, A1)

Claims (3)

(57) [Claims] In a processing method for exposing and developing a silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, a bath having a fixing ability substantially reduces thiosulfate ions. Not including and the following general formula
A method for processing a silver halide photographic light-sensitive material, comprising at least one compound represented by formula (I) as a fixing agent. General formula (I) (Wherein Q represents an atom group necessary to form a 5- or 6-membered heterocyclic ring. This heterocyclic ring may be condensed with a carbon aromatic ring or a heteroaromatic ring. R is a carboxylic acid or A salt thereof, a sulfonic acid or a salt thereof, a phosphonic acid or a salt thereof, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group or a single bond substituted with at least one of an amino group and an ammonium group. Represents an integer of 1 to 3, and M represents a cationic group.) 2. A photographic fixing power composition substantially free of thiosulfate ions and containing at least one compound represented by the general formula (I). 3. The method according to claim 1, wherein the compound of the formula (I) is represented by the following formula (II). General formula (II) (Wherein, M and R have the same meanings as in the above general formula (I), and T and U each represent CR ′ or N;
R 'represents a hydrogen atom, a halogen atom, a hydroxy group, a nitro group, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a carbonamide group, a sulfonamide group, a ureido group, a thioureido group or R. Where R 'is R
And may be the same as or different from R in formula (I). )