JPH0572696A - Method for processing silver halide photographic sensitive material, and photographic fixing composition - Google Patents

Abstract

PURPOSE:To enhance fixing performance and stability of fixing solution even in the case of a small replenishing rate by using a specified mercapto compound having a water-soluble group as a fixing agent. CONSTITUTION:The silver halide photographic sensitive material provided with at least one photosensitive silver halide emulsion layer on a support is imagewise exposed and processed by the following development processing method: The fixing bath contains substantially no thiosulfate ion and as the fixing agent at least one of compounds represented by formula I in which Q is an atomic group necessary to form a 5- or 6-membered hetero ring optionally condensed with an aromatic ring or hetero ring; R is carboxylic, sulfonic, or phosphonic acid, or one of the salts of these acids, or alkyl, alkenyl, aralkyl, or aryl group each substituted by at least one of amino and ammonium group or a simple bond; n is 1, 2, or 3; and M is a cation.

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 having excellent fixability and a low replenishing amount, and the solution stability of the bath thereafter. And a method of processing a silver halide light-sensitive material excellent in

[0002]

2. Description of the Related Art Generally, the processing of a silver halide color photographic light-sensitive material comprises a color developing process and a silver removing process. The silver produced during development is oxidized with a bleaching agent and then dissolved with a fixing agent. A ferric (III) ion complex salt (for example, an aminopolycarboxylic acid-iron (III) complex salt) is mainly used as a bleaching agent, and a thiosulfate is usually used as a fixing agent. Further, the processing of the black-and-white photographic light-sensitive material comprises a developing process and a process of removing unexposed silver halide, and unlike the processing of the color photographic light-sensitive material, the fixing process is performed without passing through the bleaching process after development. Also in this case, thiosulfate is usually used as the fixing agent.

In recent years, as the replenishment rate has been lowered, more stable liquid compositions have been desired for each treatment bath. The thiosulfate which is usually used also in the fixing bath undergoes oxidative deterioration and is sulfided to form a precipitate, and therefore sulfite is added in most cases as a preservative for preventing oxidation. However, as low replenishment progresses further, improvement of liquid stability is further desired, but it can be solved by increasing the addition of sulfite because of solubility problems and precipitation of Glauber's salt when sulfite is oxidized. It's gone.

On the other hand, from the viewpoint of speeding up, a compound having a better fixing property than thiosulfate is desired. For these reasons, it has been desired to develop a fixing agent replacing thiosulfate, which has excellent oxidative stability and fixing ability, but no good alternative compound has been found to date.

[0005]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a fixing method having excellent fixing property. Another object of the present invention is to provide a method of processing a silver halide photographic material in which a bath containing a fixing agent and a solution stability of the bath thereafter are improved even when the replenishing amount is low.

[0006]

The above objects have been achieved by the following processing method and processing composition. (1) In the processing method of exposing and developing a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, the bath having fixing ability does not substantially contain thiosulfate ion. And a method of processing a silver halide photographic light-sensitive material, comprising at least one compound represented by the following general formula (I) as a fixing agent. General formula (I)

[0007]

[Chemical 3]

In the formula, Q represents a group of atoms necessary for forming a 5- or 6-membered heterocycle. The heterocycle may be fused 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 monocyclic group substituted with at least one of an amino group or an ammonium 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 heterocycle constituted by Q. n represents an integer of 1 to 3, and M represents a cation group.

(2) A fixing composition for photographic use, which is substantially free of thiosulfate ion and contains at least one compound represented by the general formula (I).

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

R is carboxylic acid or a salt thereof (eg sodium salt, potassium salt, ammonium salt, calcium salt), sulfonic acid or a salt thereof (eg sodium salt,
Potassium salt, ammonium salt, magnesium salt, calcium salt), phosphonic acid or a salt thereof (eg sodium salt, potassium salt, ammonium salt), a substituted or unsubstituted amino group having 1 to 10 carbon atoms (eg unsubstituted amino group, At least 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). C1-C10 alkyl group substituted with one (eg, methyl group, ethyl group, propyl group, butyl group, isopropyl group, 2-hydroxypropyl group, hexyl group, octyl group), C2-C10 Alkenyl group (eg vinyl group, propenyl group Butenyl group), aralkyl group having 7 to 12 carbon atoms (eg, benzyl group, phenethyl group), aryl group having 6 to 12 carbon atoms (eg, phenyl group, 2-chlorophenyl group, 3-methoxyphenyl group, naphthyl group), carbon It represents a heterocyclic group of 1 to 10 (eg, pyridyl group, thienyl group, furyl group, triazolyl group, imidazolyl group) or a single bond. In addition, R may be a group in which any of the above-mentioned alkyl group, alkenyl group, aralkyl group, aryl group and heterocyclic group is arbitrarily combined (for example, 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), carbon number It represents an aryl group of 6 to 10 (for example, a phenyl group, a 4-methylphenyl group).

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

The heterocycle represented by the general formula (I) and R are nitro group, halogen atom (for example, chlorine atom, bromine atom), mercapto group, cyano group, and substituted or unsubstituted alkyl group (for example, 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 group (eg allyl group), aralkyl group (eg benzyl group, 4-methylbenzyl group, phenethyl group), sulfonyl group (eg methanesulfonyl group, ethanesulfonyl group, p-toluenesulfonyl group), carbamoyl group (eg unsubstituted Carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group), sulfamoyl Group (eg, unsubstituted sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group), carbonamide group (eg, acetamide group, benzamide group), sulfonamide group (eg, 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) ), A thioureido group (for example, an unsubstituted thioureido group, a methylthioureido group),
Acyl group (eg acetyl group, benzoyl group), oxycarbonyl group (eg methoxycarbonyl group, phenoxycarbonyl group), oxycarbonylamino group (eg methoxycarbonylamino group, phenoxycarbonylamino group, 2-ethylhexyloxycarbonylamino group), It may be substituted with a hydroxyl group or the like.

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

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

[0016]

[Chemical 4]

In the formula, M and R have the same meanings as in the general formula (I). T and U are C-R '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 carbonamido group, a sulfonamide 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, R ′ is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.),
Hydroxy group, nitro group, alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, methoxyethyl group, n-
Butyl group, 2-ethylhexyl group, etc.), having 2 to 1 carbon atoms
0 alkenyl group (eg, allyl group, etc.), carbon number 7 to
15 aralkyl groups (eg, benzyl group, 4-methylbenzyl group, phenethyl group, 4-methoxybenzyl group,
Etc.), aryl groups having 6 to 15 carbon atoms (eg, phenyl group, naphthyl group, 4-methanesulfonamidophenyl group, 4-methylphenyl group, etc.), carbonamido groups having 1 to 10 carbon atoms (eg, acetyl). Amino group, benzoylamino group, methoxypropionylamino group, etc.), sulfonamide group having 0 to 10 carbon atoms (eg, methanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, etc.), carbon number 1 Ureido group of 10 (for example, an unsubstituted ureido group, a methylureido group,
Phenylureido group, etc.), thioureido group having 1 to 10 carbon atoms (eg, unsubstituted thioureido group, methylthioureido group, methoxyethylthioureido group, phenylthioureido group, etc.)

Or R. However, when R'represents R, it may be the same as or different from R in the general formula (II). In the general formula (II), preferably T = U = N or T
= U = C-R ', R'is a hydrogen atom, and has 1 to 1 carbon atoms.
4 represents an alkyl group having 4 carbon atoms, and R represents an alkyl group having 1 to 4 carbon atoms, which is substituted with one or two groups selected from carboxylic acids or salts thereof, sulfonic acids or salts thereof. Specific examples of the compound of the present invention are shown below, but the present invention is not limited thereto.

[0020]

[Chemical 5]

[0021]

[Chemical 6]

[0022]

[Chemical 7]

[0023]

[Chemical 8]

[0024]

[Chemical 9]

[0025]

[Chemical 10]

[0026]

[Chemical 11]

[0027]

[Chemical formula 12]

[0028]

[Chemical 13]

[0029]

[Chemical 14]

[0030]

[Chemical 15]

[0031]

[Chemical 16]

[0032]

[Chemical 17]

The compound used in the present invention is Berichte
Der Germany Berichte der Deutschen Chemischen Gesellschaft
28, 77 (1895), JP-A-50-37436,
51-3231, U.S. Pat. No. 3,295,976,
U.S. Pat. No. 3,376,310, Berichte der Germany Chen Hemitschen Gesellschaft
er Deutschen Chemischen Gesellschaft) 22, 568
(1889), ibid. 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), US Pat. No. 2,585,3
88, 2, 541, 924, Advances in Heterocyclic Chemistry
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), Chemiche Berichte (Chem
ische Berichte) 9, 465 (1876), Japanese Patent Publication 40
-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,
No. 3,071,465, No. 2,444,605, No. 2,444,606, No. 2,444,607, No. 2,935,404, etc. It can be synthesized according to a typical synthesis example.

Synthesis Example 1 (Synthesis Method 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 with stirring at 70 ° C. for 4 hours. After the reaction, the insoluble matter was filtered off, and the solid matter obtained by drying under reduced pressure was recrystallized from 400 ml of methyl alcohol to give 45.1 g of the desired product (yield 64.
7 g) was obtained. Compounds with melting points above 300 ° C are NM
The substance was confirmed to be the target by R, mass spectrum and elemental analysis.

Synthesis Example 2 (Synthesis Method of Exemplified Compound 13) 2-Sulfoethylisothiocyanate Sodium Salt 3
Water (230 ml) was added to 0.0 g and formylhydrazine (9.6 g), and the mixture was stirred at room temperature for 2 hours. Then sodium hydroxide 6.
After adding 3 g and heating under reflux for 2 hours, concentrated hydrochloric acid under ice-cooling 13.6
ml was added, and the solid obtained by drying under reduced pressure was recrystallized from 50 ml of water to obtain 17.6 g of the desired product (yield 48.2%). 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 Method 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 dropping, heat and stir at 60 ° C for 3 hours, then add 40 ml of acetic acid and add 4
Heated to reflux for hours. After the reaction, the reaction solution was dried under reduced pressure and recrystallized from 200 ml of a mixed solvent of methyl alcohol and water at a ratio of 3: 1 to obtain 19.0 g of the desired product (yield 41.2%). Melting point 274 to 275 ° C. The obtained compound was confirmed to be the target compound by NMR, mass spectrum and elemental analysis.

Examples of the "bath having fixing ability" in the present invention include a fixing bath and a bleach-fixing bath. The fixing composition for photographic use in the present invention includes, for example, 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 / liter, more preferably 1 × 10 ^{−2 to} 3 mol / liter, particularly preferably 2 ×. It is 10 ^{-1 to} 3 mol / liter. Alternatively, the amount used in the bleach-fixing bath is 2 × 10 ^-2 to 10 mol /
L is suitable, and 2 × 10 ^{-1 to} 3 mol / l is preferable. 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%), it is 0.5.
It is preferably used at ˜2 mol / liter, more preferably 1.2 to 2 mol / liter. Further, the halogen composition is AgBr, AgBrCl, or high silver chloride (for example, A
gCl ≧ 80 mol% or more, preferably 90 to 100 mol%, more preferably 95 to 99.5 mol%), especially in the case of high silver chloride, used at 2 × 10 ⁻¹ to 1 mol / liter. Is preferred.

The term "substantially free of thiosulfate ion in the fixing ability composition used in the present invention" specifically means thiosulfate ion (for example, ammonium thiosulfate).
0.1 mol / liter or less, more preferably 0.05
It means that it is not more than 0.01 mol / liter, particularly preferably not more than 0.01 mol / liter. Thus, by using at least a relatively large amount of the compound of the present invention or only the compound of the present invention, it can be used as an effective fixing agent. As the replenishment rate has been lowered in recent years, it is desired to improve the liquid stability of each treatment bath. A problem with the stability of fixing baths (or bleach-fixing baths) and of subsequent baths is the precipitation of sulphides caused by the oxidative degradation of the thiosulfates used as fixing agents. The problem also occurs in the washing bath because the fixing solution (or the bleach-fixing solution) is brought into the washing bath during processing. Sulfite is usually used as an antioxidant to prevent this precipitation, but when the amount of replenishment is low, increasing the amount of sulfite used will cause solubility problems and oxidation of sulfite. It cannot be solved due to problems such as precipitation of Glauber's salt.

As a result of various investigations by the present inventors on a fixing agent excellent in oxidative stability instead of thiosulfate, the compound of the present invention has a fixing ability, is stable against oxidation, and precipitates even at a low replenishing amount. We found that there was no generation. On the other hand, in the bleach-fixing bath, the oxidative property of the solution itself is considerably higher than that of the fixing bath. Therefore, in the presence of thiosulfate, precipitation was observed in the bleach-fixing bath and the post-bath washing bath at low replenishment. When used only in the compound of the present invention, good liquid stability was obtained without precipitation formation. In addition, adding the compound of the present invention to a washing bath or a stabilizing bath is also effective and effective in preventing precipitation of the washing bath. Here, the concentration in these baths is preferably 10 ^{−3 to} 0.5 times the concentration of the fixing agent in the previous bath.

Next, the silver halide color photographic light-sensitive material and the processing method using the same will be described in detail. The silver halide color photographic light-sensitive material of the present invention may have at least one silver halide emulsion layer of a blue color sensitive layer, a green color sensitive layer and a red color sensitive layer provided on a support. The number and order of the silver halide emulsion layer and the non-photosensitive layer are not particularly limited. As a typical example, a silver halide photographic light-sensitive material having at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. And the photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light and red light, and in the multilayer silver halide color photographic light-sensitive material,
In general, the unit photosensitive layers are arranged in the order of the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer. For the intermediate layer, JP-A-61-43748 and JP-A-5-43748 are used.
9-113438, 59-113440, 61
Nos. 20037 and 61-20038 may contain a coupler, a DIR compound and the like, and may also contain a color mixing inhibitor as commonly used. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure can be preferably used. Usually, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Further, JP-A Nos. 57-112751, 62-200350 and 6
2-206541, 62-206543, etc., a low-sensitivity emulsion layer on the side remote from the support,
A high sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
Can be installed in order. In addition, Japanese Examined Japanese Patent Publication Sho 55-34
As described in Japanese Patent No. 932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. Also, JP-A-56-25738
No. 62-63936, the blue-sensitive layer / GL / RL from the side farthest from the support.
It can also 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. Another example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. It may be arranged in the order of layer / high-speed emulsion layer / low-speed emulsion layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material. When the silver halide color photographic light-sensitive material is a color negative film or a color reversal film, a 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% silver iodide.

When the silver halide color photographic light-sensitive material is a color photographic paper, the silver halide contained in the photographic emulsion layer is silver chlorobromide or silver chloride containing substantially no silver iodide. The following can be preferably used. The term "substantially free of silver iodide" as used herein 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 can be used. This ratio can take a wide range depending on the purpose, but 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 for a light-sensitive material suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more, more preferably 95 mol% or more. For the purpose of reducing the replenishment amount of the development processing solution, the silver chloride content is 98 to 99.9.
An almost pure silver chloride emulsion having a mol% is also preferably used.

The silver halide grains in a photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof. The grain size of silver halide may be fine grains of about 0.2 μ or less or large grains having a projected area diameter of up to about 10 μ, 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 ibid. No. 18716 (November 1979), 6
It can be prepared using the method described on page 48 or the like. U.S. Pat. Nos. 3,574,628 and 3,65
The monodisperse emulsions described in, for example, 5,394 and British Patent 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 in Gutoff, Photographic Science and Engineering.
ngineering), Vol. 14, pp. 248-257 (1970)
); U.S. Pat. Nos. 4,434,226 and 4,41
4,310, 4,433,048, 4,43
It can be easily prepared by the method described in 9,520 and British Patent 2,112,157. The crystal structure may be uniform, may have a different halogen composition between the inside and the outside, may have a layered structure, and may have a different composition by epitaxial bonding. Alternatively, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

As the silver halide emulsion, those which have been physically ripened, chemically sensitized and spectrally sensitized are usually used. 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 be introduced during the physical aging process. . Compounds used for chemical sensitization are described in JP-A-62-21.
No. 5,272, the description on page 18, lower right column to page 22, upper right column can be mentioned. The additives used in such a process are RD No. 17643 and RD No. 187.
16 and the relevant parts are summarized in the table below. Known photographic additives that 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, pages 23 to 24, page 648, right column ~ Supersensitizer, page 649, right column 4 Whitening agent page 24 5 Antifoggant page 24 to 25 page 649 right column ~ and stabilizer 6 Light absorber, page 25 to 26 page 649 right column ~ Filter dye, page 650 left column UV absorber 7 Stain inhibitor Page 25 right column page 650 left-right column 8 dye image stabilizer page 25 9 film hardening agent page 26 651 page left column 10 binder page 26 same as above 11 plasticizers and lubricants page 27 650 page right column 12 coating aid, Pages 26-27 Pages 650 Right column Surfactant 13 Antistatic agent Page 27 Same as above

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,98
It is preferable to add a compound capable of being immobilized by reacting with formaldehyde described in No. 7 and No. 4,435,503 to the light-sensitive material. Various color couplers can be used in the present invention, and specific examples thereof are RD No. mentioned above.
17643, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620,
No. 4,326,024, No. 4,401,752, No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, No. 1,476,760.
U.S. Pat. Nos. 3,973,968 and 4,314,
023, 4,511,649, European Patent No. 24
Those described in No. 9,473A and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferred, 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.
U.S. Pat. Nos. 4,500,630 and 4,540,
No. 654, No. 4,556,630, WO (PCT) 8
Those described in, for example, 8/04795 are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
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
No. 2,002, No. 3,758,308, No. 4,33
4,011, 4,327,173, West German Patent Publication No. 3,329,729, European Patent 121,365A.
No. 249,453A, US Pat. No. 3,446,6.
No. 22, No. 4,333,999, No. 4,753,87
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.
Those described in No. etc. are preferable.

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

Examples of couplers in which the coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable. Typical examples of polymerized dye forming couplers are U.S. Pat. Nos. 3,451,820 and 4,084.
0,211, 4,367,282, 4,40
9,320, 4,576,910, British Patent 2,
No. 102,173.

A coupler which releases a photographically useful residue upon coupling is also preferably used in the present invention. The DIR coupler releasing a development inhibitor is the above-mentioned R
Patents described in D17643, VII to F, JP-A-5
7-151944, 57-154234, 60
Those described in U.S. Pat. Nos. 4,184,248 and 63-37346, and U.S. Pat. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patents 2,097,140 and 2,131,188, JP-A-59-157638 and 59-170840. Those described in are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,42.
Competitive couplers described in US Pat.
No. 472, No. 4,338,393, No. 4,310,6
No. 18, etc., multi-equivalent couplers, JP-A-60-185.
950, DIR described in JP-A-62-24252, etc.
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, a coupler for releasing a dye which is recolored after separation, RD No. 11449, 24241, and a bleaching accelerator releasing coupler described in JP-A No. 61-201247, U.S. Pat. No. 4,553,477. Ligand releasing couplers described in JP-A No. 63-75747 and leuco dye releasing couplers described in JP-A-63-75747, U.S. Pat.
Examples thereof include couplers that release the fluorescent dye described in 4,181.

The coupler used in the present invention can be introduced into the photographic material by various known dispersion methods. Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,222.
No. 027 and the like, and specific examples of the high-boiling-point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used for the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di- 2-ethylhexyl phthalate, decyl phthalate, bis (2,4-
Di-t-amylphenyl) phthalate, bis (2,4-
Di-t-amylphenyl) isophthalate, bis (1,
1-diethylpropyl) phthalate etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxy) Ethyl phosphate,
Trichloropropyl phosphate, di-2-ethylhexyl phenylphosphonate, etc., Benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate etc.), amides (N, N-diethyldodecane amide, N , N-diethyllaurylamide, N-tetradecylpyrrolidone, etc., alcohols or phenols (isostearyl alcohol, 2,4-di-tert-)
Amylphenol), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivative (N, N-dibutyl-2) -Butoxy-5-t
ert octylaniline) and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and a typical example is ethyl acetate,
Butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like can be mentioned.

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.
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, US Pat. No. 4,203,716) in the presence or absence of the above high boiling point organic solvent,
Alternatively, it can be dissolved in a water-insoluble polymer soluble in an organic solvent and emulsified and dispersed in a hydrophilic colloid aqueous solution. Preferably, the homopolymer or copolymer described on pages 12 to 30 of International Publication No. WO88 / 00723 is used. Particularly, it is preferable to use an acrylamide polymer in terms of color image stabilization and the like.

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 photosensitive materials, color positive films and color reversal papers. Suitable supports that can be used in the present invention are described, for example, in RD. No. 17643, page 28,
And pp. 647, right column to 648, left column of the same No. 18716.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is 25 μm or less, preferably 20 μm or less, and the film swelling rate T _1/2 is 3.
It is preferably 0 seconds or less (preferably 15 seconds or less). The film thickness means a film thickness measured under a humidity condition of 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.), Vol. 19, No. 2, pp. 124-129, and can be measured by using a swellometer (swelling meter) of the type. T _1/2 is a color developing solution at 30 ° C. for 3 minutes. 90% of the maximum swollen film thickness reached after 15 seconds of treatment is defined as the saturated film thickness, and is defined as the time required to reach this half film thickness. The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating. Also, the swelling rate is 150 to
400% is preferable. The swelling ratio is calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness) /
It can be calculated according to the film thickness.

The color photographic light-sensitive material described above is the same as the RD described above.
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 containing an aromatic primary amine color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N diethylaniline and 3-methyl. -4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-
Examples thereof include N-ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Two or more kinds of these compounds can be used in combination depending on the purpose.

The color developer contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. It is common to include agents or antifoggants. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo [2,2,2] octane) s, etc. Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride. , Chelating agents represented by auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids (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 salts thereof, 4,4′-diamino-2 , Whitening agents such as 2'-disulfostyrene bene compounds, alkyl sulfonic acids, aryl sulfonic acids, aliphatic carboxylic acids,
You may add various surfactants, such as aromatic carboxylic acid.

However, it is preferable that benzyl alcohol is not substantially contained from the viewpoints of pollution, liquid preparation and prevention of color contamination. Here, "substantially" means 2 ml or less (more preferably not including it) per liter of color developing solution. When the reversal process is performed, black and white development is usually performed before color development. This black-and-white developer contains dihydroxybenzenes such as hydroquinone and 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.

PH of these color developing solution and black and white developing solution
Is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also do it. In particular,
When using a so-called high silver chloride light-sensitive material, the bromine ion in the color developing solution is made low and the chloride ion is made relatively large so that the photographic property and the processability are excellent, and the fluctuation of the photographic property can be suppressed. Therefore, it is particularly preferable. 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 amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area with the air in the processing tank. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The processing temperature of the color developing solution of the present invention is 20 to 20.
It is preferably 30 to 45 ° C. at 50 ° C. The 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 bleached. The bleaching process may be performed at the same time as the fixing process (bleach-fixing process) or separately. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. The processing temperature of the bleaching solution and the bleach-fixing solution of the present invention is 20 to 50 ° C, preferably 30 to 45 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 4 minutes. Examples of bleaching agents include iron (III) and cobalt (II
Compounds of polyvalent metals such as I), chromium (IV) and copper (II), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are ferricyanide; dichromate; iron (II
Organic complex salts of I) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Aminopolycarboxylic acids such as diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. it can. Of these, iron (III) aminopolycarboxylates, including iron (III) ethylenediaminetetraacetate complex salts
The complex salt is preferably persulfate from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. In particular, bleaching solutions for negative photographic materials for photography include 1,3-
A diaminopropanetetraacetic acid iron (III) complex salt is preferable from the viewpoint of bleaching ability. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5.
However, it can be processed at a lower pH for speeding up the processing. The amount of the bleaching agent used is preferably 0.05 to 1 mol per liter of the processing liquid.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleach accelerators are described in the following specifications. U.S. Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP-A-53-32736, 53-57831, 53.
-37418, 53-72623, 53-95.
No. 630, No. 53-95631, No. 53-10423.
No. 2, No. 53-124424, No. 53-141623.
No. 53-28426, RD No. 17129 (1
Compounds having a mercapto group or a disulfide group described in JP-A No. 50-140129; JP-B No. 45-8506.
No. 52-20832 and 53-32735.
Thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent No. 1,127,715, JP-A-58.
No. 16,235, iodide salt; West German Patent No. 96
Nos. 6,410 and 2,748,430, polyoxyethylene compounds; polyamine compounds described in JP-B-45-8836; other JP-A-49-42434,
49-59644, 53-94927, 54
-35727, 55-26506, 58-16
Compounds described in 3940; bromide ion and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and in particular, US Pat. No. 3,893,858 and West German Patent 1,290,
Compounds described in JP-A No. 812 and JP-A-53-95630 are preferable. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. 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 x 10 ^-4 to 1 x 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 light-sensitive material for photographing.

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 addition to the compounds of the present invention, known fixing agents other than thiosulfate ions may be used in combination in the fixing bath of the present invention. Examples of the fixing agent include thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts. The amount of the fixing agent used together is approximately the same as that of the compound of the general formula (I) of the present invention, and may be mixed with the compound of the general formula (I) in an arbitrary ratio. As a preservative for the bleach-fix solution, sulfite, bisulfite, carbonyl bisulfite adduct, and sulfinic acid compound are preferable. In order to improve the stability of the fixing solution, the fixing solution contains aminopolycarboxylic acids and organic phosphonic acid type chelating agents (preferably 1-hydroxyethylidene-1,1-diphosphonic acid and N, N, N ',
N'-ethylenediaminetetraphosphonic acid) is preferable.

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 is preferably 30 seconds to 4 minutes. The fixing solution may further contain various fluorescent whitening agents, antifoaming agents, surfactants, polyvinylpyrrolidone, methanol and the like. From the viewpoint of shortening the desilvering processing time, it is preferable that the stirring of each processing solution in the desilvering step is strengthened as much as possible. Examples of the stirring means include the methods described in JP-A Nos. 62-183460 and 62-183461. In the case of a means for colliding a jet flow, the photosensitive material is treated in the processing liquid until the collision. It is preferable to perform the treatment within 15 seconds after the introduction.

In the present invention, the crossover time from the color developing solution to the bleaching solution (the aerial time until the photosensitive material comes out of the color developing solution and enters the bleaching solution) is improved in bleaching fog and adhesion of stains on the surface of the photosensitive material. It is preferably 10 seconds or less. Further, the crossover time from the bleaching solution of the present invention to the processing solution having a fixing ability is preferably within 10 seconds from the viewpoint of improving the color recovery failure of the cyan dye. According to the method of the present invention, the replenishment amount can be reduced. Here, the replenishing amount of the fixing solution is preferably 300 to 800 ml / m ^{2 in} the case of a color photosensitive material for photographing (for example, coating amount of 4 to 12 g / m ² ), and the replenishing amount of the bleach-fixing solution is preferable. 20-50 ml
/ M ² is preferred.

The silver halide color photographic light-sensitive material used in the present invention is generally washed with water and / or stabilized after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as coupler), application, and further the temperature of rinsing water, the number of rinsing tanks (number of stages), countercurrent,
It can be set in a wide range depending on the replenishment method such as normal flow and various other conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is shown in the Journal of the Society of Moti
on Picture and Television Engineers Volume 64,
P. 248 to 253 (May 1955 issue). According to the multi-stage counter-current method described in the above literature, the amount of washing water can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problems arise. 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 and Mg ions described in JP-A-62-288838 can be used very effectively. In addition, JP-A-57-85
No. 42, isothiazolone compounds, thiabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents," Sanitary Engineering Society, "Microorganisms" Sterilization, sterilization,
The bactericides described in "Antifungal Technology" and "Encyclopedia of Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents can also be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes,
A range of 30 seconds to 5 minutes at 25 to 40 ° C. is preferably selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilizing treatment, JP-A-57-8543 and 58-58 are used.
All known methods described in Nos. 14834 and 60-220345 can be used.

In some cases, the washing treatment is further followed by a stabilizing treatment, and for example, formalin, hexamethylenetetramine, hexahydrotriazine and N-, which are used as the final bath of the color light-sensitive material for photographing, are used. A stabilizing bath containing a dye stabilizer typified by a methylol compound can be mentioned. Also in this stabilizing bath, if necessary, ammonium compounds, metal compounds such as Bi and Al, optical brighteners, various chelating agents, film pH regulators, hardeners, bactericides, fungicides, alkanolamines and surface active agents. Agents (preferably silicon-based) can also be added. As the water used in the washing step or the stabilizing step, tap water, water deionized to a Ca ion or Mg ion concentration of 5 mg / liter or less by an ion exchange resin, or water sterilized by halogen, an ultraviolet germicidal lamp, or the like Is preferably used.

The replenishing amount of the above-mentioned washing and / or stabilizing solution is 1 to 50 of the amount carried from the prebath 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 accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in U.S. Pat. No. 3,342,597, 3,342,599, RD
Schiff base type compounds described in Nos. 14,850 and 15,159, aldol compounds described in 13,924, metal salt complexes described in U.S. Pat. No. 3,719,492, JP-A-53-135628. The urethane compounds described in No. 1 can be mentioned. The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. A typical compound is JP-A-56-64339.
No. 57-144547 and No. 58-11543.
No. 8 etc.

Various processing solutions used in the present invention are 10 ° C. to 50 ° C.
Used at ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to.

As an example of the silver halide color light-sensitive material, there is one using direct positive type silver halide. Processing using this photosensitive material will be described below. A surface developing solution containing an aromatic primary amine color developing agent and having a pH of 11.5 or less after imagewise exposure of a silver halide color photographic light-sensitive material, after or after being subjected to a fogging treatment with light or a nucleating agent. It is also preferable to directly form a positive color image by performing color development, bleaching, and fixing processing in step 1. The pH of this developer is more preferably in the range of 11.0 to 10.0. The fogging treatment in the present invention includes a method of giving a second exposure to the entire surface of a photosensitive layer, which is so-called "light fogging method", and a method of developing in the presence of a nucleating agent, which is called "chemical fogging method". Either may be used. You may develop in the presence of a nucleating agent and fog light. Further, a light-sensitive material containing a nucleating agent may be fog-exposed.

Regarding the light fogging method, the above-mentioned Japanese Patent Application No.
No. 253716, page 47, line 4 to page 49, line 5, and the nucleating agent that can be used in the present invention is described on page 49, line 6 to page 67, line 2 of the specification. It is particularly preferable to use the compounds represented by the general formulas [N-1] and [N-2]. Specific examples of these include the fifth in the same specification.
[N-I-1] to [N-I-10] described on pages 6 to 58
And [N-II-1] described on pages 63 to 66 of the same specification.
The use of [N-II-12] is preferred. Regarding the nucleation accelerator that can be used in the present invention, the same specification, page 68, line 11-71.
It is described on page 3, line 3. Particularly, as specific examples thereof, use of (A-1) to (A-13) described on pages 69 to 70 is preferable.

Next, the silver halide black and white photographic light-sensitive material and the processing using the same will be described in detail. There is no particular limitation on the halogen composition of the silver halide emulsion used, and any composition such as silver chloride, silver chlorobromide, silver iodobromide, silver bromide and silver iodobromochloride may be used. The content of silver halide is preferably 10 mol% or less, more preferably 5 mol% or less. When used for forming a negative image with high contrast, the average grain size of silver halide used is fine grains (for example, 0.7
μ or less) is preferable, and 0.5 μ or less is particularly preferable. The particle size distribution is basically not limited, but it is preferably monodisperse. Here, the monodispersion means that at least 95% by weight or the number of particles is ± of the average particle size
It is composed of particles having a size within 40%. The silver halide grains in photographic emulsions are regular such as cubic, octahedral, rhombohedral and tetradecahedral.
It may have various crystalline bodies, may have irregular crystals such as spherical or tabular, or may have a composite form of these crystalline 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 No. 60-64199 and Japanese Patent Application No. 602320886, and the maximum density (Dmax) is increased. In this respect, it is preferable that the small-sized single particles are chemically sensitized, and the method of chemical sensitization is most preferably sulfur sensitization. The large size monodisperse emulsion may or may not be chemically sensitized. Since large-sized monodisperse particles generally cause black spots, they are not chemically sensitized. However, when they are chemically sensitized, it is particularly preferable to apply shallowly so that black spots do not occur.
Here, "shallowing" means that the time for chemical sensitization is shorter than the chemical sensitization of small-sized grains, the temperature is low, and the amount of the chemical sensitizer added is small.
The sensitivity difference between the large size monodisperse emulsion and the small size monodisperse 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 particle size of the small size monodisperse grains is 90% or less, preferably 80% or less of the average size of the large size silver halide monodisperse grains.

The printing light-sensitive material used in the present invention may contain a known nucleating agent in the photographic emulsion layer or other hydrophilic colloid layer to form an ultrahigh contrast image. Examples of the nucleating agent used in the present invention include RESEARCH DISC
LOSURE Item 23516 (November 1983 issue, P.
346) and the references cited therein. Development accelerators or nucleation-infectious development accelerators suitable for use in the present invention are described in 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 redox potential determined by polarography, and the sum of the polaro anode potential and the cathode potential is 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 used in the development processing of the silver halide black and white light-sensitive material of the present invention contains additives usually used (eg, developing agent, alkaline agent, pH buffering agent, preservative, chelating agent). be able to. The process of the present invention includes
Any known method can be used, and a known processing solution can be used. The treatment temperature is usually selected from 18 ° C to 50 ° C, but it 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. In the black and white developer, known developing agents such as dihydroxybenzenes (for example, hydroquinone), 1-phenyl-3-pyrazolidones, aminophenols (for example, N-methyl-p-aminophenol) and the like may be used alone or in combination. Can be used.

The dihydroxybenzene type developing agent is usually preferably used in an amount of 0.05 mol / liter to 0.8 mol / liter. Further, dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-amino-
When using a combination with phenols, the former is 0.0
5 mol / l to 0.5 mol / l, the latter of 0.
It is preferably used in an amount of not more than 06 mol / liter. Examples of sulfite preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. A black and white developer, especially a developer for graphic arts, contains 0.3 mol / liter or more of sulfite, but if added in an excessively large amount, it precipitates in the developer and causes solution contamination, so the upper limit is 1.2 mol / liter. Is preferred.

The alkaline agents used in the developer of the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate, potassium triphosphate, sodium silicate, potassium silicate and the like. 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, toluethylene glycol, dimethylformamide, methyl cellosolve,
Organic solvents such as hexylene glycol, ethanol and methanol: 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt and other mercapto compounds, 5-nitroindazole and other indazole compounds, 5 -Antifoggant or black pepper inhibitor such as benztriazole-based compound such as methylbenztriazole may be contained, and if necessary, toning agent, surfactant, defoaming agent, water softener, A hardener, etc. may be included. The compounds described in JP-A-56-24347 are used as silver stain preventing agents, and the development unevenness preventing agents are disclosed in JP-A-62-21265.
Japanese Patent Application No. 60-10 as a compound and a dissolution aid described in No. 1
The compound described in 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, acetols) described in JP-A-60-93433 are used as a buffer. Oxime), phenols (for example, 5-sulfosalicylic acid), tertiary phosphate (for example, sodium salt, potassium salt) and the like are used. The fixer 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 salts thereof), if necessary, in addition to the fixing agent, and preferably has a pH of 3. 8 or more, more preferably 4.
It has 0 to 7.5. In the fixing bath of the present invention, a known fixing agent other than thiosulfate ion may be used together with the compound of the present invention. Examples of the fixing agent include thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts. The amount of the fixing agent used in combination is the same as that of the compound of the general formula (I) of the present invention, and may be mixed with the compound of the general formula (I) in an arbitrary ratio. The water-soluble aluminum salt mainly used as a hardening agent in the fixing solution is a compound generally known as a hardening agent for an acidic hardening fixing solution,
Examples include aluminum chloride, aluminum sulfate, and potassium alum. As the above-mentioned dibasic acid, tartaric acid or its derivative, citric acid or its derivative can be used alone or in combination of two or more kinds. It is effective that these compounds contain 0.005 mol or more per liter of the fixer, and particularly 0.01 mol / liter to 0.03 mol / liter is particularly effective. Specifically, tartaric acid,
Examples include potassium tartrate, sodium tartrate, sodium potassium tartrate, ammonium tartrate, potassium ammonium tartrate, and the like.

If desired, the fixer may further contain preservatives (eg, sulfite, bisulfite), pH buffers (eg, acetic acid, boric acid), pH adjusters (eg, ammonia, sulfuric acid), and improve image preservation. Agents (for example, potassium iodide) and chelating agents can be included. Since the pH of the developing solution is high, the pH buffer is used in an amount of 10 to 40 g / liter, more preferably 18 to 25 g / liter. The fixing temperature and time are the same as in the case of development, and the temperature is about 20 ° C. to about 50 ° C.
0 second to 1 minute is preferable. Here, the replenishing amount of the fixing solution is preferably 50 to 300 ml / m ² or less.

As the washing water, those mentioned above can be used. Further, a stabilizing solution may be used instead of the washing water. The roller-conveying type automatic developing machine is described in U.S. Pat. Nos. 3,025,779 and 3,545,971 and the like, and is herein simply referred to as a roller-conveying type processor. The roller transport type processor comprises four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, stopping step), but it is most preferable to follow these four steps. .. Here, in the water washing step, water saving treatment can be performed by using 2-3 stages of countercurrent water washing. The black-and-white photographic light-sensitive material according to the present invention includes ordinary black-and-white silver halide photographic light-sensitive materials (for example, black-and-white light-sensitive material for photographing, black-and-white light sensitive material for X ray, black-and-white light sensitive material for printing), infrared light for laser scanner. Sensitive materials, etc. can be mentioned.

[0089]

When the compound of the present invention is used, the stability (especially, no sulfurization, etc.) of a fixing solution or a fixing solution having a bleaching ability (for example, a bleach-fixing solution) can be improved and a good fixing ability can be obtained. It is possible to obtain a treatment composition or treatment liquid having Further, when the compound of the present invention is used, stable processing can be carried out even if the replenishing amount of the fixing solution or the bleach-fixing solution is drastically reduced.

[0090]

EXAMPLES Examples of the present invention will be specifically shown below, but the present invention is not limited thereto. Example 1 On a subbed cellulose triacetate film support,
A sample 101, which is a multi-layer color light-sensitive material 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 by the number 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 ... 6x10 ^-4 2nd 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, variation coefficient of sphere equivalent diameter 29%, normal crystal, twin Crystal mixed particles, diameter / thickness ratio 2.5) Coating amount of silver ...... 0.5 Gelatin ...... 0.8 ExS-1 …… 1.0 × 10 ^-4 ExS-2 …… 3.0 × 10 ^-4 ExS-3 ・ ・ ・1 × 10 ^-5 ExC-3 ・ ・ ・ 0.22 ExC-4 ・ ・ ・ 0.02 Cpd-5 ・ ・ ・ 3 × 10 ^-4 4th layer (second red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type, sphere equivalent diameter 0.55 μm, coefficient of variation of sphere equivalent 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 ... 5x10 ^-4

Fifth Layer (Third Red Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, sphere equivalent diameter 0.7 μm, variation coefficient of sphere equivalent diameter 30%, normal crystal, Twin mixed particles, diameter / thickness ratio 2) Coating amount of silver ・ ・ ・ 0.7 Gelatin ・ ・ ・ 0.8 ExS-1 ・ ・ ・ 1 × 10 ^-4 ExS-2 ・ ・ ・ 3 × 10 ^-4 ExS-3 ...... 1 x 10 ^-5 ExC-5 ...... 0.05 ExC-6 ...... 0.06 Solv-1 ...... 0.15 Solv-2 ...... 0.08 Cpd-5 ...... 3x10 ^-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, variation coefficient of sphere equivalent diameter 28%, normal crystal, twin Crystal mixed particles, diameter / thickness ratio 2.5) Coating amount of silver ・ ・ ・ 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 8th Layer (second green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type, sphere equivalent diameter 0.55 μm, variation coefficient of sphere equivalent diameter 20%, normal crystal, twin crystal 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, variation coefficient of sphere equivalent diameter 30%, normal crystal, Twin mixed particles, diameter / thickness ratio of 2.0) Coating amount of silver: 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 Yellow colloidal silver: 0.05 Cpd-1: 0.2 Solv-1: 0.15 Cpd-5: 4 × 10 ^{− 4} 11th layer (first blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type, sphere equivalent diameter 0.5 μm, variation coefficient of sphere equivalent diameter 15%, octahedral grains) 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, variation coefficient of sphere equivalent diameter 25%, normal crystal, Twin mixed particles, diameter / thickness ratio of 4.5) Coating amount of silver: 0.5 gelatin: 0.6 ExS-8: 1 × 10 ^-4 ExY-16 :: 0.12 Solv-1: 0.04 Cpd-5 2 × 10 ^-4 13th layer (first protective layer) Fine grain silver iodobromide (average grain 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 × 10 ^-4

14th layer (second protective layer) Gelatin: 0.9 Polymethylmethacrylate particles (diameter: 1.5 μm): 0.2 Cpd-5: 4 × 10 ^-4 H-1: 0. 4. In addition to the above components, a surfactant was added to each layer as a coating aid. The sample prepared as described above was used as 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]

[Chemical 18]

[0100]

[Chemical 19]

[0101]

[Chemical 20]

[0102]

[Chemical 21]

[0103]

[Chemical formula 22]

[0104]

[Chemical formula 23]

[0105]

[Chemical formula 24]

[0106]

[Chemical 25]

[0107]

[Chemical formula 26]

[0108]

[Chemical 27]

[0109]

[Chemical 28]

[0110]

[Chemical 29]

The dried film thickness of the support of the sample 101 prepared at this time and the coating layer excluding the undercoat layer of the support was 17.6 μm.
And the swelling rate (T _1/2 ) was 8 seconds. The prepared sample was cut and processed to have a width of 35 mm, and after exposure, a running treatment was carried out by using an automatic developing machine according to the processing recipe shown below until the cumulative replenishment amount of the fixer became 3 times the mother liquor tank capacity.

Processing Process Processing Time Processing temperature Replenishment amount Replenishment tank capacity Color development 3 minutes 15 seconds 38 ° C 15 ml 20 liters Bleach 4 minutes 30 seconds 38 ° C 10 ml 40 liters Water wash 2 minutes 10 seconds 35 ° C 10 ml 20 liters Settling 4 minutes 20 seconds 38 ℃ 30ml 30 liters or 15ml Washing with water (1) 1 minute 05 seconds 35 ℃ 10 liters from (2) to (1) Countercurrent piping system. Washing with water (2) 1 minute 00 seconds 35 ℃ 20ml 10 liters Stability 1 minute 05 seconds 38 ℃ 10ml 10 liters Dry 4 minutes 20 seconds 55 ℃ Replenishment amount per 35mm width 1m length

Next, the composition of the processing liquid will be described. (Color developer) 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 sulphate 2.4 3.6 4- (N-ethyl-N-β-hydroxyethylamino) 4.5 7.2-2-Methylaniline sulphate Add water 1.0 liter 1.0 liter pH 10.05 10.10

(Bleach) Mother liquor (g) Replenisher (g) 1,3-Propylenediaminetetraacetic acid Ferric Ammonium 144.0 206.0 Mu monohydrate Ammonium bromide 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 (adjust with ammonia water (27%) 3.0 2.8

(Fixer) 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 Fixer; ammonium thiosulfate aqueous solution (70 wt%) 170.0 ml 240.0 ml or Table 1 Addition of 0.8 mol 1.1 mol water as described in 1.0 liter 1.0 liter pH 6.7 6.7

(Washing liquid) common to mother liquor and replenishing liquid Tap water was mixed with H type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type anion exchange resin (Amberlite IR-400). Water was passed through the packed mixed-bed column to adjust the concentration of calcium and magnesium ions to 3 mg / liter or less, and subsequently, 20 mg / liter of sodium isocyanurate dichloride and 0.15 g / liter of sodium sulfate were added. The pH of this liquid was in the range of 6.5-7.5.

(Stabilizer) Mother liquor (g) Replenisher (g) Formalin (37%) 2.0 ml 3.0 ml Polyoxyethylene-p-monononylphenyl ether 0.3 0.45 ter ((average degree of polymerization 10) disodium ethylenediaminetetraacetate After addition of salt 0.05 0.08 water and 1.0 liter 1.0 liter pH 5.0-8.0 5.0-8.0 After the running process was completed, the same sample as the sample for running process was used and the fixing time was shortened to 2 minutes and 3 minutes. The amount of silver remaining in the unexposed area of the sample after this treatment was measured using a fluorescent X-ray analyzer, and the presence or absence of precipitation in the fixing bath and the washing bath (1) was visually examined.
The results are shown in Table 1.

[0118]

[Table 1]

From Table 1, when the compound of the present invention is used,
It was found that precipitation was not generated even during the running process, the liquid stability was good, and desilvering was possible with a fixing time of 3 minutes, which is clearly superior to thiosulfate.
This effect is particularly remarkable when the replenishment rate is low.

Example 2 The compound-1 of Example 1 was replaced with the compounds 2, 3, 9, 12, and 1.
The same test as in Example 1 was performed by substituting 3, 14, 20, 23, 25, 26, or 32, respectively. As a result, as in Example 1, the fixing ability was high, and good results were obtained in that precipitation was not generated even during the running process. This effect was particularly remarkable when the replenishment rate was low.

Example 3 On a paper support laminated on both sides with polyethylene, a multi-layer color photographic paper having the following layer constitution was prepared. The coating liquid was prepared as follows. Preparation of first layer coating solution Yellow coupler (exY) 19.1 g and color image stabilizer (cpd-1) 4.4 g and color image stabilizer (cpd-)
7) 0.7 g of ethyl acetate 27.2 cc and solvent (so
lv-1) 8.2 g was added and dissolved, and this solution was added with 10% sodium dodecylbenzene sulfonate 8 cc 10%.
It was emulsified and dispersed in 185 cc of gelatin aqueous solution. On the other hand, a silver chlorobromide emulsion (cubic, 3: 7 mixture of 0.88 μm average particle size and 0.70 μm average particle size (silver molar ratio). Coefficients of variation of particle size distribution are 0.08 and 0.10, (Each emulsion contains 0.2 mol% of silver bromide localized on the grain surface) and the following blue-sensitive sensitizing dye is added to a large-sized emulsion in an amount of 2.0 × 10 ^-4 mol per mol of silver. In addition, for small-sized emulsions, 2.5 × 10 ⁻⁴ mol of each was added and then sulfur-sensitized. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the following composition. The 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 hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. The following were used as the spectral sensitizing dye for each layer. Blue-sensitive emulsion layer

[0122]

[Chemical 30]

(2.0 × 10 ^-4 mol each for large size emulsion and 2.5 × 10 ^-4 mol each for small size emulsion per mol of silver halide) Green-sensitive emulsion layer

[0124]

[Chemical 31]

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

[0126]

[Chemical 32]

(1 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]

[Chemical 33]

(0.9 × 10 ⁻⁴ mol for large size emulsion and 1.1 × 10 ⁻⁴ mol for small size emulsion per mol of silver halide) For red-sensitive emulsion layer The following compounds are silver halide 1
2.6 × 10 ⁻³ mol was added per mol.

[0130]

[Chemical 34]

For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl)-
5-mercaptotetrazole with silver halide 1
8.5 × 10 ⁻⁵ moles, 7.7 × 10 ⁻⁴ moles per mole,
2.5 × 10 ⁻⁴ mol was added. Also, 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]

[Chemical 35]

[0133]

[Chemical 36]

(Layer Structure) The composition of each layer is shown below. Numbers represent coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver. Support Polyethylene laminated paper [Polyethylene on the first layer side contains a white pigment (TiO ₂ ) and a bluish dye (ultraviolet)] First layer (blue sensitive layer) The 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 mixing 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 of particles having an average particle size of 0.55 μm and those having an average particle size of 0.39 μm (Ag molar ratio). Particle size distribution) Coefficient of variation is 0.10 and 0.08, and each emulsion contains 0.8 mol% of AgBr localized on the grain surface.) 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 absorbing layer) Gelatin 1.58 Ultraviolet absorbing agent (uv-1) 0.47 Color mixing inhibitor (cpd-5) 0.05 Solvent (solv-5) 0.24

Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of particles having an average particle size of 0.58 μm and those having an average particle size of 0.45 μm (Ag molar ratio). Grain size distribution) Coefficient of variation was 0.09 and 0.11, and each emulsion contained 0.6 mol% of AgBr locally in 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 (UV absorbing layer) ) Gelatin 0.53 Ultraviolet 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]

[Chemical 37]

[0139]

[Chemical 38]

[0140]

[Chemical Formula 39]

[0141]

[Chemical 40]

[0142]

[Chemical 41]

[0143]

[Chemical 42]

[0144]

[Chemical 43]

[0145]

[Chemical 44]

After exposing the above light-sensitive material, continuous processing (running test) was carried out using a paper processor until the tank capacity for bleach-fixing was doubled in the following processing steps. Ning test). Treatment process Temperature Time Replenishment amount Tank capacity Color development 35 ° C 45 seconds 109 ml 17 liter Bleach fixing 35 ° C 45 seconds 61 ml 17 liters or 30 ml 10 liters Rinse 35 ° C 30 seconds-10 liters Rinse 35 ° C 30 seconds-10 liters Rinse 35 ° C 30 seconds 300 ml 10 liters Dry 80 ° C 60 seconds * Replenishment amount is per 1 m ² of light-sensitive material * For bleach-fix solution, bleach-fix replenisher and rinse solution (12
1 ml) is replenished. * (3 tank countercurrent system from rinse to)

The composition of each processing solution is as follows. Color developer Tank solution Replenisher Water 800ml 800ml Ethylenediamine-N, N, N, N-tetramethylenphosphonic acid 3.0g 3.0g Triethanolamine 5.0g 5.0g Potassium chloride 3.1g-Potassium bromide 0.015g -Potassium carbonate 25g 25g hydrazinodiacetic acid 5.0g 7.0g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0g 9.5g optical brightener (WHITEX-4 manufactured by Sumitomo Chemical Co., Ltd.) 1.0 g 2.5 g Water added 1000 ml 1000 ml pH (potassium hydroxide added) 10.05 10.60

Bleach-fixing solution Tank solution Replenishing solution Replenishing solution Water 600 ml 150 ml 150 ml Ammonium thiosulfate (70 wt%) 100 ml 245 ml 245 ml or the compound of the present invention 0.4 mol 1.0 mol 1.0 mol ammonium sulfite 45 g 105 g 105 g ethylenediamine tetra 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 Water added 1 liter 1 liter 1 liter pH 5.80 5.60 5.40

Rinsing liquid (tank liquid and replenishing liquid are the same) Ion-exchanged water (calcium and magnesium are each 3 ppm or less) After the running treatment, the presence or absence of precipitates in the bleach-fix bath and rinse bath was visually inspected. It can be seen from Table 2 that when the compound of the present invention is used as a fixing agent in place of thiosulfate, no precipitate is formed even during the running process and the solution stability is excellent. Further, this effect is particularly remarkable when the replenishment is low.

[0150]

[Table 2]

Example 4 The compound-1 of Example 3 was converted to the compounds-3, 7, 9, 14, and 2.
Example 3 in place of 0, 26, 29, or 32
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 rate was low.

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 solution of silver nitrate (5 g as silver nitrate) and 0.15 g of potassium iodide were added to a container kept at 60 ° C. with 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 the double jet method. The addition flow rate at this time was accelerated so that the flow rate at the end of the addition was 5 times that at the start of the addition. After the addition was completed, the soluble salts were removed at 35 ° C by the precipitation method, the temperature was raised to 40 ° C, and 75 g of gelatin was added to adjust the pH.
Was adjusted to 6.7. The obtained 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%. Gold,
Chemical sensitization was performed by using sulfur sensitization together.

Preparation of photographic material As a surface protective layer, in addition to gelatin, an average molecular weight of 8,000 was used.
An aqueous gelatin solution containing polyacrylamide, sodium styrene sulfonate, fine particles of polymethylmethacrylate (average particle size 3.0 μm), polyethylene oxide, and a hardening agent 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 an amount of 500.
200 mg / 1 mol of potassium iodide at a ratio of mg / 1 mol Ag
It was added in the proportion of Ag. Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 2,6bis (hydroxyamino) -4-diethylamino-1,3,5-triazine and nitrone as stabilizers, anti-drying fog A photographic material was prepared by adding trimethylolpropane as an agent, a coating aid, and a film hardener to prepare a coating solution, and coating and drying the coating solution on both sides of a polyethylene terephthalate support simultaneously with the surface protective layers. The coated silver amount of this photographic material is 2 g / m ² per side. The swelling rate according to the above definition was 180%.

This photosensitive material was exposed to 50% of X-rays, and then processed with the following developing solution, fixing solution and washing solution. Processing process Processing time Processing temperature Compensation amount Tank capacity Development 13.7 seconds 35 ℃ 20ml (+ diluent 10ml) 15 liter Fixing 12.5 seconds 32 ℃ 10ml (+ diluent 30ml) 15 liter 5ml (+ dilution) Liquid 15 ml) Washing with water 6.2 seconds 20 ° C 500 ml 10 liter Squeeze roller washing tank 200 ml * Replenishment amount: Amount per sheet of photosensitive material (10 inches x 12 inches)

(Developer) Mother liquor (g) Replenisher (g) Potassium hydroxide 24 60 Sodium sulfite 40 100 Potassium sulfite 50 125 Diethylenetriaminepentaacetic acid 2.4 6 Boric acid 10 25 Hydroquinone 35 87.5 Diethylin glycol 11. 2 28 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 2.5 6.25 5-methylbenzotriazole 0.06 0.15 pH 10.05 11.00

(Fixer) or fixer Mother liquor (g) Replenisher (g) Replenisher (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 liquid) Mother liquor (g) Replenishing liquid (g) Ethylenediaminetetraacetic acid disodium salt 0.5 0.5 Dihydrate 50 sheets in quarter size (Development rate of 1 film is 40
%) Running treatment was continued until the cumulative replenishment amount of the fixer became 3 times the mother liquor tank capacity.

When the photosensitive material was developed, the circulating stirring liquid amount of the developing solution was set to 20 liters / minute, and when it was not developed, it was set to 6 liters / minute. After the running process was completed, the same sample as the running process sample was used and the fixing time was shortened to 10.5 seconds and 11.5, and the process was performed. Then, the amount of residual silver in the unexposed portion of the sample after this treatment was measured using a fluorescent X-ray analyzer. Also, the presence or absence of precipitation in the fixing bath was visually examined. The results are shown in Table 3.

[0159]

[Table 3]

From Table 3, when the compound of the present invention is used,
It was found that precipitation was not generated even during the running process, the liquid stability was good, and desilvering was possible with a fixing time of 11.5 seconds, which is clearly superior to thiosulfate. This effect is particularly remarkable when the replenishment rate is low.

Example 6 The compound-1 of Example 5 was converted to the compounds-3, 5, 10, 12,
The same test as in Example 5 was conducted by substituting 14, 19, 26, or 32 for each. As a result, as in the case of Example 5, good results were obtained in that the fixing ability was high and no precipitate was formed during the running process. Further, this effect is particularly remarkable when the replenishing amount is low.

Example 7 (Preparation of Photosensitive Emulsion) 4 × 10 ⁻⁷ mol of iridium (III) chloride per mol of silver was added to a gelatin aqueous 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 and potassium bromide were added simultaneously for 60 minutes, and the pAg was maintained at 7.8 during that period to obtain an average grain size of 0.28μ and an average silver iodide content of A cubic monodisperse emulsion having an amount of 0.3 mol% was prepared. This emulsion was desalted by the flocculation method and then 4 mol per mol of silver.
After adding 0 g of inactive gelatin, the temperature was kept at 50 ° C., and 5,5′-dichloro-9-ethyl-3,3′-bis (3-sulfopropyl) oxacarbocyanine was used as a sensitizing dye.
It was added to a KI solution of 10 ⁻³ mol per mol of silver, and the temperature was lowered for 15 minutes. (Coating of Photosensitive Emulsion Layer) This emulsion was redissolved and the following hydrazine derivative was added at 40 ° C.

[0163]

[Chemical 45]

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

[0165]

[Chemical 46]

(Coating of protective layer) On this, as a protective layer,
Gelatin 1.5 g / m ² , polymethylmethacrylate particles (average particle size 2.5 μ) 0.3 g / m ² , AgCl fine particles (0.08 μ) so that the Ag amount becomes 0.3 g / m ² .
The following surfactants were used for coating.

[0167]

[Chemical 47]

These samples were prepared in a large size (50.8 cm ×
61.0 cm) and cut with 3200 ° K tungsten light to 5
After 0% blackening exposure, 200 sheets were processed according to the following processing recipe. Processing process Processing time Processing temperature Replenishment amount Image 30 seconds 34 ° C 240ml Fixing 30 seconds 34 ° C 390ml 250ml Water wash 30 seconds 20 ° C 2 liters Replenishment amount is shown as amount per 1 m ² of photosensitive material ..

(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 ethylenediaminetetraacetic acid disodium 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 6-dimethylamino-1- Hexanol 4.0 g Sodium p-toluenesulfonate 15.0 g 5-Sulfosalicylic acid 30.0 g Water is added to 1 liter, potassium hydroxide is added to adjust to pH 11.7.

(Fixer) Mother liquor = replenisher Ammonium thiosulfate 190.0 g or compound of the present invention 1 mol Sodium sulfite 22.0 g Ethylenediaminetetraacetic acid disodium 0.1 g Tartaric acid 3.0 g Ammonia water (27%) 10.0 g Acetic acid (90%) 30.0 g Aluminum sulphate (27%) 35.0 g Add water to 1 liter, add sodium hydroxide to adjust to pH 4.8

The presence or absence of precipitates in the fixer after this series of continuous treatments was visually inspected. Further, the amount of residual silver in the unexposed portion of the treated sample immediately before the end of the series of treatments was examined by a fluorescent X-ray analyzer. From Table 4, it can be seen that when the compound of the present invention is used, the fixing ability is excellent, and even when a large amount of treatment is performed, precipitation is not generated and the liquid stability is excellent. Further, this effect is remarkable especially when the replenishment is low.

[0172]

[Table 4]

Example 8 Compound-1 of Example 7 was converted to compound 9, 13, 20 or 2
A test similar to that in Example 7 was performed in place of each of No. 5 and No. 5.
As a result, as in the case of Example 7, good results were obtained in that the fixing ability was high and no precipitation was generated during the running treatment. This effect was particularly remarkable when the supplementation was low.

Example 9 Silver halide grains were precipitated by the double jet method,
After physical ripening and desalting, it is chemically ripened and then silver chloroiodobromide (bromine content 30 mol%, iodine content 0.1 mol%)
An emulsion was obtained. The silver halide grains contained in this emulsion had an average diameter of 0.3 micron. 0.6 mol of silver halide was contained in 1 kg of this emulsion. 1 of this emulsion
Weigh each kg, dissolve by heating at 40 ℃, and then sensitize the following dyes ^{* 1}
70 ml of a 0.05 wt% methanol solution was added, and a predetermined amount of an aqueous solution of sodium bromide was further added. Next, 25 ml of 1.0 wt% methanol solution of the following dye ^{* 2}
In addition, 30 ml of 1.0 wt% aqueous solution of 1-hydroxy-3,5-dichlorotriazine sodium salt was further added, and 40 ml of 1.0 wt% aqueous solution of dodecylbenzenesulfonic acid sodium salt was further added and stirred. 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 subjected to 50% blackening exposure using a sensitometer having a light source with a color temperature of 2666 ° K.

[0175]

[Chemical 48]

Then, according to the following processing recipe, running processing was carried out until the cumulative replenishing amount of the fixing solution became three times the capacity of the mother liquor tank. Processing process Processing time Processing temperature Replenishment amount Tank capacity Image 20 seconds 38 ° C 320ml 18 liters Settling 20 seconds 38 ° C 320ml 18 liters 220ml Water wash 20 seconds 20 ° C 2 liters 18 liters * Replenishment amount: 1m Amount per ²

(Developer) Mother liquor = replenisher Metol 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 liter with addition of 0.5 g water

(Fixer) Mother liquor = Replenisher Ammonium thiosulfate 200 ml or 1 mol of sodium bisulfite 12.0 g Disodium ethylenediaminetetraacetate 0.1 g Tartaric acid 3.0 g Ammonia water (27%) 7. 0 g acetic acid (90%) 20.0 g aluminum sulphate (27%) 35.0 g Add water to 1 liter, add sodium hydroxide to fix solution at pH 4.2 and fix solution at pH 4.0 It was The presence or absence of precipitates in the fixer after the running treatment was visually inspected. Furthermore, the amount of residual silver in the unexposed portion of the treated sample immediately before the end of the running treatment 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 is used, the fixing ability is high and the liquid stability is excellent in that precipitation does not occur even when a large amount of treatment is carried out. Further, this effect is noticeable at a low replenishing amount.

Claims (3)

[Claims] 1. A bath having a fixing ability in a processing method in which a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support is exposed and then subjected to a development treatment is substantially thiosulfate ion-containing. Not included, and the following general formula
A method for processing a silver halide photographic light-sensitive material, comprising at least one compound represented by (I) as a fixing agent. General formula (I) (In the formula, Q represents a group of atoms necessary for forming a 5- or 6-membered heterocycle. This heterocycle may be condensed with a carbon aromatic ring or a heteroaromatic ring. R is a carboxylic acid or It represents 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 or an ammonium group. Represents an integer of 1 to 3, and M represents a cationic group.) 2. A fixing composition for photographic use, which is substantially free of thiosulfate ion and contains at least one compound represented by the general formula (I). 3. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the compound of the general formula (I) is represented by the following general formula (II). General formula (II) (In the formula, M and R have the same meanings as those in the general formula (I). T and U represent C—R ′ 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 carbonamido group, a sulfonamide group, a ureido group, a thioureido group or R. However, R'is R
When representing, it may be the same as or different from R in the general formula (I). )