JPH01206340A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To promote the desilverization of the sensitive material by incorporating the ferric complex salt of at least one kind of a chelating agent selected from specified, chelating agent groups and at least one kind of specified compds. in a bleaching solution. CONSTITUTION:The ferric complex salt of at least one kind of the chelating agent selected from the specified chelating agent groups and at least one kind of the compds. shown by formulas I-III, are incorporated in the bleaching solution. In formulas I and II, M is hydrogen atom, alkaline metal atom, ammonium or a group shown by formula IV. In formula IV, X<1>, X<2> and X<3> are each hydrogen atom or alkyl group, and R and R<1> are each alkyl, alkylene, aryl or a heterocyclic ring group. In formula III, A is (n) valent aliphatic bonding group or an aromatic bonding group, X is -O- or -S- atom, R<1> and R<2> are each a lower alkyl group which may be substituted, R<3> and R<4> are each a lower alkyl group, groups R<1> and R<2>, R<1> and A, R<1> and R<3>, R<2> and A or R<2> and R<3> together with each other may form a ring. And, Y is an anion, (l) is 0 or 1, (m) is 0 or 1, (n) is 1, 2 or 3, (p) is 0 or 1, (q) is 0, 1, 2 or 3. They are selected so as to be electrically neutralized. Thus, the rapid desilverization of the sensitive material can be effected.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to exposed silver halide color photographic material F4.
Developing, bleaching, and fixing (hereinafter referred to as color imaginative material),
This invention relates to a development processing method (hereinafter simply referred to as "processing"), in particular, an improvement that accelerates the bleaching action, shortens the processing time, and performs sufficient bleaching to form color photographic images of good quality. The present invention relates to a development processing method. (Prior Art) Generally, the basic steps in processing color photonic materials are a color development step and a desilvering step. That is, the exposed silver halide color photographic material is subjected to a color development process. Here, silver halide is reduced by a color developing agent to produce silver, and the oxidized color developing agent reacts with a color former to provide a dye image. Afterwards, the color photographic material is subjected to a desilvering process. Here, the particles generated in the previous process are oxidized by the action of an oxidizing agent (commonly called a bleaching agent), and then dissolved and removed by a complexing agent of ionized particles, commonly called a fixing agent. Therefore, only a dye image is produced in the photographic material that has gone through the process of Koit et al. In addition to the two basic steps of color development and desilvering mentioned above, the actual development process includes auxiliary steps to maintain the photographic and physical quality of the image, or to improve the storage stability of the image. Contains. For example, a hardening bath to prevent excessive softening of the photosensitive layer during processing, a stopping bath to effectively stop the development reaction, an image stabilizing bath to stabilize the image, or a stripping bath to remove the backing layer of the support. Examples include membrane baths. In addition, the desilvering process described above is carried out in two steps, with the bleaching bath and fixing bath being separate baths, and in other cases, the processing process is simplified and the bleaching agent and fixing agent coexist for the purpose of speeding up processing and saving labor. In some cases, it is carried out in one step using a bleach-fixing bath. In recent years, from the viewpoint of rapid processing and prevention of environmental pollution in color photographic materials, ferric ion complex salts (e.g., ferric ion complex salts of aminopolycarboxylic acids, etc.), especially ethylenediaminetetra Iron acetate (I[[)
Bleaching treatment methods based on complex salts are mainly used. However, since ferric ion salt has a relatively small oxidizing power and a bleaching blade is insufficient, products using it as a bleaching agent are, for example, dyes with low halogenation limits mainly based on silver chlorobromide emulsions. When bleaching or bleach-fixing photographic materials, it is possible to achieve the desired purpose, but high-sensitivity, color-sensitized, and When processing 2-halogenated color photographic materials, especially 1-shade color reversal materials that use high-silver emulsions, and color negative light-repellent materials for photography, the bleaching effect may be insufficient and desilvering may become defective. However, it has the disadvantage that it takes a long time to bleach. Furthermore, in color photosensitive materials, an enhancing dye is generally used for the purpose of color sensitization. In particular, when using high silver or high aspect ratio tabular grains with the aim of creating a high window, halogenation! I
A problem arises in that the enhancing dye adsorbed on the I surface inhibits the bleaching of the silver produced by /% silver halide development. Persulfates are known as bleaching agents other than the second iii-ion complex salts, and persulfates are usually used as a bleaching solution by adding chloride to the persulfates. However, the disadvantage of bleaching solutions using persulfates is that they have a weaker bleaching edge than ferric ion complexes and take a significantly longer time to bleach. Bleach agents that are not polluting or corrosive to equipment have a weak bleaching blade; therefore, bleaching agents that have a weak bleaching blade, especially bleach solutions using ferric ion complex salts or persulfates, are also used. Schiff was desired to increase the bleaching capacity of bleach-fix solutions. Conventionally, it has been proposed to add various bleaching accelerators to processing baths as a means of increasing the bleaching ability of bleaching solutions or bleach-fixing solutions that use ferric ion complex salts such as ethylenediaminetetraacetic acid iron salts as bleaching agents. For example, various mercapto compounds such as those described in U.S. Pat. Compounds having a disulfide bond, thiazolidine derivatives as described in Japanese Patent Publication No. 53-9854, isothiourea derivatives as described in Japanese Patent Publication No. 53-94927, Japanese Patent Publication No. 45-8506, 49
Thiourea derivatives such as those described in JP-A-26586, JP-A-4! Examples include thioamide compounds as described in J-42349, dithiocarbamates as described in JP-A-55-26506, and the like. Some of these bleach accelerators do have a bleach accelerating effect, but the effect is not necessarily sufficient.
In addition, especially in bleach-fix solutions, they were extremely unstable and lost their effectiveness in a short period of time, so they were not necessarily suitable for practical use. Additionally, other bleach accelerators, such as U.S. Pat.
, 748.136, phenylene-linked ammonium salts as described in Japanese Patent Publication No. 54-12056, U.S. Pat.
These include amine compounds such as those described in No. 552.834. Although these compounds are stable in bleach and bleach-fix solutions, their bleaching accelerating effect is weak, and they are not necessarily sufficient for practical use in bleach-fix solutions using the above-mentioned ferric ethylenediaminetetraacetic acid complex salt as a bleaching agent. A high bleaching rate cannot be obtained. Also, Research Disclosure 24023 (1984
(April 2013), JP-A-60-230653, JP-A No. 62-22
No. 2252 describes a treatment method in which two or more kinds of ferric aminopolycarboxylic acid complex salts are used in combination, but these methods also failed to provide a satisfactory bleaching rate. (Object of the Invention) Therefore, the first object of the present invention is to provide a processing method for quickly desilvering a color photosensitive material. A second object of the present invention is to provide a rapid desilvering method with stable photographic performance. A third object of the present invention is to provide a rapid desilvering method that causes fewer pollution problems. A fourth object of the present invention is to provide an inexpensive, highly practical and rapid desilvering method. (Means for solving the problem) The above objective could be achieved by the method described below. That is, in a method in which an imagewise exposed silver halide color photographic light-sensitive material is color-developed and then treated with a bleaching solution, the bleaching solution contains a ferric complex salt of at least one chelating agent selected from the following chelating agent group; The following general formula (
This was achieved by containing at least one compound selected from A), (B), and (C). Chelating agent general formula (A) R-3M general formula (B) R-3・S-R' In the formula, M is a hydrogen atom, an alkali metal atom, or ammonium, where X
I, Xz, and XI may be the same or different, and each represents a hydrogen atom or an alkyl group. The alkyl group preferably has 1 to 3 carbon atoms. Also, R
and R' represent an alkyl group, an alkylene group, an aryl group, or a heterocyclic residue, which may be the same or different, and the alkyl group preferably has 1 to 5 carbon atoms, most preferably 1 to 3 carbon atoms. . The alkylene group preferably has 2 to 5 carbon atoms. Examples of the ring group include phenyl group and naphthyl group, with phenyl group being particularly preferred.Heterocyclic residues include nitrogen-containing six-membered rings such as pyridine and triazine, azole, pyrazole,
Nitrogen-containing 5-membered rings such as triazole and thiadiazole are preferred, and particularly preferred are cases in which two or more of the ring-forming atoms are nitrogen atoms. The above-mentioned X', It may be substituted with a substituent such as a sulfonamide group. Among the -S formulas (A) and (B), preferred ones are represented by general 2N) to (■).General formula (1) In the formula, R+ and Rz may be the same or different, and each represents a hydrogen atom, a substituted or unsubstituted lower alkyl group (preferably 1 to 5 carbon atoms, particularly preferably a methyl group, an ethyl group, or a propyl group) or an acyl group ( preferably has 1 to 3 carbon atoms, such as an acetyl group or a propionyl group, and n is 1.
It is an integer of ~3. R9 and R2 may be linked to each other to form a ring. R,,R, are particularly preferably substituted or unsubstituted lower alkyl groups. Here, examples of the substituent that R+ and Rz have include a hydroxyl group, a carboxyl group, a sulfo group, and an amino group. General Formula (II) In the formula, R,, R, have the same meanings as R1 and RZ in General Formula (1). n is an integer from 1 to 3. R3 and R4 may be linked to each other to form a ring. As Rs and Ra, substituted or unsubstituted lower alkyl groups are particularly preferred. Here, examples of the substituent that R'l and R4 have include a hydroxyl group, a carboxyl group, a sulfo group, and an amino group. General formula (I [I) -N General formula (IV) N = N General formula (V) N = N In the formula, R3 is a hydrogen atom, a halogen atom (e.g., a chlorine atom, a bromine atom, etc.), an amino group, a substituted or an unsubstituted lower alkyl group (preferably 1 to 5 carbon atoms, particularly preferably a methyl group, ethyl group, or propyl group), an amino group containing an alkyl group (methylamine group, ethylamino group, dimethylamino group, diethylamino group) (such as a group). Here, the substituent that R1 has is a hydroxyl group,
Examples include carboxyl group, sulfo group, and amino group. General formula (Vl) In the formula, Ri and Rt may be the same or different, and each represents a hydrogen atom, an alkyl group that may have a substituent (preferably a lower alkyl group, such as a methyl group, an ethyl group, a propyl group) ), a phenyl group that may have a substituent, or a heterocyclic group that may have a substituent (more specifically, it contains at least one heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, etc.) R4 represents a hydrogen atom or a lower alkyl group which may have a substituent; (For example, a methyl group, an ethyl group, etc., preferably having 1 to 3 carbon atoms). Here, examples of the substituent that R1-R1 has include a hydroxyl group, a carboxyl group, a sulfo group, an amino group, and a lower alkyl group. R9 represents a hydrogen atom or a carboxyl group. General formula (■) In the formula, R8 Ro, RI! may be the same or different,
Each represents a hydrogen atom or a lower alkyl group (eg, methyl group, ethyl group, etc., preferably having 1 to 3 carbon atoms). R1° and R11 or Rtz may be linked to each other to form a ring. X is a substituent (for example, a lower alkyl group such as a methyl group,
alkoxyalkyl groups such as acetoxymethyl groups)
represents an amino group, a sulfonic acid group, or a carboxyl group that may have R1° to R1t are particularly preferably a hydrogen atom, a methyl group or an ethyl group, and X is preferably an amino group or a dialkylamino group. Specific examples of compounds represented by formulas (1) to (■) are shown below. (1)-+1+ (1)-+21 (Riichi (3) (I)-(7) (I)-(8J (T) -(J (H)-(1) (II) -(*+ ( If ) −(31 (II) −(4) ([I) −(51 (n) −(5) δH (II) −(7) (III) −(11 −N (III) −<2) − N (I) -(3) -N (III) -(4) (III) -(5) (IV) -(1) -N t1 (IV) -(2) -N (IV)-(3 ) −N (V) −(1) (V ) −(2) H (Vl) −(1) (Vl ) −(2) (■) −(3) (Vl ) −(4) (■) − (5) (■)-(6) (■) -(1) (■)-(2) (■)-(3) (■)-(41 (■)-(5) (■)-(6 ) (W) -(73 (■) -(3) (Vff) -(91 (W) -(1G) (■) -(11) All of the above compounds can be synthesized using known methods, In particular, for compounds of general formula (i), US Pat.
tt,rrByr't+j明aS,G. 3chwarzenbacb at al,,He
1v, Chim. Human eta,,31. //4'7(/F!j), lt. Q., elinton et al., J., Am., C.
hem. Sac,,70. TajOc/Yhiro, r), general formula (
Regarding the compound II), JP-A No. 3-Tayo 430, and the compounds of general formulas (5) and (1'/), JP-A No. 3-V, general formula (V ) compounds are described in Japanese Patent Application Publication No. Shoj/-tl'jtr, J7-70.
No. 743, No. 13-10/62, General formula (Vl)
Regarding the compound, Japanese Patent Publication No. 3-yrzttt,
Regarding the compound of the general formula (■), reference can be made to the specification of JP-A-2003-2003-2-CO/Hiro-err, and JP-A-3-2μ Tako No. 7. General formula (0) Here, human is an n-valent aliphatic linking group, aromatic linking group, or heterocyclic linking group, and (when H=t, human is a mere aliphatic group, aromatic group, or heterocyclic group). ) The aliphatic linker group represented by a human can include an alkylene group having 3 to 11 carbon atoms (eg, trimethylene, hexamethylene, cyclohexylene, etc.). Examples of the aromatic linking group include an aIJ-lene group having 6 carbon atoms/l (eg, phenylene, naphthylene, etc.). Examples of heterocyclic linking groups include heterocyclic groups (e.g., thiophene, furantriazine, pyridine,
piperidine, etc.). Here, the number of aliphatic linking groups, aromatic linking groups, and peterocyclic linking groups is usually one, but two or more are linked.

[Moyo(, The linking form can be direct or covalent linking group (for example, -〇-
1-S-1R-3o2-N-1-1-C〇- or a linking group formed from these linking groups, and R may be linked via a lower alkyl group. Also, this aliphatic i! M! , aromatic linking group, hete I:
The linking group may have a substituent. Examples of the substituent include an alkoxy group, a halogen atom, an alkyl group, a hydroxy group, a carboxy group, a sulfo group, a sulfonamide group, and a sulfamoyl group. X represents 10-1-S-5R, u 4■ N- represents a lower alkyl group (e.g. methyl group, ethyl group, etc.), R and R are substituted or unsubstituted lower alkyl groups,
(For example, methyl group, ethyl group, propyl group, isopropyl group, etc.), and the substituents include:
Hydroxy group, lower alkoxy group (e.g., methoxy group, methoxyethoxy group, hydroxynidoxy group, etc.),
Amino groups (eg, unsubstituted amino group, dimethylamino group, N-hydroxyethyl-N-methylamine group, etc.) are preferred. Here, when there are two or more substituents, they may be the same or different. R3 is the number of carbon atoms/-! lower alkylene group (methylene,
Y represents an anion (halide ion (chloride ion, bromide ion, etc.), nitrate ion, sulfate ion, p-toluenesulfonate, oxalate, etc.). Furthermore, R1 and R2 are carbon atoms or heteroatoms (e.g. eR
element, nitrogen atom, sulfur atom] to form a two-membered or six-membered heterocycle (e.g. pyrrolidine ring, bi-lysine ring, morpholine ring, triazine ring, imidazolidine ring, etc.). good. R (or R2) and human are connected via a carbon atom or a terror atom (e.g. oxygen atom, nitrogen atom, sulfur atom),
! or 6-membered heterocycles (eg, hydroxyquinoline ring, hydroxyindole ring, isoindoline ring, etc.). Furthermore, R'' (or R2) and R3 are carbon atoms or heteroatoms (e.g., oxygen atom, nitrogen atom, sulfur atom)
Connect through and! A is O or 71m is O or 11n is I, co or 3, p is O or l. , and q represents O%l, co, or 3. Specific compounds included in the present invention are listed below, but are not limited thereto. C-(/ ) C-1-z)
c-((+) I C-(J) C-(≠) C-(r) CII2N(CH2C)i201-I) 2p) r) Ta) CH3■ CI-(2NCH2CH20H H3 Q-(/to)
C-(/!(-(ty) c-<1t) CH2N(C112CH20CH2C112011). ?) ri) l) Ko-(13) (-(-ψ) H)2 (l-<1riC-C26) The compound of general formula (C) can be synthesized by the generally well-known method described in the following literature. U.S. Patent No. 4,552,834, Special Publication No. 54-12,
No. 056, JP-A-51-192,953 The amount of the compounds of general formulas (A), (B), and (C) used in the present invention to be added to the processing solution depends on the type of photographic material to be processed;
Although it differs depending on the treatment temperature, the time required for the intended treatment, etc., it is appropriate to have 1X10-' to 10-1 mol, preferably 1X10-' to 5X10-'' mol, per 11 of the treatment liquid.Next, the present invention 0 The bleaching agents of the present invention are of the following nine types. +31 1. 2-diaminopropanetetraacetic acid ferric complex salt -(411,2-cyclohexanediaminetetraacetic acid ferric complex salt
Iron complex salt K -+51 Glycol ether diamine tetraacetic acid ferric complex salt K - (61 Iminoniacetic acid ferric complex salt - (7) N-methyliminodiacetic acid ferric complex salt K1
81 1,4-Diaminobutanetetraacetic acid ferric complex salt -(911,5-diaminopentanetetraacetic acid ferric complex salt) These bleaching agents may be used in China, but it is preferable to use two or more of them in combination. In addition to the above bleaching agents, examples of bleaching agents used in combination include ferric ethylenediaminetetraacetic acid, ferric nitrilotriacetate, ferric hydroxyethyliminodiacetic acid, and ferric complex salts of ethylenediaminetetraacetic acid. Among the bleaching agents of the present invention, K-
(11 and K -+21, K -+21 and K
-(41K -(21) and ferric complex salt of ethylenediaminetetraacetic acid, but the combination of K -+21 and K -[4+ is the most preferred. When containing two or more types of bleaching agents, -(1 )
Karani-[91 is preferably at least 40% of the total bleaching agent, particularly preferably from 50 to 90%. In the present invention, the amount of bleach per 11 bleaching solutions is 0.0
5 mol to 1 mol, preferably 0.1 mol to 0.5 mol
It is a mole. Aminopolycarboxylic acid ferric complex salts may be used in the form of complex salts, or may be used in the form of ferric salts, such as ferric sulfate, ferric chloride,
A ferric ion complex salt may be formed in a solution using an aminopolycarboxylic acid with ferric nitrate, ferric ammonium sulfate, ferric phosphate, or the like. When used in the form of complex salts,
One type of complex salt may be used, or two or more types of complex salts may be used. On the other hand, when forming a complex salt in a solution using a ferric salt and an aminopolycarboxylic acid, the ferric salt is
fl type or two or more types may be used. Furthermore, one type or two or more types of aminopolycarboxylic acids may be used. In any case, it is preferable to use the aminopolycarboxylic acid in excess of the amount required to form the ferric ion complex. Aminopolycarboxylic acids and their ferric complex salts are usually preferably used in the form of alkali metal salts or ammonium salts, and ammonium salts are particularly preferred from the viewpoint of solubility. Further, the bleach solution or bleach-fix solution containing the above-mentioned ferric ion complex may contain a metal ion complex salt other than iron, such as cobalt or copper. These bleach accelerators can also be used by being added to the pre-bath of the processing solution having bleaching ability of the present invention. In addition to the bleaching agent and the above-mentioned compounds, the bleaching solution constituting the present invention includes bromides such as potassium bromide, sodium bromide,
Rehalogenating agents such as ammonium bromide or chlorides such as potassium chloride, sodium chloride, ammonium chloride can be included. The concentration of the rehalogenating agent is 0.00% per 11 parts of the bleaching solution. 1-5
mol, preferably 0.5 to 3 mol. In addition, nitrates such as sodium nitrate and ammonium nitrate,
One or more inorganic acids having pH slowing ability such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, Additives known to be commonly used in bleaching solutions, such as R acids and their salts, can be added. Furthermore, the processing temperature of the bleaching solution is preferably 35 to 50°C,
38-45°C is more preferable. The amount of bleaching solution to be refilled is 50 to 200 ml per 1 photosensitive material.
1 is preferred, but more preferably 100 to 500 mj! It is. The treatment time of the bleaching step is preferably as short as possible for desilvering, but a particularly preferred time is from 30 seconds to 80 seconds. Further, from the viewpoint of rapid processing, it is preferable to carry out sufficient stirring, and jet stirring as described in JP-A-62-183640 is particularly preferable. Furthermore, in the case of a bleaching solution using a ferric aminopolycarboxylic acid complex salt and the accelerator of the present invention, surface stains may occur on the photosensitive material in the processing solution;
It was found that the problem could be completely prevented by adjusting to 4.5. Therefore, the preferred pH of the bleaching solution in the present invention is 3.
-5.3, particularly preferably pH 3.5-4.5. In this pH range, the desilvering property is also the best. Following the bleaching step of the present invention, a treatment is generally performed with a treatment liquid having fixing ability. In addition to the fixing solution, examples of the processing solution having fixing ability include a bleach-fixing solution as described in JP-A-61-75352. In the present invention, the amount of bleach per 11 bleach-fix solutions is 0.
05 mole to 0.5 mole, preferably 0.1 mole to
It is 0.4 mol. The bleach-fix solution also contains fixing agents such as thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, and potassium thiosulfate, thiocyanates such as sodium thiocyanate, ammonium thiocyanate, and potassium thiocyanate, and thiourea. , thioether, etc. can be used. The amount of these fixing agents is 0.3 mol to 3 mol, preferably 0.5 mol per 11 bleach-fixing solutions.
mol to 2 mol. In addition to the above-mentioned bleaching agent and fixing agent, the bleach-fixing solution may contain compounds contained in the bleaching solution. The bleach-fix solution contains sulfites as preservatives, such as sodium sulfite, potassium sulfite, ammonium sulfite, and bisulfite adducts of hydroxylamine, hydrazine, aldehyde compounds, such as acetaldehyde sodium bisulfite, p-toluenesulfinic acid. Sulfinic acid compounds such as sodium can be contained. Furthermore, various fluorescent brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol, etc. can be contained. The pH of the bleach-fix solution is 4.0 to 9.0, preferably 5.0.
~8.0, more preferably 6.0~7°5. Further, the preferred temperature range for the bleach-fix solution is the same as that for the bleach solution. The replenishment amount of bleach-fixing solution is 300 per d of photosensitive material.
3000mj from mj+! is preferred, more preferably 300 mI to 1000 mI! It is. In the processing method of the present invention, the fixing solution can contain all the compounds contained in the bleach-fixing solution. The pH of the fixer is 3.0 to 9.0, preferably 5.0 to 8.
．． 0, the processing time is preferably 20 seconds to 10 minutes, and 30 seconds to
4 minutes is more preferred, and the preferred concentration and temperature of the fixing agent included are the same as those for the bleach-fix solution. It is preferable to add 0.01 mol/1 or more of a chelating agent whose stability constant for iron(III> is equal to or higher than that of ethylenediaminetetraacetic acid) to the bleach-fixing solution or the fixing solution. , 1-hydroxyethylidene-1゜l-diphosphonic acid, N, N, N
',N'-ethylenediaminetetramethylenephosphonic acid) is preferred. When a bleaching, bleach-fixing or fixing step is immediately followed by a washing or stabilizing step, it is preferred to introduce some or all of these overflow liquids into the bleaching, bleach-fixing, fixing, etc. processing solution. The present invention is effective in any treatment that combines a bleach bath, bleach-fix bath, fix bath, etc. as a desilvering step. Examples of the desilvering process include the following:
It is not limited to these. Magnetism 1 Bleach constant magnetization 2 Bleach-Water wash constant fixation-3 Bleach-bleach fixing inhibition 4 As the bleaching-bleach fixing constant attachment desilvering process, the above-mentioned inhibition 1 and 3 are most preferable. Further, although the desilvering step is usually carried out after the developing step, a bath for water washing, rinsing, bleaching acceleration, etc. may be provided between these steps. Further, in each step, a forward flow or self-flow multistage treatment method is preferred, and a two-stage or three-stage countercurrent treatment method is particularly preferred. The color developer used in the present invention contains a known aromatic primary amine color developing agent. Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto. D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N-ethyl- N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-'t N-ethyl-N-(β-
hydroxyethyl)amino]aniline D-64-amino-3-methyl-N-ethyl-N-(β
-(methanesulfonamide)ethyltwoaniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p-phenylenediamine D-94-amino-3-methyl-N -ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-ethoxyetheraniline D-114-amino-3-methyl-N-ethyl-N-β
-Butoxyetheraniline Among the above p-fluorinated diamine derivatives, Exemplified Compound D-5 is particularly preferred. In addition, these p-phenylene diamine gm forms may be salts such as sulfate, hydrochloride, gnitite, p-)luenesulfonate, etc. of the aromatic-grade amine developing agent. The amount used is preferably about 0.1 g to about 20 g per developer IIl.
1 and more preferably from about 0.5 g to about Log. In addition, sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts may be added as preservatives to the color developer as necessary. can do. However, in order to improve the color development properties of the color developer, it is preferable that the sulfite ion is substantially not contained. Here, "substantially not contained" means 0.00% in terms of sodium sulfite per 12 of the color developer. It should not contain more than 5 g/l, preferably less than 0.2 g/E, more preferably not at all. In addition, as a compound that directly preserves the color developing agent, various hydroxylamines, Tokuma Sho 6L-18655, etc.
Hydroxamic acids described in No. 9, hydrazines and hydrazides described in No. 61-170756, and hydrazides described in No. 61-188
Phenols described in No. 742 and No. 61-203253, α-hydroxyketones and aminoketones described in No. 61-188741, and/or No. 61-48
It is preferable to add various saccharides described in No. 0616, and when used in combination with the above compounds, Japanese Patent Application No. 61-147823, No. 61-166674, No. 61-165621,
Monoamines described in No. 61-164515, No. 61-170789, No. 61-168159, etc., No. 61-173595, No. 61-164515, No. 6
Diamines described in No. 1-186560, etc., No. 61-1
No. 65621 and polyamines described in No. 61-169789, polyamisos described in No. 61-188619, nitroxy radicals described in No. 61-197760, alcohols described in No. 61-186561 and No. 61-197419. It is preferable to use the oximes described in No. 61-198987, and the tertiary amines described in No. 61-26/5149. Other preservatives include BM4 of various degrees as described in JP-A-57-44148 and JP-A-57-53749, JP-A-59
- Salicylic acids described in No. 180588, JP-A-54-3
Alkanolamines described in No. 532, JP-A-56-9
Polyethyleneimines described in No. 4349, U.S. Patent No. 3
．． The aromatic polyhydroxy compound described in No. 746,544 may be included if necessary, and addition of an aromatic polyhydroxy compound is particularly preferred. The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11. The color developer may contain other known developer component compounds. In order to maintain the above pH, it is preferable to use various 121m agents. Specific examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium tetraborate (borax), potassium tetraborate, O-
Sodium hydroxybenzoate (sodium salicylate), potassium O-hydroxybenzoate, 5-sulfo-2
-sodium hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds. The amount of the buffer added to the color developer is 0.1 mol/1
It is preferably at least 0.1 mol/j! ~0
．． Particularly preferred is 4 mol/l. In addition, various chelating agents can be used in the color developer as an anti-settling agent for calcium or magnesium or to improve the stability of the color developer. As the chelating agent, organic acid compounds are preferred, such as aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids. Specific examples are shown below, but the invention is not limited to these. Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-)rimethylenephosphonic acid, ethylenediamine-N,N,N'N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, -'1. 2-diaminopropane tetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid,
2-phosphonobutane-1,2,4-)licarboxylic acid, 1
-hydroxyethylidene-1,1-diphosphonic acid, N,
N'-bis(2-hydroxybenzyl)ethylenecyamine-N,N''-diacetic acid Two or more of these chelating agents may be used in combination as necessary. The amount of these chelating agents added depends on the color developer. It is sufficient as long as the amount is sufficient to sequester the metal ions inside.6 For example, l
j! It is about 0.1g to Log per unit. Any development accelerator can be added to the color developer if necessary. However, it is preferable that the color developer of the present invention does not actually contain benzyl alcohol in terms of pollution, liquid preparation properties, and color stain prevention.
, where "substantially" means developer 1j! This means that it contains less than or equal to 2, preferably none at all. As the low development accelerator, Japanese Patent Publications Nos. 37-16088 and 37-598? No. 3B-7826, No. 44-
No. 12380, No. 45-9019 and U.S. Patent No. 3.
813,241 etc., JP-A-52-49829 and JP-A-52-15554
p-phinidine diamine compounds represented by the following Nos., JP-A No. 50-137726, JP-B No. 44-30074,
Quaternary ammonium salts disclosed in JP-A-56-156826 and JP-A-52-43429, etc., U.S. Patent No. 2
, No. 494,903, No. 3,128゜182, No. 4,
No. 230.796, No. 3,253.919, Special Publication No. 4
No. 1-11431, U.S.'ff Grant No. 2,482,546
No. 2,596,926 and No. 3,582.346
Amine compounds described in Japanese Patent Publication No. 37-16088
No. 42-25201, US C1#ff! 3,128
, No. 183, Special Publication No. 41-11431, No. 42-23
Polyalkylene oxides such as those disclosed in No. 883 and US Pat. No. 3,532.501, other l-phenyl-3-pyrazolidones, imidazoles, and the like may be added as necessary. In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of antifoggants include benzotriazole, 6-nidropenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole. Representative examples include nitrogen-containing heterocyclic compounds such as , 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine. The color developer used in the present invention may contain a fluorescent brightener.As the optical brightener, 4゜4'-diamino-2,2゛-disulfostilbene compounds are preferred. , the amount added is θ~5g/2, preferably 0.1g~4g
/2. Further, various surfactants such as alkylsulfonic acid, ary-phosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added as necessary. The processing temperature of the color developer of the present invention is 20-50°C, preferably 30-45°C. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes. The replenishment amount is preferably small, but is 100 to 1500 d - preferably 100 to 800 d - per photosensitive material, more preferably 100 d.
~400. In Z, the color developing bath may be divided into two or more baths as necessary, and the color developing replenisher may be replenished from the first bath or the last bath, thereby shortening the developing time and reducing the amount of replenishment. . The processing method of the present invention can also be used for color reversal processing.
A so-called black-and-white first developer used in the reversal processing of color photographic light-sensitive materials, or a developer used in the processing of black-and-white bright light-sensitive materials can be used. In addition, various well-known additives that are generally added to black and white developers can be included. Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, preservatives such as sulfites, and alkali compounds such as sodium hydroxide, sodium carbonate and potassium carbonate. Accelerators, consisting of potassium bromide, inorganic or organic inhibitors such as 2-methylbenzimidazole and methylbenzthiazole, water softeners such as polyphosphates, trace amounts of iodides and mercapto compounds. Examples include development inhibitors. The processing method of the present invention comprises processing steps such as color development, bleaching, and bleach-fixing as described above. Here, after the bleach-fixing process, it is common practice to perform treatment processes such as water washing and stabilization, but after the bleach-fixing process, the stabilization process is performed without actually washing with water for one time. It is also possible to use convenient processing methods. The rinsing water used in the rinsing process may contain known additives as necessary.9 For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid;
It is possible to use disinfectants and fungicides to prevent the growth of various bacteria and algae (e.g., isothiazolone, chlorine-based seedlings, benzotriazole, etc.), and surfactants to prevent dryness and unevenness. can. Or L, E
. 'r4esL,'Water Quality C
r1terta'+ Phot, Sci, and
Eng,, vol, 9. Na6+page344~3
59 (1965) and the like can also be used. As the stabilizing solution used in the stabilization step, a processing solution that stabilizes the dye image is used.
l Ability-enhancing liquids, aldehydes (for example, hol, marine)
A liquid containing , etc. can be used. The stabilizing liquid includes
Ammonium compound, Bl, Aj! if necessary. Metal compounds such as, fluorescent brighteners, chelating agents (for example, 1-hydroxyethylidene-1,1-diphosphonic acid), bactericides, fungicides, hardeners, surfactants, and the like can be used. In addition, the water washing step and the stabilization step are preferably performed using a multi-stage countercurrent method, and the number of stages is preferably 2 to 4. The replenishment amount is 1 to 50 times the amount brought in from the previous bath per unit area, preferably 2 to 30 times. times, more preferably 2 to 15 times. The water used in these washing steps or stabilization steps includes tap water, as well as Ca
It is preferable to use water that has been deionized to have a Mg concentration of 6 degrees/i or less, or that has been sterilized using halogen, an ultraviolet germicidal lamp, or the like. In each of the above processing steps for photosensitive materials, when continuous processing is performed using an automatic processor, concentration of the processing solution due to evaporation may occur, especially when the processing amount is small or the opening area of the processing solution is large. becomes. In order to correct such concentration of the processing liquid, it is preferable to replenish an appropriate amount of water or correction liquid. The present invention can be applied to various color photosensitive materials. Color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper,
Typical examples include direct positive color photosensitive materials. The effects of the present invention are particularly remarkable in photosensitive materials with a large amount of coated silver, and are preferably used in the case of color negative films and color reversal films.The preferred amount of coated silver is lr+?
3 g to 15 g, preferably 4 g to 10 g. The preferred halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, which contains about 30 mol% or less of silver iodide. be. Particularly preferred is silver iodobromide containing from about 2 mole percent to about 25 mole percent silver iodide. Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof. The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns (and may be a polydisperse emulsion or a monodisperse emulsion. Used in the present invention) Silver halide photographic emulsions that can be produced are described, for example, in Research Disclosure (RD), No. 17643.
(December 1978), pp. 22-23~"1. Emulsion preparation ([!mulsian preparation an
dtypes)”, and the same 18716 (197
November 9), 648 pages, graphic ``Physics and Chemistry of Photography'', published by Paul Montell (p. 16fktdas)
. Chamic et Ph1sique Photog
raphique paul montel+1967
), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F. Duffin, Photograph
icB+1ulsion Chemistry (Fo
cal Pr5ss+ 1966) ). “Production and Coating of Photographic Emulsions” by Zellikman et al., published by Focal Press (V, L, Zellk++ an at a
l、Makingand Coating Pho
tographic E+5ulsion+F
ocal Press. 1.964), etc. U.S. Patent Nos. 3,574,628 and 3,655.39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413.748 are also preferred. Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described in Cutoff, Photographic Science and Engineering.
ence and Engineering),
No. 14@, pp. 248-257 (1970); U.S. Patent No. 4.434゜226, No. 4,414,310
No. 4,433,048, No. 4,439.520 and British Patent No. 2,112.157. It can be made by A. The crystal structure may be --like, the inside and outside may have different halogen compositions, it may have a stone-like structure, or silver halides of different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as rotane silver or lead oxide. Mixtures of particles in different crystalline forms may also be used. The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are Research Disclosure Sou 17
643 and the same 18716, 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 Research Disclosures, and the relevant descriptions are shown in the table below. Additive type R1) 17643 RD1871
61 Chemical sensitizers page 23 Page 648 right column 2RF5 degree increase agent Same as above 4 Brightening agent page 24 Ultraviolet absorber 8 Dye image stabilizer page 25 9 Hardener page 26 page 651 left column 10
Binder Page 26 Same as above 11 Plasticizer, lubricant Page 27 Page 650 Anti-degradation agent Various color couplers can be used in the present invention, and specific examples thereof can be found in the above-mentioned Research Disclosure (
RD) 17643, ■-C-G. As a yellow coupler, for example, U.S. Patent Tube 3.93
3.501, 4.022.620, 4.3
No. 26.024, No. 4,401゜752, Special Publication No. 5
No. 8-10739, British patent cylinder 1.425. ．． 020, No. 1.476.760, etc. are preferred. As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat. FL
o, 619, 4.351897, European Patent No. 73.636, US Pat. No. 3,061,432, 3. 725. No. 067, Research Disclosure N124220 (June 1984), Japanese Patent Publication No. 1986
-33552, Research Disclosure m24
230 (June 1984), JP-A-60-43659, U.S. Patent No. 4.500,630, U.S. Patent No. 4.540.
Particularly preferred are those described in No. 654 and the like. Cyan couplers include phenolic and naphthol couplers, and are disclosed in U.S. Pat. No. 4,052,212.
No. 4,146,396, No. 4,228.23
No. 3, No. 4.296.200, No. 2.369.9
No. 29, No. 2,801.171, No. 2.772.
No. 162, No. 2.895,825, No. 3,772
．． No. 002, No. 3.758, 308, No. 4.33
4.011, 4.327.173, West German Patent Publication No. 3.329,729, European Patent No. 121.365
A, U.S. Patent No. 3.446.622, U.S. Patent No. 4.33
No. 3,999, No. 4,45L55.9, No. 4,4
27.767, European Patent No. 161.626A, etc. are preferred. Colored couplers to correct unnecessary absorption of coloring dyes are described in Research Disclosure No. 17643.
- Section G, U.S. Patent No. 4,163゜670, Special Publication No. 1983
-39413, U.S. Patent No. 4,004,929, U.S. Patent No. 4.138.258, British Patent No. 1.146.36
The one described in No. 8 is preferred. Couplers that allow coloring dyes to develop appropriate diffusivity include U.S. Patent No. 4.366.237 and British Patent No. 2.125.
．． 570, European Patent No. 96.570 and German Patent Publication No. 3.234.533 are preferred. Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,451,820; o80.211, British Patent No. 4.367.282, British Patent No. 2,102.
It is described in No. 173, etc. Force pullers that release photographically useful residues upon camping can also be preferably used in the present invention. The DIR coupler releasing the development inhibitor is RD17643 as previously described.
, Patents described in sections ■ to F, Japanese Patent Application Laid-Open No. 57-15194
No. 4, No. 57-154234, No. 60-184248
Preferred are those described in US Pat. No. 4,248,962. As a coupler that releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2.097.140;
No. 2,131.188, JP 59-157638
No. 59-170840 is preferred. Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4.130.427, U.S. Pat. , the multi-equivalent coupler described in JP-A No. 4.31.0.618, etc., JP-A-60-185950
, DIR redox compound or DIR coupler releasing coupler or DIR described in JP-A-62-24252 etc.
Coupler-emitting coupler or redox, a coupler releasing a dye which recolors after separation as described in EP 17.3.302A, R,D, Separation 11449, EP 24241
, a bleach accelerator-releasing coupler described in JP-A No. 61-201247, and a ligand-releasing coupler described in US Pat. No. 4,553.477. Specific examples of color couplers that can be used in the present invention are listed below, but the invention is not limited thereto. C1-+2) Cr-+31 CP-(41 CF-(51 Naw I 7-fil Molecular weight approx. 40.000 Cr-+71 cr-(8) Cr-(91 (1+-αQ H 9-H) Cr-Fil H C111□(1) Cp-QJ OH C,l-01 f4 Cr-09 C(-Ql OH1 Or-SCHxCHtCOt)I Cr-Ql OH Cy-α OH C,-CI- Cr-(2) Low Hz \ Hair Cf-(2) OH L Cr-(24) c,-(25) C((26) Cr-(27) Cr(28) OH c,-(29) ゝ(t)CsH++ Cr( 30) c, -(31) Cf-(32) Cr-(33) N=N Cr-(34) H c,-(35) Cr-(36) i1 C3゜L+ Cr(39) I CP-( 40) 11 C11 Cr-(41) H "+?, 4-(44) Cr-(45) I 0 houses-(46) 01 amount ■ C7(47) ■ f C,-(48) H (,- (49) c, -(50) C7--(51). Straw c, -(53) c, -(54) c, -(55) c, -(56) 1°C, I11? c, -(57)Cr-(58)tI+13C/)-(59)rσCr(60) The coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods.Oil-in-water droplet dispersion method Examples of high-boiling point solvents used in the above are described in U.S. Patent No. 2,322.027 etc. Specific examples of high-boiling point organic solvents with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method As, phthalate fL/acid ester 11 (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amyl phenyl)
Phthalate, bis(2,4-di-t-amylphenyl)
isophthalate, bis(1,1-diethylpropyl) phthalate, etc.), esters of phosphoric or phosphonic acids (triphenol phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethyl phosphate, etc.) xyl phosphate, tridodecyl phosphate, triptoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-
p-hydroxybenzoate, etc.), amide [(N, N
-diethyldodecaneamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (stearyl alcohol,
2.4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl)
sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibuty-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin , dodecylbenzene, diisopropylnaphthalene, etc.). Further, 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 typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone,
-Ethoxyethyl acetate, dimethylformamide and the like. Specific examples of the latex dispersion process, effects, and latex for impregnation are disclosed in U.S. Pat. It is described in .230, etc. The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal vapor. Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of N117643, and the right column of page 647 to the left column of page 648 of the same issue 18716. (Example) Examples of the present invention are shown below, but the present invention is not limited thereto. Example-1 On a subbed cellulose triacetate film support,
A multilayer color photosensitive material A consisting of each layer having the composition shown below was prepared. (Composition of photosensitive layer) The coating amount is expressed in g/rd units of solder for silver halide and colloidal silver, and the amount expressed in g/rd units for couplers, additives and gelatin.
The number of moles of the enhancing dye is expressed per mole of silver halide in the same layer. 11th (Prevention of Hellishing N) Black colloid ill 0. 2
Gelatin 1.3ExM-9
0,06 UV-10,03 uv-20,06 UV-30,06 Solv-10,15 SoLv-20,15 Salv-30,05 2nd layer (middle layer) Gelatin 1. 0UV-1
0,03 ExC-40,02 ExF-10,004 Solv'-10,1 Solv-20,1 3rd N (low-sensitivity red-sensitive emulsion N) Silver iodobromide emulsion (Ag [4 mol%, uniform-Agl type , equivalent sphere diameter 0.5μ, coefficient of variation of equivalent sphere diameter 20%, plate-shaped particles, diameter/thickness ratio 3.0) Coating amount 1. 2 Silver iodobromide emulsion (Ag 13 mol%, uniform Agl type, equivalent sphere diameter 0.3 μ, coefficient of variation of equivalent sphere diameter 15%, spherical grains, diameter/thickness ratio 1.0) Amount per coating 0. 6 Gelatin 1.0ExS-1
4X10-'ExS-24X10-' ExC-10,05 ExC-20,50 ExC-30,03 ExC-40,12 ExC-50,01 No. 41W (high-frequency red emulsion layer) Silver iodobromide emulsion ( Ag16 mol%, internal high Agl type with core-shell ratio 1:1, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 15%, plate-shaped particles, diameter/thickness ratio 5.0) Coating amount l O,7 Gelatin 1.0ExS-1
3X10-'ExS=2 2.3XIO-'ExC-
60.11 ExC-70,05 ExC-40,05 Solv-10,05 Solv-30,05 5th N (middle layer) Gelatin 0. 5Cpd-
1-0,1 Solv-10,05 6th layer (low-temperature glaucoma emulsion layer) Silver iodobromide emulsion (Ag14 mol%, surface height Agl type with core-shell ratio 1:1, equivalent sphere diameter 0.5μ, Coefficient of variation of equivalent sphere diameter 15%, plate-shaped particles, diameter/W, ratio 4.0) Coating amount 111 0. 35 Silver iodobromide emulsion (AgI 3 mol%, uniform Agl type, equivalent sphere diameter 0.3 μ, coefficient of variation of equivalent sphere diameter 25%, spherical grains, diameter/thickness ratio 1.0) Coated silver 1 0.20 Gelatin 1.0ExS-3
5X10-'ExS-43X10-'ExS-51xlo-'ExM-8'0.4 ExM-90,07 ExM-100,02 ExY-110,03 Solv-10,3 Solv-40,05 7th N (high sensitivity ) 3 emulsion layer) Silver iodobromide emulsion (Ag 14 mol%, internal high Agl type with core-shell ratio 1:3, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 20%, plate-like grains, diameter/ff , ratio 5.0) Coated silver amount 0. 8 Gelatin 0.5ExS-
35X10-'EχS-43XIO-'ExS-51XIO-' ExM-80,1 ExM-90,02 ExY-110,03 ExC-20,03 ExM-140,01 Solv-10,2 Solv-40,01 8th N (Middle layer) Gelatin 0.5Cpd-1
0.05 Solv-L 0.02 No. 9ji
(Donor layer for interlayer effect on red-sensitive layer) Silver iodobromide emulsion (
Ag 12 mol%, internal high Agl type with core-shell ratio 2:1, equivalent sphere diameter 1.0 μ, coefficient of variation of equivalent sphere diameter 15%, plate-like particles, diameter/thickness ratio 6.0) Coated silver amount 0.35 iodine Silver bromide emulsion (Ag 12 mol%, internal high Agl type with core-shell ratio 1:1, equivalent sphere diameter 0.4 tt, coefficient of variation of equivalent sphere diameter 20%, plate-like grains, diameter/thickness ratio 6.0) Coating Silver amount 0.20 Gelatin 0. 5ExS-
3axxo-'ExY-1'3 0. 11ExM
-120,03 ExM-140,10 Solv-10,20 10th layer (yellow filter N) Yellow colloidal silver o, 05 Gelatin 0. 5Cpd-20,1
3 Solv-10,13 Cpd-10,10 11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag 14.5 mol%, uniform Agl type, equivalent sphere diameter 0.7μ, equivalent sphere diameter Coefficient of variation 15%, plate-shaped particles, diameter/thickness ratio 7.0) Coated silver amount 0. 3 Silver iodobromide emulsion (AgI 3 mol%, uniform Agl type, equivalent sphere diameter 0.3 μ, coefficient of variation of equivalent sphere diameter 25!! (, plate-like grains, diameter/thickness ratio 7.0) Coated silver ji O ,15 Gelatin 0・5EχS−
62X10-' ExC-160,05 ExC-20,10 ExC-30,02 ExY-130,07 ExY-1510 Solv-10,20 12th layer (high sensitivity blue-sensitive emulsion rM) Silver iodobromide emulsion (Ag110 mol %, internal high AgI type, equivalent sphere diameter 1.θμ, coefficient of variation of equivalent sphere diameter 2553, multiple twinned plate-like particles, diameter/brightness ratio 2.0) coating! Il amount
0. 5 Gelatin 0.5ExS-6
1xlo-' ExY-150,20 ExY-130,0f Solv, -10,10 1311th! (1st protective layer) Gelatin 0.8UV-40
,l UV-50,15 Solv-10,01 Solv-20,01 No. 1471I (Second protection N) Fine grain bromide emulsion (Ag [2 moles!!≦, uniform λgI type, equivalent sphere diameter 0.07μ) 0.5 Gelatin 0.45 Polymethyl methacrylate particle diameter 1.5μ 0.2H-10,
4 cpct-50,5 Cpd-60,5 In addition to the above components, each layer contains an emulsion stabilizer Cp d -
3 (0,04g/rrr) surfactant cpd-4 (0,
02 g/rd) was added as a coating aid. UV-1 UV-2 UV-4 M UV-5 R=(:, H+y Solv-1 Tricresyl phosphate 5olv-2 Diptyl phthalate olv-3 Solv-4 Cpd-1 0 ■ p d-2 p d-3 υn Pd-4 cpct-s CP d-6 EχC-20H (i) C4HvOCNII xC-3 H ■ xC-4 0i+ xC-5 H ■ C1+. / xC-6 i1 ■ 11iCCC11s ♂ lh C(C1li)z xC- 7 H EχC-8 oL, wt, approximately 20,000 ExC-9 ExC-10 ExC-11 xM-12 xY-13 xY-14 xY-15 ExC-16 H Here R-5CIItCIIzCOOCHsExS-I ExS-2 ExS -3 ExS-4 ExS-5 ExS-6 !(-1 CIl-CIl SOX-CIl! C0NII
Cl1zCIIz=CI 5oz-C1lz C
0NII-C1+! ExF-] II Cz If s C2II 5 The sample prepared above was exposed to 10 CMS using a light source with a color temperature of 4800'K, and was treated with the following treatment steps and treatment liquid. In addition, each bleaching agent, chelating agent, and bleaching accelerator shown in Table 1 was used as the bleaching solution. Processing process Processing time Temperature color development 2 minutes 30 seconds 40℃ bleaching
50 seconds 40℃ fixation
1 minute 30 seconds 40°C stable ■ 30
Seconds 40℃ Stable ■ 30 seconds 40℃ Drying 1 minute 60℃ (color developer) Diethylenetriaminepentaacetic acid 1.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate
30.0g potassium bromide
1.4g potassium iodide 1.
3■Hydroxyamine sulfate 2.4g4-(
Add 5.0g of N-ethyl-N-β-hydroxyethylamino-2-methylaniline sulfate and water.
11 pH 10,20 (Bleach solution) Bleach agent (Table-1) 0.3M chelating agent (Table-1) 0.03M aqueous ammonia 7. Omj! 6 Ammonium acid 10.0g Ammonium bromide
160.0g bleach accelerator (Table 1)
Add 5xlO-'M water
11p8 4. 4(
Fixer) Ethylenediaminetetraacetic acid disodium salt 12.0g 1-hydroxyethylidene-1,1-diphosphonic acid 10.0g Sodium sulfite 4.0g Ammonium thousand osulfate aqueous solution (70% w/v) 175.0g Sodium bisulfite 4.6g Sodium toluenesulfinate 5.0g Add water 1.01pH 6,6 (stabilizing solution) Formalin (37% w/v) 1.0mm!
Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3g 5-chloro-2-methylisothiazolin-3-one 0.05g Add water 1. Ofi, the bleach solution does not contain
The compounds described in 1 were added, and the respective bleaching accelerating abilities were compared based on the amount of residual silver. The amount of residual iI was determined by fluorescent X-ray analysis. The results are shown in Table-1. Table-1 *R represents a comparative example. **EDTA-Ethylenediaminetetraacetic acid As shown in Table 1, if a bleaching solution containing both the bleaching agent and the bleaching accelerator of the present invention is used, a specifically excellent desilvering performance can be obtained. Example - On a subbed cellulose triacetate film support,
I'i! A multilayer color photosensitive material B was prepared by coating. (rg, optical layer composition) The number corresponding to each component indicates the coating amount expressed in g/rrf units, and for silver halide, it indicates the coating amount in terms of silver. However, for sensitizing dyes, the same - The amount of halogen to be applied per mole of chemical compound is expressed in moles. (Sample B) 1st layer; antihalation layer black colloid! 1 bar 0.18 Gelatin 0.40 2nd layer; Middle layer 2.5-di-t-pentadecylhydroquinone 0.18EX-10
,07 EX-30,02 EX-120,002 U-10,06 0-20,08 U-30,10 HB-5-10,10 HBS-20,02 Gelatin 1.04 Third layer (first red Sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0)
．． 6μ, coefficient of variation with respect to particle size 0.15) Silver 0.55 Sensitizing Dye 1 6.9X10-' Sensitizing Dye II 1.8X10-' Sensitizing Dye I
I 3. lXl0-'enhancing dye rV'
4.0X10-'EX-20,35
0 HBS-10,005 EX-100,020 Gelatin 1.20 No. 4N (second red-sensitive emulsion M) Tabular silver iodobromide emulsion (silver iodide 10 mol%, average a diameter 0.7μ, average aspect ratio 5.5, average thickness 0.2μ
) Resentment 1.0 aggravation pigment!
5. 1X10 Bow Multiplying Dye 11L
1.4X10-' sensitizing dye III
2.3X10-' Exacerbating Dye IV 3
．． 0XIO-'EX-20,400 EX-30,050 EX-100,015 Gelatin 1.30 No. 51N (
3rd red emulsion N) Silver iodobromide emulsion (16 mol% of iodobromide, average grain size 1
．． 1μ)! Amber 1. 60 sensitizing dye IX 5.4X
10-' Exacerbating dye f[1,4X10-S Exacerbating dye n[2,4xtO-' Exacerbating dye IV 3.1xlO-' Snake
-30,240 EX-40,120 HBS-10,22 HBS-20,10 Gelatin 1.63 No. 61 (middle layer) EX-50,040 HBS-10,020 EX-120,004 Gelatin 0.80 No. 7 Layer (first green emulsion N) Tabular silver iodobromide emulsion (6 mol% iodide, average grain size 0.6μ, average aspect ratio 6.0, average thickness 0.15
) Silver 0.40・Sensitizing dye V
3.0X10-'sensitizing dye V[1,0X
LO-' Exacerbating dye■ 3.8X10-'EX-6
0,260 EX-10,021 EX-70,030 EX-80,025 8BS-10,100 HBS-40,010 Gelatin 0.75 8th layer (second green emulsion layer) Monodisperse silver iodobromide emulsion (Silver iodide 9 mol%, average a diameter 0
．． 7μ, coefficient of variation between particle size 0.18) 0.80 Sensitizing dye V 2. lXl0-'sensitizing dye Vl, 7.0X10-'enhancing dye■ 2.6XLO-'EX-60,18
0 EX-80,010 EX-10,008 EX-70,012 HBS-10,160 HBS-40,008 Gelatin 1.10 9th layer (3rd green emulsion fil) Silver iodobromide emulsion (silver iodide 12 mol%, average particle size 1.0
μ) Daughter 1.2 Sensitizing dye V
3.5X10 bow sensitizing dye V!
8.0X10-' aggravating dye ■ 3,
0XIO-'EX-60,06S EX-110,030 EX-I Q,025
HBS-10,25 HBS-20,t. Gelatin 1.74 1st O layer (
Yellow filter layer) Yellow colloid! 2 Silver 0.05EX
-50,08 1 (BS-30,03 Gelatin 0.95 11th layer (
First blue emulsion N) Tabular silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0)
．． 6μ, average aspect ratio 5.7, average thickness 0.15)
Silver 0.24 mesmerizing dye■
3.5X10-'EX-90,85 EX-80,12 HBS-10,28 Gelatin 1.28 12th layer (second emulsion F monodisperse silver iodobromide emulsion (silver iodide 10 moles!! A, average particle size 0.8 μ, coefficient of variation regarding particle size 0.16)
0. 45 Sensitizing dye ■ 2. lXl0-'EX-9
0,20 EX-100,015 HBS-10,03 Gelatin 0.46 No. 137!
(Third blue-sensitive emulsion N) Silver iodobromide emulsion (silver iodide 14 mol%, average grain size 1.3
μ) Silver 0.77 Intensifying dye ■
2.2X10-'EX-90,20 8BS-10,07 Gelatin 0.69 14th layer (
1st protective layer) Silver iodobromide emulsion (imt mole iodide?≦, average grain size 0.
07μ) Daughter 0.5υ−4
0,LI U-50,17 HBS-10,90 Gelatin 1.00 15th layer (2nd layer polymethyl acrylate particles (diameter 1.51 m) 0,54S-10
, 15 3-20,05 Gelatin 0.72 In addition to the above components, gelatin hardening agent H-1 and a surfactant were added to each layer. U-1, Example 1 (7) Same as UV-1 υ-2; Same as UV-2 of Example 1 U-3; Same as Example 1 (7) UV-3 Same as U-41 of Example 1 (7) UV-46: Same U-5; υV-5 of Example 1
EX-1 same as EX-1; EX-2 same as ExC-9 of Example 1; EX-3 same as ExC-2 of Example 1, EX-1 (7) EX
Same EX-4 as C-4, same E as ExC-7 of Example 1
X-5, EX-6 same as cpd-1 of Example 1, same as Exc-8 of Example 1 but with an average molecular weight of 30,000 EX-7, EX-8 same as ExM-12 of Example 1, EX-9 same as EXY-13 of Example 1, EX of Example 1
EX-10i same as Y-15 Same as EXC-16 of Example 1. However, R-SCHCOOCH. Summer CH. EX-11; Same as ExC-9 of Example 1, but R-H EX-12 S-1; S-2, same as Cpd-5 of Example 1; HBS-1i, same as Cpd-6 of Example 1) licresyl phosphate HBS-2,
Dib, tylphthalate HBS-3i bis(2-ethylexyl) phthalate HBS-4, Example 10) Same H as S o I v-4
-1; The same amplifying dye (C11 zSOiv (L; 1lzJ 5) U
tllazHs group C18゜■ ■ The sample prepared as above was exposed to 2.5 CMS using a light source with a color temperature of 4800@, and was treated with the following treatment steps and treatment liquid. The bleaching solution and bleach-fixing solution each contain 5 x 10 of each accelerator listed in Table-2.
-'mol/j! Added. A desilvering test was conducted in the same manner as in Example 1, and the results shown in Table 2 were obtained. Processing process Processing time Temperature color development 2 minutes 30 seconds 40℃ bleaching
30 seconds 38℃ bleach fixing 1
Minutes Wash with water at 38℃ 1 minute
Stable at 38℃ 30 seconds 3
Dry at 8℃ for 1 minute at 60℃ (
Color developer) Same as Example 1 (Bleach solution) Bleach agent (Table 2) 0.34 mol ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium bromide 180.0g Bleach accelerator (n-1)
3.0g ammonium nitrate
10.0g ammonia water (27%)
Add 15.0ml water 1. O
j! pH 4.2 (Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50.0g Ethylenediaminetetraacetic acid disodium salt 5.0g Sodium sulfite 12.0g Sodium toluenesulfinate 5.0g Ammonium thiosulfate aqueous solution (70% @ /v) 240.0g ammonia water (27%) 6.0mj! Add water 1.01p)I
'y, 2 (Washing water) A hotbed type in which tap water was filled with an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm 7nd Haas) and an OH-type anion exchange resin (Amberlite IR-400). Water was passed through the column to reduce the concentration of calcium and magnesium ions to 3/It or less, and then sodium dichloride isocyanurate 20/L and sodium sulfate 0. 15g/! was added. The pH of this solution was in the range of 6.5-7.5. (Stabilizing liquid) Polmarine (37%) 2.0ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3g Ethylenediaminetetraacetic acid disodium salt 0.05g Add water 1. 0ILpH5,0-
8,0 Table-2 In case of two types of bleach, addition table of 0.17 mol/l each.
As can be seen from 2, if the present invention is used, excellent desilvering performance can be obtained even in bleach-bleach-fix processing. Especially l, 3
-Diaminopropanetetraacetic acid ferric complex salt (K -(2)
) allows for the quickest desilvering. (Processing No.
20) Furthermore, the combination of two types of bleaching agents is preferred, and in particular, the combination of Ni-(2) and Ni-(4) (Nα31) was the most preferred combination. Kasenmasu-1 A multilayer color photosensitive material C was prepared by coating each layer having the composition shown below on an undercoated cellulose triacetate film support. (Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/n (units). For silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, the coating amount in the same layer The coating amount per mole of silver halide is shown in moles. 1st layer (antihalation N) Black colloidal silver 0.2 Gelatin 1.0 Ultraviolet absorber UV
-10,05 Same UV-20.1 Same UV-30.1 Dispersion oil 0IL-10,02 2nd layer (middle N) Fine grain silver bromide (average particle size 0.07μ) 0.15 Gelatin 1.0th layer 3 layers (first red-sensitive emulsion layer) Emulsion A 1. 42 Gelatin 0.9 Sensitizing dye A
2.0xlO-'sensitizing dye B
1.0X10-'sensitizing dye C0,3X10
-' cp-b O,35Cp-
co, 052 Cp-do, 047D-
10,023 D-20,035 HBS-10,10 HBS-20,10 4th layer (middle layer) Gelatin 0.8cp-b
o, 10HBS-10,05 5th layer (second red-sensitive emulsion layer) Emulsion A 1.38 Gelatin 1.0 Sensitizing dye A
1.5X10-' sensitizing dye B
2.0X10-'sensitizing dye CO,5X10
-' cp-b o, ts. Cp-d 0.027D-
10,005 D-20,010 HBS-10,050 HBS-20,060 6th layer (third red-sensitive emulsion layer) Emulsion E 2.08 Gelatin 1.5 Cp-ao, 0
60 Cp-cO, 024 cp-a o, 038D-
10,006 HBS-10,12 No. 711 (middle layer) Gelatin 1.0Cpd-A
0.05HBS-20.05 8th layer (first green sensitive layer) Monodisperse silver iodobromide emulsion (silver iodide 3 mol%, average grain size 0.4
μm, coefficient of variation 19%) 0.64 Monodisperse silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.7
μm, coefficient of variation 18%) 1.12 Gelatin 1.0 Aggravating dye D
lXl0-'sensitizing dye E
4X10-'sensitizing dye F
lXl0-'cp-h
o, 20cp-r
o, 61 cp-g
o, 084Cp-k 0
．． 035Cp-10,036 D-30,041 D-40,018 HBS-10,25 HBS-20,45 9th layer (second green-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 7 mol% , average particle size 1.0
8m, coefficient of variation 18%) 2.07 gelatin ], 5 sensitizing dye D
1.5X10-' sensitizing dye E
2.3X10-' sensitizing dye F
1.5X10-'cp-r
o, 007cp-h
o, 012Cp-g
0. 009HBS-20,088 10th layer (middle layer) Yellow colloid II O,06 gelatin 1.2Cpd-A
0.3HBS-10,3 11th layer (first blue emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.4
μm1 variation coefficient 20%) 0.31 Monodisperse silver iodobromide emulsion (silver iodide 5 mol%, average grain size 0.9
μm, coefficient of variation 17%) 0.38 Gelatin 2.0 Exacerbating dye G
lXl0-'sensitizing dye HlX
l0-' Cp-io, 63 Cp-j O, 57D-1
0,020 D-40,015) (BS-10,05 12th calendar (second blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 8 mol%, average grain size 1.3
8m1 coefficient of variation 18%) 0.77 Gelatin 0. 5 sensitizing dye G 5X10-' sensitizing dye H5
X10-' Cp-+0.10 Cp-jO,10 D-40,00HBS-20,10 13th layer (middle N) Gelatin 0. 5Cp −
m 0. ILJV-1
0.l UV-20,l UV-30,I HBS-10,05 HBS-20,05 14th N (protective layer) Monodisperse silver iodobromide emulsion (silver iodide 4 mol%, average grain size 0.0
5μ, coefficient of variation 10%) 0.1 Gelatin 1.5 Polymethylmetharylate particles (average 1.5μ) 0, l 5-1 0. 23-2
0. 2. -L gelatin hardening agent--1 was added to the other surfactants. 0 ~ = = Q
O huge
Q [(JHs [)-30H 10:- Ro O. : 〇
−〇
Q1I ba:C: 1 = False O 0li1 0,5. I 9 1 0 Qu
j Q −1
I CL αQ
Q B5-1 1,. Ct H5 ) (BS-2 ni-1 UV-1 Same as above UV-2 C(CH Conoco U"/-3 Compound cp dA HH H A desilvering test was conducted in the same manner as in Example 1.Furthermore, the adhesion of stains on the surface of the treated film was visually observed.The composition of the bleaching solution used is shown below.(Bleach solution) 1.3-diaminopropane tetra Ferric ammonium acetate salt (K - (21) 0.25 mol ethylenediaminetetraacetic acid ferric ammonium trihydrate 0.1 mol ethylenediaminetetraacetic acid disodium salt 5.0 g aqueous ammonia (27%) 7.0 mj! Ammonium nitrate 10.0g ammonium bromide
100.0g bleach accelerator (each compound in Table 3 and no additives) Add water and 11p
H (Table-3) The results are shown in Table-3. Table 3 0: No stain Δ: Slight stain ×: Stain .47) shows excellent desilvering performance. Moreover, at this pH, an unexpected effect was obtained in that not only the desilvering performance but also the stains adhering to the processed film were improved. Example-T On a subbed cellulose triacetate film support,
Sample p, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared. (Composition of photosensitive layer) For silver halide, colloidal silver and couplers, the coating amount is expressed in g/nf units of silver, and for sensitizing dyes, the number of moles per mole of Sl halide in the same layer is used. It was shown in 1st FJ: Antihalation layer black colloidal silver silver coating gk0. 2 Gelatin 2. 2uv-t
o・lUV-2,0・
2 Cpd-10,05 Solv-10,01 Solv-20,01 Solv-30,08 2nd N: Intermediate layer fine grain silver bromide (equivalent sphere diameter 0.07μ) Silver coating amount 0.15 Gelatin 1.0Cpd-2
0,2 3rd Pi: First red-sensitive emulsion layer silver iodobromide emulsion (Agro+, o mol%, internal high Agl type, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 14%, tetradecahedral grains) Silver Coating amount 0.26 Silver iodobromide emulsion (Ag (4.0 mol%, internal high Agl type, equivalent sphere diameter 0.4μ, coefficient of variation of equivalent sphere diameter 22%, tetradecahedral grain) Coating amount m 0.2 Gelatin 1.0ExS-14
,5xlO-'molExS-21,exto-'molExS-30,4xlO-'molExS-40,3xlO-'molExC-10,33 ExC-20,009 ExC-30,023 ExC-60,14 4 layers: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (Agl + 6 mol%, internal high AgT type, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 4. 0) Silver coating amount 0.55 Gelatin 07 ExS-13XIO-' ExS-21X l O-'ExS-30,3XIO-'ExS-40,3xlO-' ExC-30,05 ExC-40,10 ExC-60, 08 5th notification: 3rd red-sensitive emulsion layer silver iodobromide emulsion (Agl to, o mol%, internal high Ag
Type I, equivalent sphere diameter 1.2μ, coefficient of variation of equivalent sphere diameter 28%, plate-like particles, diameter/thickness ratio 6.0) Silver coated l 0.9 Gelatin 0.6ExS-12x
lO-' ExS-20, exto-' ExS-30, 2xlO-' ExC-40,07 ExC-50,06 Solv-10,12 Solv-20,12 6th layer: Intermediate layer gelatin 1.0Cpd-40
, 1 7th layer: 1st green-sensitive emulsion layer Silver iodobromide emulsion (Ag I io, Q-ID, inner diameter Agl type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 14%, 14 (hedral grain) Silver coating amount 0.2 Silver iodobromide emulsion (Ag 14.0 mol%. Internal high AEI type, equivalent sphere diameter 0.4 μ, coefficient of variation of equivalent sphere diameter 22%, tetradecahedral grain) Silver coating amount 0 .1 Gelatin 1.2ExS-55
xlO-' ExS-62 (Ag1 10 mol%, internally high iodine type, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 25%, plate-shaped particles, diameter/thickness ratio 3.0) Silver coating amount 0.4 Gelatin 0.35ExS- 5
3,5xto-'ExS-61,4X10-'ExS-70,7X10-' ExM-10,09 ExM-30,01 Solv-10,15 9th layer: Intermediate layer gelatin 0.5 10th Jii
: Third green emulsion layer Silver iodobromide emulsion (A g ! 10.0 mol χ. Internal amount Ag, type I 1 sphere equivalent diameter 1.2μ. Coefficient of variation of sphere equivalent diameter 28%, plate-like grains, diameter /thickness ratio 6.0) S coating amount 1, 0 Gelatin 0.8ExS-52
X10-'ExS-60,8X10-'ExS-70,8xlO-' ExM-30,01 ExM 4 0.04Ex
C-40,005 Solv-10,2 No. 1173: Yellow filter layer Cpd-30,05 Gelatin 0.5Solv-10
, 1 tZa: Intermediate layer gelatin 0.5Cpd-20,
1 137th! l: First blue-sensitive emulsion layer silver iodobromide emulsion (Agr 10 mol%, internal high iodine type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter !4%, !tetrahedral grains) Silver coating amount 0 ．． 1 Silver iodobromide emulsion (Ag + 4.0 mol τ, internal high iodine type, equivalent sphere diameter 0.4μ, coefficient of variation of equivalent sphere diameter 22%, 14-hedral grains) Silver coating amount 0.05 Gelatin 1.0ExS-83
xlO-' ExY-10,53 ExY-20,02 Solv-10,15 14th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (A g 1 19.0-ILI. Internal high AgI type, equivalent to sphere) Diameter 1.0μ, coefficient of variation of equivalent sphere diameter! 6%, tetradecahedral particles) Silver coating amount 0.19 Gelatin 0.3ExS-82
X10-' ExY-10,22 Solv-10,07 No. 15: Intermediate layer fine grain silver iodobromide (Ag 12 mol χ, uniform type 1 sphere equivalent diameter 0.13 μ) Silver coating 1 0.2 Gelatin 0.36 No. 16FJ
: Third blue-sensitive emulsion layer Silver iodobromide emulsion (Ag 1 14.0 mol X. Internal high Ag summer type 5 sphere equivalent diameter 1.5μ. sphere) "Coefficient of variation of light diameter 28%, plate-like grain, diameter /thickness ratio 5.0) Silver coating amount 1.0 Gelatin 0.5ExS-81
,5XIO°4 ExY-10,2 Solv71 0.07 17th layer:
First protective layer gelatin 1.8uv-t
o, tUV-20,2 Solv-10,01 Solv-20,01 18th layer: 2nd protective layer Fine grain silver bromide (equivalent sphere diameter 0.07μ) Silver coating amount 0.18 Gelatin 0.7 Polymethyl Methacrylate particles (diameter 1.5μ) 0.2 W-10,02 H-10,4 Cpd-51,0 V-1 COCOOCH. x/y = 7 /3 (mMt above b) V-2 xM-3 xC-1 xC-3 xC-6 ExC-4 ExC-5 C+zH□ xM-1 CH. Heat xM-2 xM-4 xY-I xY-2 xS-1 xS-2 xS-3 C,H. C,H. Ext-6C,H. l Ext-8 olv-1 oLv-3 pd-3 pd-4 pd-5 C,F,,So□NHCH,CH□CHt 0CHx
CHz N (CH3)3CH, -CH5O,CH,
C0NH-CH! CH, -CH5O, CH, CONH-
CH. The photosensitive material prepared as described above was cut to a width of 35 m/m, and after image exposure was given under the condition of rsO 1600, running processing was performed separately for each bleaching solution using the following processing steps and processing solutions. . Table 4 Processing process* Photosensitive material 35n/n width 1m length Drying is 60
℃ for 1 minute. In the above treatment steps, the stabilization steps ■, ■, and ■ are from ■ to ■.
, a countercurrent method was adopted from ■ to ■. Next, the composition of each treatment liquid used is shown. (Color developer) Mother solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.1 1.11-Hydroxyaminethene-1,1-diphosphonic acid 2.0 2.2 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 32.0 Potassium bromide 1.4 0.7 Potassium iodide
1.3■ -Hydroxyamine sulfate 2.4 2.64-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate 4.5 5.0 Add water 11 Iffp H10
,0010,05 (Bleach solution) Mother liquor (g) Replenisher solution (g) 1.3-diaminopropanetetraacetic acid ferric ammonium salt (K-+21) 0.25 mol 0.3
Mol ethylenediaminetetraacetic acid ferric ammonium dihydrate 0.1 mol 0.12 mol ethylenediaminetetraacetic acid disodium salt 5.0 6.0 Aqueous ammonia (27%) 7.0 m 12 1.0
ml ammonium nitrate 10.0 10
．． 0 Bleach accelerator (Table-5) 6X10-” roll 6
X10-'Molar ammonium bromide 180.0
220 bleach accelerator (each compound in Table 3 and no additives)
Add water 11 1! pH4,
43,5 (Fixer) Mother liquor (g) Replenisher (g) Ammonium 1000 sulfate (70% H/v) 240 ml 260 m
l Sodium sulfite 1820 Ethylenediaminetetraacetic acid ferric ammonium trihydrate 90 100 Ethylenediaminetetraacetic acid disodium dihydrate 9.0 10.0 Ethylenediamine-N,N. N',N'-tetramethylenephosphonic acid 6.0 8.0 Add water iz 1pppH6,56
,0 (stable solution) Mother solution and replenisher common, same as Example-1, each after running treatment for 7 days at 30m per day Example-
A desilvering test was conducted in the same manner as in 1. The results are shown in Table-5. Table 5 As shown in Table 5, if the present invention is used, rapid desilvering is possible even during running processing. Especially when bleach accelerator (II)-Ill is used (N15
The best desilvering performance was obtained for 1). Example 5 When the processing method of the present invention described in Example 4 was carried out using the following color negative film, good effects similar to those in Example 4 could be obtained. Fuji Color Super HR100 (emulsion number 6266689) Fuji Photo Film Co., Ltd. Fuji Color Super HR200 (523009) Fuji Color Super 1 (R400 (315059) Fuji Color Super HR1600 (723005) Konica Color GX100 (emulsion number 106) manufactured by Konica Corporation )same
GX400 (〃 861) Same GX3
200 (-751) Eastman Kodak Company Kodacolor VRGloo (emulsion number 5095 104) VRG200 (5096 034) VRG400 (5097 123) VR1000 (5090 254) Example-6 Example-1 of the following patent The silver halide color photographic light-sensitive material (color negative film) described in Example 3 of the present invention
When treated with 40 patients, Example 1 of the following patent was obtained.
Effects similar to those described in 1 were observed, and it was also observed that the treatment method of the present invention similarly exhibited excellent effects. Japanese Patent Publication No. 57-151994 No. 57-94752 European Patent Publication No. 161626A No. 60-143331 No. 60-185950 No. 60-138548 Patent Applicant: Fuji Photo Film Co., Ltd. July 7th, 2017 Director General of the Patent Office, I1.
Thing! Indication of 1986 η Application No. J///7 2, Title of the invention Processing method for silver halide color photographic light-sensitive materials 3, Relationship to the case of the person making the amendment Person of the patent applicant Location 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Address name (520) Fuji Photo Film Co., Ltd. 4. Date of amendment order 1985 (month/day) (shipment date) 5. Subject of amendment Specification 6. Engraving of the statement of contents of the amendment (contents changed) None) will be submitted.

Claims (1)

[Scope of Claims] A method of processing an imagewise exposed silver halide color photographic light-sensitive material with a bleaching solution after color development, wherein the bleaching solution contains at least one chelating agent selected from the following chelating agent group. Iron complex salts, and the following general formulas (A), (B), and (C)
1. A method for processing a silver halide color photographic material, comprising at least one compound selected from the following. Chelating agent [diethylenetriaminepentaacetic acid 1,3-diaminopropanetetraacetic acid 1,2-diaminopropanetetraacetic acid 1,2-cyclohexanediaminetetraacetic acid glycol ether diaminetetraacetic acid iminodiacetic acid N-methyliminodiacetic acid 1,4-diaminobutanetetraacetic acid Acetic acid 1,5-diaminopentanetetraacetic acid] General formula (A) R-SM General formula (B) R-S・S-R^1 (In the formula, M is a hydrogen atom, an alkali metal atom, ammonium, or ▲ mathematical formula, There are chemical formulas, tables, etc. ▼. Here, X^1, X^2, and X^3 represent a hydrogen atom and an alkyl group, respectively. Also, R and R^1 represent an alkyl group, an alkylene group, an aryl group, and a hetero Represents a ring residue.) General formula [C] ▲ Numerical formulas, chemical formulas, tables, etc. (represents a monovalent aliphatic group, aromatic group, heterocyclic group or hydrogen atom), X is -O-, -S
−, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R^
1, R^2 represents a substituted or unsubstituted lower alkyl group, R^3 represents a lower alkylene group, and R^4 represents a lower alkyl group. Here R^1 and R^2, R^1 and A
, R^1 and R^3, R^2 and A, or R^2 and R^3 may be connected to form a ring. Y represents an anion, l
is 0 or 1, m is 0 or 1, n is 1, 2 or 3, p is 0
or 1 and q represents 0, 1, 2 or 3. q is chosen to be an electrically neutral molecule. )