JPH01254958A - Solution and method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a bleaching solution superior in silver bleaching ability and high in stability by incorporating the ferric complex salt of an organic acid or its salt and an N-containing heterocyclic compound. CONSTITUTION:The processing solution to be used for the bleaching solution for a silver halide color photographic sensitive material contains the ferric complex salt of the compound represented by formula A and the compound represented by general formula S-I or S-II, and in these formulae, each of A1-A4 is -CH2OH, COOM, or -PO3M1M2; each of M, M1, M2 is H, Na, K, or ammonium; X is 3-6C alkylene; Z is an atomic group necessary to form a hetero ring; Q is a heterocyclic residue combined with -SO3M2, -COOM2, -OH, or -NR1R2; each of M1 and M2 in S-II is H, alkali metal, quaternary ammonium, or quaternary phosphonium; and each of R1 and R2 is or alkyl, thus permitting the obtained processing solution to be superior in silver bleaching ability, and improved in stability.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a processing solution and processing method for silver halide color photographic light-sensitive materials. The present invention relates to a processing solution and processing method for silver halide color photographic light-sensitive materials (hereinafter sometimes simply referred to as "photosensitive materials") that have excellent stability and can be rapidly processed. [Background of the Invention] Processing of light-sensitive materials basically consists of two steps: color development and desilvering, and desilvering consists of a bleaching and fixing step or a bleach-fixing step. In addition to this, rinsing treatment, stabilization treatment, etc. are added as additional treatment steps. The processing solution with bleaching ability used in the desilvering process of photosensitive materials contains 1 red blood salt as an oxidizing agent to bleach the image silver.
Inorganic oxidizing agents such as dichromate were widely used. However, some serious drawbacks have been pointed out to processing solutions containing these inorganic oxidizing agents that have bleaching ability. Although it is relatively good, it has unfavorable properties in terms of pollution prevention, as it may be decomposed by light and generate cyanide ions and hexavalent chromium ions that are harmful to the human body. Furthermore, processing liquids containing these inorganic oxidizing agents have the disadvantage that it is difficult to reuse the waste liquid after treatment without discarding it. On the other hand, metal complex salts of organic acids such as aminopolycarboxylic acid metal complex salts have been used as oxidizing agents as they have fewer pollution problems and meet the requirements of speeding up and simplifying the treatment and making it possible to reuse the waste liquid. Treatment liquids have come to be used. However, processing solutions using metal complex salts of organic acids have a slow oxidizing power, so they have the disadvantage that the bleaching rate (oxidation rate) of image silver (metallic silver) formed in the development process is slow. 0 For example, iron ethylenediaminetetraacetate (iron ethylenediaminetetraacetate), which is considered to have the strongest bleaching effect among aminopolycarboxylic acid metal complex salts,
m) Complex salts have been put to practical use in some areas as bleaching solutions and bleach-fixing solutions, but they can also be used in high-sensitivity silver halide color photographic materials containing silver bromide and silver iodobromide emulsions, especially as silver halide. Color vapor for photography, color negative film for photography, and color reversal film containing silver iodide and a high amount of silver have the disadvantage that bleaching blades are insufficient and the bleaching process requires a long time. In addition, in development processing methods in which a large amount of photosensitive material is continuously processed using an automatic processor, etc., in order to avoid deterioration of the performance of the bleaching solution due to changes in the concentration of the components, it is necessary to keep the components of the processing solution within a constant concentration range. A means is necessary. In recent years, as such means, from the economic and pollution viewpoints, the so-called concentrated and low replenishment method, in which these replenishers are concentrated and refilled in small amounts, has been developed.
Another method has been proposed in which a regenerant is added to the overflow liquid and the overflow liquid is used again as a replenisher. In particular, in bleaching solutions, organic m-ferrous rust salts 1, such as ethylenediaminetetraacetic acid iron(II) complex salts produced by bleaching developed silver, are converted into ethylenediaminetetraacetic acid iron(m) complex salts, i.e. organic acid ferric salts, by aeration. A method has been put into practical use in which the salt is oxidized back to a complex salt, a regenerating agent is added to supplement the missing components, and the mixture is used again as a replenisher. However, in recent years, so-called compact laboratories (also known as mini-labs) have emerged in order to shorten the processing time of silver halide color photographic materials and reduce collection and delivery costs. There is a strong need to reduce the installation area of the machine, and recycling processing is not desirable because it requires complicated labor and management, and also requires processing space. Therefore, it is preferable to use a concentrated low replenishment method that performs low replenishment without performing regeneration processing, but if the amount of replenishment of the bleaching solution is extremely reduced, the concentration of color developer components brought into the bleaching solution will increase.
In addition, it becomes more susceptible to the effects of concentration due to evaporation, and the accumulation of color developer components increases more and more. As described above, when the concentration of color developer components in the bleaching solution increases, the mixing ratio of color developer crude drugs and sulfites, which are reducing components, increases, inhibiting the bleaching reaction, and making it easy to cause failures called desilvering failures. Become. In order to improve these shortcomings, Research Disclosure (Research Disclosure)
) No. 24023 and the specific aminopolycarboxylic acid No. 2 described in JP-A No. 62-222252.
Techniques using iron complex salts and mixtures thereof have been proposed. However, it has been found that these techniques have various drawbacks. For example, 1 described in the above literature or patent publication
Although the ferric complex salts of 3-propanediaminetetraacetic acid have extremely strong oxidizing power and are suitable for rapid processing, it has been found that staining is likely to occur due to the above-mentioned strong oxidizing power. This staining becomes particularly noticeable when components of the color developing solution are brought into the bleaching solution by running or when the bleaching solution is replenished at a low level. Furthermore, according to our study results, it has been found that silver sludge is also more likely to occur when 1,3-propanediaminetetraacetic acid ferric complex salt is used. In addition, in recent years, there has been a trend in minilabs to use a waterless washing process (stabilization process) in which the amount of water used for washing is greatly reduced using a specific chemical. The stability of the processing solution tends to deteriorate. This tendency has been increasingly emphasized in rapid processing in recent years. [Object of the Invention] Therefore, the first object of the present invention is to provide a processing liquid and a processing method which are excellent in silver source white blade and have improved stability of the processing liquid. A second object of the present invention is to provide a processing solution and a processing method for photosensitive materials which have excellent processing stability and are improved in the occurrence of precipitation during processing. [Structure of the Invention] As a result of intensive research to solve the above-mentioned problems, the present inventors have developed a ferric complex salt of a compound represented by the following general formula [A] and a general formula [S-1] or [S- It has been found that this can be achieved with a processing solution for photosensitive materials containing a compound represented by [TI]. Further, in a method for processing a photosensitive material, which immediately after color development is treated with a bleaching solution and subsequently treated with a processing solution having a fixing ability, the bleaching solution is a ferric compound of a compound represented by the following general formula [A]. Complex salts and general formula [S-IF or [S
The present invention was based on the discovery that the above object can be achieved by using a treatment liquid containing a compound represented by [-n]. General formula [A] [In the formula, A and ~A may be the same or different,
-C) represents lffiOH, -COOM or -POJIMt. M, Ml+L are hydrogen atoms, sodium, and
Represents potassium or ammonium, X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms,] General formula [S-I
] , 7z1, N' In the formula, 2 represents an atomic group necessary to form a heterocycle. General formula [S-1 Q-SM. In the formula, q is -8O3Mx, -C00M2. Represents a heterocyclic residue directly or indirectly bound to at least one selected from the group consisting of OH and -NR+R*, M,
M represents a hydrogen atom, an alkali metal, a quaternary ammonium, or a quaternary phosphonium, and R1 and R2 represent a hydrogen atom or a substituted or unsubstituted alkyl group. [Specific Structure of the Invention] Next, the compound represented by the general formula [A] will be described in detail. A, ~^4 may be the same or different, and -c
H, oll represents -COOM or -P03MsMx, and M, M, and M are respectively hydrogen atoms, sodium,
It represents potassium or ammonium, X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms (for example, propylene, butylene, pentamethylene, etc.), and examples of the substituent include a hydroxyl group. Preferred specific examples of the compound represented by the general formula [A] are shown below. (A-1) (A-2) (A-3) (A-5) (A-6) (A-7) (A-8) These compounds (A-1) to (A-8) are In addition to the above, sodium salts, potassium salts, or ammonium salts of these may be used as desired. From the viewpoint of the desired effects of the present invention, ammonium salts of these ferric complex salts are preferably used. Among the above compound examples, those particularly preferably used in the present invention are (A-1), (A-2), (A-4),
(A-'7), particularly preferred is (A-'7).
-1). The ferric chain bottle of the compound represented by the general formula [A] is bleaching solution 1! The range of 0.002 mol to 0.5 mol per L is preferably used, more preferably 0.01 mol to 0.5 mol.
45 mol, particularly preferably 0.05 mol to 0.05 mol.
The range is 4 moles. The bleaching solution of the present invention includes a ferric complex salt of the compound represented by the general formula [A], and other aminopolycarboxylic acid ferric complex salts.
Iron complex salts (e.g. ferric complex salts of ethylenediaminetetraacetic acid,
diethylenetriaminepentaacetic acid ferric complex salt, 1,2-cyclohexanediaminetetraacetic acid ferric complex salt, glycol ether diamine tetraacetic acid ferric complex salt, etc.). In particular, it is preferable to use it in combination with ferric chain salt of ethylenediaminetetraacetic acid from the economic point of view and from the point of view of less bleaching fog. The bleaching solution according to the present invention has the general formula [S-■] and /
or [S-11:] (hereinafter also referred to as the compound of the present invention). Specific examples of the compound represented by the general formula [S-I] are shown below, but the invention is not limited thereto. S-I S-
2H S-9S-10 11ll S-175-18 Methods for synthesizing these compounds are well known and can be easily synthesized by those skilled in the art. For these compounds, reference can be made to, for example, "New Experimental Chemistry Course 14@" (published by Maruzen). Specific examples of the heterocyclic residue represented by Q in the general formula [II] include an oxazole ring, a thiazole ring, an imidazole ring, a selenazole ring, a triazole ring, a tetrazole ring, a thiadiazole ring, an oxadiazole ring, a bentazole ring, Pyrimidine ring, thiasia ring, triazine ring, thiadiazine ring, etc., or rings fused with other carbocycles or petero rings, such as benzothiazole ring, benzotriazole ring, benzimidazole ring, benzoxazole ring,
Examples include a benzoselenazole ring, a naphthoxazole ring, a triazaindolizine ring, a diazaindolizine ring, and a tetraazaindolizine ring. Among the mercapto heterocyclic compounds represented by the general formula [S-II], those represented by the following general formula [S-■] are preferred. General formula [S-m] In general formula [S-III], Y and z are independent nitrogen atoms or CR'(R' is a hydrogen atom 1H-substituted or unsubstituted alkyl group, ° or substituted or unsubstituted aryl ) represents a group, Bs is -8O3M--CO
It is an organic residue substituted with at least one member selected from the group consisting of , propyl group, hexyl group, dodecyl group, octadecyl group, etc.), aryl group having 6 to 20 carbon atoms (e.g. phenyl group, naphthyl group, etc.), Ll is -s
+, -〇-5-N-1-CO-1-SO-, and -SO
, -, where n is 0 or II]. In addition to these alkyl groups and aryl groups, halogen atoms (F, C1, Br, etc.), alkoxy groups (methoxy group, methoxyethoxy group, etc.), aryloxy groups (R2
or aryl group), aryl group (when R2 is an alkyl group), amide group (acetamide group, benzoylamide group, etc.), carbamoyl group (unsubstituted carbamoyl group, phenylcarbamoyl group, methylcarbamoyl group, etc.), sulfonamide groups (methanesulfonamide group, phenylsulfonamide group, etc.), sulfamoyl group (unsubstituted sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, etc.), sulfonyl group (methylsulfonyl group,
phenylsulfonyl group, etc.), sulfinyl group (methylsulfinyl group, phenylsulfinyl group, etc.), cyano group, alkoxycarbonyl group (methoxycarbonyl group, etc.)
, an aryloxycarbonyl group (such as a phenoxycarbonyl group), and a nitro group. Here, the substituents of R3 are -3OJ", -COOM",
When two or more -OH and -NR'R'' are present, they may be the same or different. MI and M2 each mean the same as M and M2 explained in general formula [S-II]. Specific examples of compounds preferably used in the present invention are shown below.The following blanks indicate CHtCH*CHtOH. That is, U.S. Pat. Nos. 2,585,388 and 2,541,924.
No., Special Publication No. 42-21842, Japanese Patent Publication No. 53-5016
No. 9, British Patent No. 1,275,701, D. A. Virginis et al., “Journal of Heterocyclic Chemistry” (D. A. BergeSet, al., “
Journal ofHeterocyclic Ch.
volume 15, page 981 (1978)
, °The Chemist-ry of Heterocyclic Chemistry, Imidazole and Derivatives, Partoe
"Terocyclic Chemistry" lm1
dazole and derivatives par
tI), pp. 336-9, Chemical Abstract, 5
8.7921 (1963), p. 394, E. Hogarth, “Journal of the Chemical Society” (E.
, Japan oggarth “Journal of Chem
ical 5ociety”>pages 1160-7 (194
9), and S. R. Saradler, W. Caro, “Organic Functional Group Prevalence”, Academic Press (S. R. Saladler, W. Niaro, “Organ”)
ic Fanetional GroupPrepar
ation” Academic Press) 31
pp. 2-5, (1968), M. Jamton et al.
amdon, et, al, ), Pourtin de U Société Jimique de France (Bulletin
de la 5ociete chimique de
France), 723 pages (1954), D.
^, Shirley, D.W., Alley, “Journal of the American Chemical Society” (D.A.
, 5hirley, D.W., AIIey, J.Am.
er, Chem, Soc, ), 79.4922 pages (
1954), A. Wohl, W. Marchwald, Beritzchte (A. Wohl, W. Marchwald,
Her, ) ()'In Chemical Society Journal) Volume 22, 568
Page (1889), “Journal of the American Chemical Society” (J. Ag+er, Chem, Soc,) 44.1502~
1 [1 page, U.S. Patent No. 3,017.270, British Patent 9
No. 40,159, Special Publication No. 49-8334334, 1977
No. 5-59463, Advanced in Heterocyclic Chemistry
erocyclic chemistry), 9
．． pp. 165-209 (1968), West German Patent 2,71
No. 6,707. The Chemistry of Heterocyclic Compounds, Imidazole and Derivatives
Cbemistry of Heterocycle
c Co*poun-ds, lm1dazole
and Derivatives), Vol.
l384 pages, Organic Synthesis (Org, 5
ynt-h,) IV, p. 569 (1963),
Berichte (Ber, ),” p. 465 (1975)
, “Journal of the American Chemical Society” (J, Amer, Chem. Soc,) 45, p. 239 (1923), JP-A-5
No. 0-89034, No. 53-28426, No. 55-2
No. 1007, Special Publication No. 40-28496, etc. When the compound of the present invention is used in a bleaching solution,
Although it varies depending on the type of compound, in general, bleaching solution 11
It may be 0.5+sg to 20g per serving, but especially 11mg to 5
It is preferable to add g. When the bleaching solution according to the present invention contains at least one of imidazole and its derivatives as described below or compounds represented by the following general formulas [11 to [IX], the desired effects of the present invention are better achieved, Furthermore, the present invention has the additional effect of improving precipitation caused by silver in the bleaching solution. More preferably used. General formula [Ico[In the formula, Q represents an atomic group necessary to form a nitrogen-containing heterocycle (including those in which 5- to 6-membered unsaturated rings are condensed), R8 is a hydrogen atom, Alkyl group having 1 to 6 carbon atoms, cycloalkyl group, aryl group, heterocyclic group (5 to 6
[11] In the formula E, R1 and R3 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, carboxy group,
Amino group, acyl group having I to 3 carbon atoms, aryl group,
Or represents an alkenyl group. A represents an or n1-valent heterocyclic residue (including those in which 5- to 6-membered unsaturated rings are condensed), and X is =S, =0, or =N
Here, R and R' have the same meaning as R8 and R1, respectively, X' has the same meaning as X, and Z represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue, an alkyl Represents a group, R'' hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue (including those in which 5 to 6 Ji unsaturated rings are fused) or represents an amino group% n, ~n,
and +111'''-Ill each represent an integer from 1 to 6. and R5 may each represent -B-9Z, and R, and R1, R and R', R, and R1 are each bonded to form a ring. In addition, the compound represented by this formula also includes ethanolated products and salts thereof. General formula [I[1] In the formula, R6 and R? are a hydrogen atom and the number of carbon atoms, respectively. 1 to 6 alkyl groups, hydroxy groups, carboxy groups,
Amino group, acyl group having 1 to 3 carbon atoms, aryl group,
It represents an alkenyl group or -B, -, Zl represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue, and R1/ represents -S-B, -Y. n is an integer from 1 to 6\R? represent. ] General formula [IV] In formula 1, R1 and R represent each, and R+o is an alkyl group or -(C1lt)nss
Represents Os e. (However, R1゜ is -(CH*)nms
When Ose, Q represents 0, and when it is an alkyl group, Q represents 1. )Ge represents an anion. n represents an integer from 1 to 6. ] General formula [v] [In the formula, Q represents an atomic group necessary to form a nitrogen-containing heterocycle (including those in which 5- to 6-membered unsaturated rings or saturated rings are condensed), and R1 , is a hydrogen atom, an alkali metal atom, and Q' is synonymous with Q. ] General formula [Vl] [In the formula, D6, DI, D, and D4 each represent a simple bond, an alkylene group having 1 to 8 carbon atoms, or a vinylene group, and Q+, q8, Qs, and q4 each represent 0
．． Represents 1 or 2. Further, the ring formed together with the sulfur atom may be further condensed with a 5- to G-membered saturated or unsaturated ring. General formula [■] R + R + 4 I Rlt R + s R11 In the formula, X t H COOM ', -H, -OH
. 505M', C0NHz, -5OrNHt. -N Hz, -S H, -CN, C0tRr
a, -S O-Rls, ORre, N R+sR
, t, -S RI-, -S O-R, a, -NH
COR, #. -NH5OtR1s, -0COR+* or -8OeR+
*, Y represents R+s R+fiR+ or a hydrogen atom, m and n each represent 1 to 10
represents an integer. Rll+ Rjl+ R+s, R14+
RIIl+ R1 and R1 each represent a hydrogen atom, a lower alkyl group, an acyl group, or a kyl group, and R1 is -N RtoRttlo Rt
t or -8R□, R3° and RlI each represent a hydrogen atom or a lower alkyl group, and R□ represents an atomic group necessary to form a ring by bonding with R1. RlO or R21 may be combined with R+s to form a ring. M' represents a hydrogen atom or a cation. ] General formula [■
] 1? ts RlO (H)x (G・)z (H)y In the formula, Ar is a divalent aryl group or 2 which is a combination of an aryl group and an oxygen atom and/or an alkylene group.
B and B each represent a lower alkylene group, R, , R, , R□ and Rta each represent a hydroxy-substituted lower alkylene group, K and y
represents 0 or 1, respectively. G' represents an anion, 2
represents 0, 1 or 2. ] General formula [IX] iI [wherein Rf and R5° each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, R31 represents a hydrogen atom or an alkyl group, and R32 represents a urea atom or a carboxy represents a group. ] Compounds represented by general formulas [I] to [IX] preferably used in the present invention or imidazole and its derivatives as described below are compounds generally used as bleach accelerators, and hereinafter, the bleach accelerators of the present invention That's what it means. Typical specific examples of the bleaching accelerator of the present invention represented by the general formulas [11 to []X] include, but are not limited to, the following. Exemplified compound (J-5) (1-6) C1t C
H! C00TI CI-7) (1-8)(I
t-1) (II-2) (n-3) (It-4) (II-5) S ≧ )1. N-C5NIINHCS-N1(t(n-7))1tN-CSNH(CHz)JHC3-NHt(It
-8) (II-9) (II-10) '(II-11) (It-12) (II-13) (II-14) (It-15) (It-16) (II-17) ( n-18) (II-19) (II-20) (II-21) (II-22) ■ (II-24) (II-25) (II-26) (II-27) (I[1- 1) (I
[l-2) (Ill-3)
(I[l-4) (In-5)
(I[l-6) (I[1-7)
(I[l-8) (I[-9)
(II-1o) (Ill-11) Cm-12) (I[I-13) Cml-13 ) C[l-35) (V-1) (V-2) (
V-3> (V-4)
(V-6) (V-7) (V-
8) (V-9) (V-1
0) (V-11) NH! (V-12) (V-13
)(V-14) (V-15) (V-16) (V-18) (V-21) (V-2
2) (V -23) H (V-24) (V-25) (V-26) (V-27) (V-28) (V-29) ■ (V-30) (Vl-1) ( Vl-2)
(Vl-1) (Vl-4) (Vl-5
) (Vl-6) (Vl-7)
(Vl-8) (Vl-,
9) (Vl-10) (W-o)
('Vl-12)11)I (W-+3) (Vl-+4)
(■-+5)ull (Vl-16) (■-17)(■
-1) (■-2) (■-3) (■-4) (■-5) (■-6) (■-7) (■-8) (■-9) (■-10) (■ -11) (■-12) (■-13) HSCH2CH2NCH2C) I? C0NT. CH3 (■-14) H2O) I2CH2H) IGHzCHzOH (■-15
) H5CH2CI2NG)I2GH2OH■ 2H5 (■-1) CHJ(C1bCHtOH)* (■-2) (■-3) CHJ(C1lltCH*OII)t (■-4) @ CHtlfH(CHyCHtOH)t CIIJ(CHzCHtOII)t ( IX-1) (IX-2)
(IX-3) (IX
-4) (ff-5) +1 Below margin imidazole and its derivatives A'-I A'-2 A'-3A' -4 In addition to the bleaching accelerator of the present invention exemplified above, patent application No. 6O-
Exemplary compound No., I-2, I-4-7, I-9-1 described on pages 51 to 115 of the specification of No. 21i3568
3. l-16~21, ■-23, ■-24, 1-25,
27, Knee 30-36. l-38, ll-2~5゜II
-7~10, ■ -12~20. ll-22~2
5. ll-27, ■-29 to 33, H-35, 36
, 11-38-41. ll-43, ■-45~55,
■-57~60, ■-62~64, ■-67~71, I
9g to I-73&-79, ■-81 to 84, ■-86
, 11-101, 102, II-104-110.
If-112~119, ll-121~124, l
l-125, ll-128 to 144. ll-145,
H-148-155. ll-157, m-4, I[
I-6~8, [-10,11, ■-13, m-15~1
8, III-20, ■-22, ■-23, m-25,
m-27, ■-29 to 32, m-35, 36, IV-3
, ff-4, V-3~6°V-8~14, V'-11i
~311. V-40~42. V-44~46, ■
-48~66, ■-68~70, ■-72~74°V-
76-79. V-81, 82, V-84~100
, V-102~108. V-110, V-11
2,113, V-116~119, V-121~12
3, V-125-130. V-132 to 144, V-
146~162, V-164~+74, V-176~1
84, ■-4, ■-7, Vl-10, 71-12,
Vl-13, VT-16,7'1-19. Vl-2
1,■-22. Vl-25゜■-27~34, ■-36
, ■-3, ■-6. ■-13, m=19, VIr-20
and exemplified compounds (m-2) to ([-3) described on pages 22 to 25 of JP-A No. 6.3-17445,
(m=5) ~(m-10), (m-12) ~(+11
1-45), (m-47) to (m-50>, Cm-5
2) to (m-54), (Illr-563~(
Compounds such as m-63) and (III-65) can also be used similarly. These bleach accelerators may be used alone or in combination of two or more, and the amount added is generally about 0 per 12 bleaching solutions.
．． Good results are obtained in the range of 0.01 to 100 g. However, in general, if the amount added is too small, the bleaching promotion effect will be small, and if the amount added is too large, precipitation may occur and contaminate the photosensitive material being processed. The amount is preferably 0.05 to 50 g per liter, and more preferably 0.05 to 15 g per 11 of the bleaching solution. The general formulas [S-I] to [S-U] and [I] to [IX
] When adding the represented compound to a bleaching solution, it may be added and dissolved as is, but it is common to dissolve it in water, alkali, organic acid, etc. before adding it, and add methanol as necessary. It can also be added after being dissolved in an organic solvent such as ethanol, acetone, or the like. The processing temperature of the bleach solution of the present invention is 20°C to 45°C, preferably 25°C to 42°C. In the bleaching solution of the present invention, a halide such as ammonium bromide is usually added. It is possible to make the concentration. Lowering the concentration of the halide also has the effect of preventing thickening of the kit and precipitation of the oxidizing agent. Another effect is that silver sludge is less likely to occur. The halides used in the present invention include ammonium chloride, sodium chloride, potassium chloride, ammonium bromide,
Examples include sodium bromide and potassium bromide, but ammonium chloride and ammonium bromide are preferred. In particular, ammonium bromide has a great effect of promoting bleaching and is preferably used. The halide concentration is between O.OS and 3 moles per liter of bleach solution, preferably 0.00. lO to 2.0 mol, particularly preferably 0
, 15 to 1.5 moles. The bleaching solution of the present invention includes various salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. pH
The H buffering agent may be contained alone or in combination of two or more. In addition, various optical brighteners, antifoaming agents, or surfactants can be contained. In order to highly effectively achieve the object of the present invention, the bleaching solution of the present invention preferably contains an Il buffer, particularly a buffer having a buffering capacity at rpH 3 to 7. Such a buffer having a buffering capacity at pH 3 = 7 is a buffer that requires the addition of 2 CO2 at a rate of 5 g/Ji or more in order to change the ρ11 value of an aqueous solution containing a certain amount of buffer from DH3 to p117. Preferably used buffering agents include the following general formula [III, [Xml or [Xml
Examples include organic compounds represented by the formula and inorganic compounds such as compounds containing at least 61 nitrogen, phosphorus, or boron atoms. General formula [III -COOH In the formula, A represents a hydrogen atom or an organic compound group. General formula [X II ] B-PO3)+2 In the formula, B represents a hydrogen atom or an organic compound group. General formula [Xml In the formula, C'', D, and E each represent a hydrogen atom or an organic compound group, provided that at least one of C', D, and H is an organic compound group. Specific examples of buffers used are listed below. Preferred compounds as fatty acids are acrylic acid. Adipic acid, acetylene dicarboxylic acid, acetoacetic acid, azelaic acid, isocrotonic acid, isopropylmalonic acid,
Isobutyric acid, itaconic acid, isovaleric acid, ethylmalonic acid,
Caproic acid, formic acid, valeric acid, citric acid, glycolic acid,
Glutaric acid, crotonic acid, chlorfumaric acid, α-chloropropionic acid, gluconic acid, glyceric acid, β-chloropropionic acid, succinic acid, cyanacetic acid, diethyl acetic acid,
Diethylmalonic acid, dichloroacetic acid, citraconic acid, dimethylmalonic acid, oxalic acid, d-tartaric acid, ff1eso-
tartaric acid, trichlorolactic acid, tricarballylic acid, trimethylacetic acid, lactic acid, vinylacetic acid, pimelic acid, and tartaric acid,
Vucic acid, fumaric acid, propionic acid, propylmalonic acid, maleic acid, malonic acid, mesaconic acid, methylmalonic acid, monochloroacetic acid, n-acetic acid, malic acid, aspartic acid, DL-alanine, glutamic acid, 3,3-dimethyl -Glutaric acid, etc. Preferred compounds with acids having a cyclic structure include ascorbic acid, atrobeic acid, allocinnamic acid, benzoic acid, isophthalic acid, oxybenzoic acid (m-, p-), chlorobenzoic acid (o
-, m-1p-), chlorphenylacetic acid (0-1ts-
, p-), cinnamic acid, salicylic acid, dioxybenzoic acid (2,3, 2,4, 2,5, 2,6, 3,4,3,5)
, cyclobutane-1,1-dicarboxylic acid, cyclobutane-1,2-dicarboxylic acid (Trans-1Cis-)
, cyclopropane-1,1-dicarboxylic acid, cyclopropane-1,2-dicarboxylic acid (Trans-, C15-
), cyclohexane-1,1-dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid (Trans-1Cf
s-), cyclohexyl acetic acid, cyclopentane-1,
1-dicarboxylic acid, 3,5-dinitrobenzoic acid, 2,
4-dinitrophenediphenylic acid, sulfanilic acid, terephthalic acid, toluic acid (0-, m-1p-), naphthoic acid (α-1β-), nicotinic acid, nitroanisole (o-, ta-1p-), nitro Acrylic acid, nitrophenylic acid #(o-, ■-, p-), p-nitrophenethol. Pyromucic acid, uric acid, hippuric acid, barbituric acid, picolinic acid, booruric acid, phenylacetic acid, phenyl acid, phthalic acid, fluorobenzoic acid (0-1o-1p-), bromobenzoic acid (0-1o-2p-) ), hexahydrobenzoic acid, benzylic acid, dfL-madelic acid, mesitylenic acid, methoxybenzoic acid (0-1-, p-), methoxycinnamic acid (
o-1I-1p-), p-methoxyphenylacetic acid,
Examples include gallic acid and aminobenzoic acid (o-11-1p-). Preferred amine compounds include isoamylamine, isobutylamine, isopropylamine, ethylamine, ethylenediamine, diisoamylamine, diisobutylamine, diethylamine, diethylenetriamine, dipropylamine, dimethylamine, tetraethylenepentamine, tetramethylenediamine, triethylamine, Trimethylamine, trimethyldiamine, ■-
Butylamine, 5ec-butylamine, tert-butylamine, ■-propylamine, pentamethylenediamine, hexamethylenetetramine, quinoline, o-)luidine, aminobenzenesulfonic acid (0-11-1p-
), N-methylbenzylamine, methylbendifuramine (〇-di-1, p-), 2-methylhyberidine, N-methoxybenzylamine, methoxybenzylamine (o-, ta-, p-), benzylamine, conine , diethylbenzylamine, cyclohexylamine, piperazine, etc. Preferred inorganic acids are nitrous acid and phosphorous acid. Examples include hypophosphorous acid, boric acid, phosphoric acid, birophosphoric acid, triphosphoric acid, metatriphosphoric acid, polyphosphoric acid, and polymetaphosphoric acid. Other preferred organic compounds include R-(2-acetamido)iminodiacetic acid, N-(2-acetamido)
-2-aminoethanesulfonic acid, bis(2-hydroxyethyl)iminotris(hydroxymethyl)methane,
2-(N-morpholino)ethanesulfonic acid, 3-(N
-morpholino)-2-hydroxypropanesulfonic acid,
Piperazine-N,N'-bis(2-ethanesulfonic acid)
, ethylenediamine diacetic acid, ethylenediamine-2-propionic acid, β-aminoethiiminoniacetic acid, etc.
Other preferable organic phosphoric acids include aminomethylphosphonic acid-N,N-diacetic acid, 2-phosphonoethyliminodiacetic acid, 2-phosphonobutane-1,2,4-)-ricarboxylic acid, and the following ( P-1) ~ (P-:I4)
Examples include: Among these, fatty acids, acids with a cyclic structure, amine compounds, and inorganic salts are more preferred, and fatty acids and amine compounds are particularly preferred. Among organic acids, acetic acid is slightly less effective than the above-mentioned compounds.
Preferably, when 50% (molar ratio) or more is the ferric complex salt of the compound represented by the general formula [A], or when the compound represented by the general formula [A]
The ferric complex salt of the compound represented by A] is 0.2 mol/f
If it is more than L, use 0.5 to 3 mo with high acetic acid content.
It has been found that a l/i range, preferably a range of 0.8 to 2 mol/liter, is extremely effective for liquid stability (floating object prevention effect). CH-Cool ( CH2-PO3H2 CP-11) (P-15) 05H2 ■ PO3H2 CH2COOH When the processing solution having fixing ability according to the present invention is a bleach-fix solution, the bleaching agent used in the bleach-fix solution is: Ferric complex salts of aminocarboxylic acids or aminophosphonic acids are preferred; the aminocarboxylic acids and aminophosphonic acids are amino compounds having at least two or more carboxylic acid groups and amino compounds having at least two or more phosphonic acid groups, respectively. represents a compound, preferably represented by the following general formula [XXr
] and [XXII]. General Formula [XXI] General Formula [XXff] In the formula, E is a substituted or unsubstituted alkylene group. 2 represents a cycloalkylene group, a phenylene group, -Ra5ORazORaz-1-RaJRaz-, 2 represents) N-R8: +-As, ) N-As, and R? , ~R63 represents a substituted or unsubstituted alkylene group, A, ~A6 are hydrogen atoms, -OH1-C00M, -
POJ, and 2M represents a hydrogen atom or an alkali metal atom. Next, preferred specific examples of the compounds represented by the general formulas [XXI] and [XXI[] are listed below. [Exemplary Compound II] [XXl-11 ethylenediaminetetraacetic acid [XX[-
2] Diethylenetriaminepentaacetic acid [XXr-3]ethylenediamine-N-(β-hydroxyethyl)-N,
N', N''-) diacetic acid [XXl-4] 1,3-propylenediaminetetraacetic acid [XX[-5] triethylenetetraminehexaacetic acid [XXl-'6]cyclohexanediaminetetraacetic acid [XX[-7]1 .2-Diaminopropanetetraacetic acid [XXl-8]1,3-diaminopropane-2-ol-tetraacetic acid [XX[-9]ethyl ether diaminetetraacetic acid [X
XI-101 Glycol ether diamine tetraacetic acid [X
r-13] Ethylenediaminetetraacetic acid disodium salt [XXl-14] Ethylenediaminetetraacetic acid tetra(
trimethylammonium) salt [XXl-15] Ethylenediaminetetraacetic acid tetrasodium salt [XXl-16] Diethylenetriaminepentaacetic acid pentasodium salt [X XI-17] Ethylenediamine-N-(β-hydroxyethyl)-N, N', N' -Triacetic acid sodium salt [X Methylenephosphonic acid [XXI-22]Cyclohexanediaminetetramethylenephosphonic acid [X)
l-4] Nitrilotripropionic acid [XXI[-5] Nitrotrimethylenephosphonic acid [XX[[-6] Iminodimethylenephosphonic acid [X■-7] Hydroxyethyliminodimethylenephononic acid [XXI[-8] Nitrilotripropionic acid Trisodium acetate salt Among these aminocarboxylic acids and aminophosphonic acids, compounds particularly preferably used from the viewpoint of the desired effects of the present invention include (XX[-1), (XXI-2), (XX[-
4), (XXI-6), (X)ff-7), (X
-10), (XX[-19), (XX[[-1),
(XXll-5) is mentioned. Among these, particularly preferred from the viewpoint of the desired effects of the present invention are (X
XI-4). The ferric complex salt of an organic acid according to the present invention is a free acid (hydrogen salt), an alkali metal salt such as a sodium salt, a potassium salt, a lithium salt, or an ammonium salt, or a water-soluble amine salt such as a triethanolamine salt. etc., but potassium salts, sodium salts and ammonium salts are preferably used. At least one type of these ferric complex salts may be used, but two or more types can also be used in combination. The amount to be used can be arbitrarily selected and needs to be selected depending on the amount of silver and silver halide composition of the photosensitive material to be processed. For example, bleach-fix solution 1! 0.01 per L
It can be used in a mole or more, preferably 0.05 to 1.0 mole. Note that it is desirable to use the replenisher in a highly concentrated form with the highest solubility in order to achieve high concentration and low replenishment. The preferred replenishment amount of the bleaching solution according to the present invention is 20 to 500 g per rn' of silver halide color photographic light-sensitive material.
(2), particularly preferably 301 to 350, and even more preferably 40 to 300
- stand, most preferably 50tJL to 250a
I see it. A so-called fixing agent is essential to the fixing solution and bleach-fixing solution according to the present invention. As fixing agents, compounds which react with silver halides to form complex salts in aqueous solution, such as thiosulfates such as potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate;
Examples include thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, thioethers, and the like. Ammonium sulfate is preferably used as it is good as a fixing agent. In addition to these fixing agents, fixing solutions and bleach-fixing solutions include boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate,! i) A pHI buffer consisting of various salts such as potassium carbonate, acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination. Furthermore, alkali halide or ammonium halide 1 to 1
For example, it is desirable to contain large amounts of rehalogenating agents such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, etc., and pH buffering agents such as borates, oxalates, acetates, carbonates, and phosphates. , alkylamines, polyethylene oxides, etc., which are known to be added to ordinary fixing solutions and bleach-fixing solutions, can be appropriately added. The fixing agent is used in an amount of 0.1 mol or more per processing solution, preferably in the range of 0.6 mol to 4 mol, particularly preferably 0.9 mol to 3.0 mol, from the viewpoint of the desired effect of the present invention. molar range, particularly preferably from 1.1 mol to 2.0 mol
Used in the molar range. In the present invention, in order to increase the activity of the bleach solution or bleach-fix solution, air or oxygen may be blown into the processing bath and processing replenisher storage tank as desired.
Alternatively, a suitable oxidizing agent such as hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate. When carrying out the method of the present invention, silver may be recovered from the fixer or bleach-fixer by known methods. For example, electrolysis method (described in Buddhist Patent No. 2,299,667), precipitation method (described in JP-A-52-73037, second patent No. 2,331,220), ion exchange method (described in JP-A No. 2,331,220) The metal substitution method (described in British Patent No. 1,353,805) and the like can be effectively used. It is particularly preferable to recover silver in-line from the tank solution, as this improves suitability for rapid processing, but it is also possible to recover silver from the overflow waste solution and reuse it. The fixing solution and the bleach-fixing solution according to the present invention exhibit the desired effects of the present invention better when the replenishment amount thereof is 800 m or less per rn' of light-sensitive material. In particular, photosensitive material 1 hit 650 meters in 2011, especially 30 meters in particular.
Obtain remarkable effects when using 400 layer sentences. °Also, when the fixing solution and bleach-fixing solution according to the present invention contain 0.1 g/l to 10 g/l of iodide (ammonium iodide, potassium iodide, sodium iodide, lithium iodide, etc.), This further enhances the effects of the present invention. Especially 0.3g
/l~Sg/l, especially 0-5g/text~3g/l
Good results are obtained, most preferably between 0.8 g/Jl and 2 g/Jl. When a compound represented by the following general formula [FA] or a compound of the following compound group [FB] is added to the processing liquid (fixer or bleach-fixer) having fixing ability according to the present invention, the present invention is applied. Not only does it achieve the desired effect better, but also
It is more preferably used in the present invention because it promotes the effect that very little sludge is generated when a small amount of light-sensitive material is processed over a long period of time using a fixer or a bleach-fixer. (wherein R' and R'' each represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or a nitrogen-containing heterocycle,
(n' represents 2 or 3) Specific exemplary compounds represented by the general formula [FA] are shown below. These compounds represented by the general formula [FA] are
, 335,181 and U.S. Pat. No. 3,260,7
It can be synthesized by a general method as described in the specification of No. 18. Compound group [FB] FB-1 Thiourea FB-2 Ammonium iodide FB-3 Potassium iodide FB-4 Ammonium thiocyanate FB-5 Potassium thiocyanate FB-6 Sodium thiocyanate FB-7 Thiocyanocatechol These, the above-mentioned general The compound represented by the formula [FA] and the compound of the compound group [FB] may be used alone,
Also, two or more types may be used in combination. For example, thiourea, ammonium thiocyanate and ammonium iodide, thiourea and ammonium thiocyanate, (FA-12)
and thiourea, (FA-12) and ammonium thiocyanate, (FA-12) and ammonium iodide, (FA-
12) and (FA-32), (FA-12) and (F
A-38) etc. are mentioned as preferred examples. Further, the addition amount of the compound represented by the general formula [FA] and the compound of the compound group [FB] is 0.00% per 1 fL of the treatment liquid.
Good results are obtained in the range of 1 g to 200 g. Particularly preferred is a range of 0.2g to 100g, and 0.2g to 100g.
Particularly preferred is a range of 5g to sob. The pH of the bleaching solution of the present invention is in the range of 2 to 8, preferably in the range of 13 to 7 from the viewpoint of the effects of the present invention, and particularly preferably in the range of 4 to 6. Most preferably the pH is in the range of 4.5 to 5.8. The pH of the fixing solution and bleach-fixing solution used in the present invention is in the range of 4 to 8. Sulfites and sulfite-releasing compounds according to the invention include potassium sulfite, sodium sulfite, ammonium sulfite, ammonium bisulfite. Potassium hydrogen sulfite, sodium hydrogen sulfite, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, and the like can be mentioned. Furthermore, the following general formula [B-
1] or [B-2] are also included. General formula [B-1] F: +5 R17-C-OH Kan03M General formula [B-2] In the formula, R17 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
R18 is an optionally substituted carbon a1-5 alkyl group,
X is an alkali metal atom, R19 and R20 are hydrogen atoms or optionally substituted alkyl groups having 1 to 5 carbon atoms, n is 0
Represents an integer of ~4. Specific examples of compounds represented by the above general formulas are described below, but the present invention is not limited thereto.Hereinafter, compounds represented by general formulas [E-1] and [B-2] A preferred specific example is shown below. B-1 Formaldehyde Sodium bisulfite B-2 Acetaldehyde Sodium sulfite B-3 Propionaldehyde! ! Sodium sulfite B-4 Butyraldehyde Sodium bisulfite B-5 Succinic aldehyde Sodium bisulfite B-6 Glutaraldehyde Sodium bis bisulfite B-7 β-Methylglutaraldehyde Sodium bis bisulfite B-8 Maleic acid dialdehyde Sodium bis bisulfite These sulfites and sulfite-releasing compounds are required in an amount of at least 0.1 mole as sulfite per 12 mols of fixer or bleach-fix solution, preferably in the range of 0.12 mol/1 to 0.65 mol/cross; 15 mol/cross to 0.50 mol/
Particularly preferred is a range of 0.20 mol/l, especially 0.20 mol/l.
The range is preferably from 1 to 0.40 mol/liter. However, the number of moles of these sulfites and sulfite-releasing compounds are shown in values converted to sulfite. The total processing time of the bleaching solution and the processing solution (fixing solution or bleach-fixing solution) having fixing ability according to the present invention is preferably 3 minutes and 45 seconds or less, and the total time is more preferably 20 seconds to 3 minutes and 20 seconds. The desired effects of the present invention are best achieved when the duration is particularly preferably from 40 seconds to 3 minutes, particularly preferably from 60 seconds to 2 minutes and 40 seconds. Further, the bleaching time can be arbitrarily selected within the above-mentioned total time range, but from the viewpoint of the desired effect of the present invention, it is preferably 1 minute and 30 seconds or less, particularly 10 seconds to 70 seconds. The processing time of the processing liquid having a fixing ability, which is particularly preferably 20 seconds to 55 seconds, can be arbitrarily selected within the above-mentioned total range, but from the viewpoint of the desired effect of the present invention, it is preferably 3 minutes.
0 seconds or less, particularly preferably in the range of 10 seconds to 2 minutes 40 seconds, particularly preferably 20 seconds to 2 minutes
It is in the range of seconds. In the processing method of the present invention, it is preferable to apply forced liquid agitation to the bleaching solution, fixing solution, and bleach-fixing solution. This is from the perspective of The term "forced liquid stirring" as used herein means adding a stirring means to forcibly stir the liquid, rather than the usual diffusion and movement of the liquid. Examples of forced stirring means include the following methods. 1. High-pressure spray treatment method or spraying is a stirring method 2. Air bubbling treatment method 3. Ultrasonic oscillation treatment method 4. Vibration treatment method High-pressure spray treatment method refers to a discharge pressure of 0.1 kg/am''
Refers to a method in which processing is performed by spraying a processing liquid directly onto the photosensitive material from a spray nozzle while applying the above pressure.
The agitation method for spraying means that the discharge pressure from the nozzle is 0.1 kg/
Directly pour the processing liquid into the processing liquid by applying a pressure higher than crn',
This refers to a method of processing photosensitive materials by spraying them, and generally a pressure pump or a liquid pump is used as the pressure source. Pressure pumps include plunger pumps, gear pumps,
There are magnet pumps and cascade pumps, such as the 15-LPM type, 110-111F type, and 2 manufactured by Maruyama Seisakusho.
0-BFM type, 25-BFM type, etc. are known as examples. In addition, as a liquid pump, for example, MD-8 manufactured by Ikki Co., Ltd.
Type, MD-10 type, III-20Rg, MO-3
0Rfi, MD-55R type, MDK-25 type, MDK-
There are 32 types. On the other hand, the nozzle and spray nozzle are straight type. There are fan-shaped, circular, full-face, annular, etc. types, and the stronger the impact force, the more effective it is that it causes slight vibrations to the photosensitive material to be subjected to ζ processing. The impact force of the spray is determined primarily by the flow rate (1/5 inch) and the spray pressure (kg/crn'). Therefore, a pressurizing device is required that can adjust the pressure in proportion to the number of spray nozzles in order to fully exhibit the effect. The most preferable pressure is 0.3 to lokg/crr+'; if the pressure is smaller than this, no effect can be obtained, and if it is too large, the photosensitive material may be scratched or damaged. Next, in the air bubbling processing method, a sparger is installed at the bottom of the lower transport roller of the processing liquid tank, air or inert gas is sent to the sparger, and the air bubbles discharged from the sparger's mouth vibrate the photosensitive material. Furthermore, this is a method in which the processing liquid is brought into effective contact with the front, back, and side surfaces of the photosensitive material. Suitable materials for the sparger include corrosion-resistant materials such as hard PVC, polyethylene-coated stainless steel, and sintered metal. Even better results can be obtained by changing the value from 5■ to 15■. Air can be supplied using an air compressor, such as Hitachi's Bebicon (0.4KW, BU7L), or an air pump, such as Iwaki's air pump (Ap220y).
f! Examples include ri. The amount of air is 21 per liter rack of automatic developing machine.
/win to 3 (1m /win is required, 5-way /
Even more preferable results can be obtained from 200 to 200 cm. The amount of air or inert gas must be adjusted depending on the size of the processing liquid tank and the amount of photosensitive material. Preferably, an amount of active gas is delivered. Next, the ultrasonic oscillation processing method is a method in which an ultrasonic oscillator is installed in the bottom or side wall space of the processing liquid tank of an automatic processor and irradiates ultrasonic waves onto the photosensitive material to increase the efficiency of development promotion. . As the ultrasonic oscillator, for example, a magnetostrictive nickel vibrator (horn type), a magnetostrictive barium titanate vibrator (holder type), etc. manufactured by Ultrasound Kogyo Co., Ltd. are used. The transducer frequency of the ultrasonic oscillator is 5 to 1000K.
Hz is used, but ultrasonic waves of 10 to 50 K) Iz are preferable in terms of the desired effect of the present invention and damage to automatic processor equipment.As a method of irradiating the photosensitive material with ultrasonic waves, The photosensitive material can be directly irradiated with ultrasonic waves or indirectly irradiated with a reflector, but since the ultrasonic waves attenuate in proportion to the irradiation distance, direct irradiation is preferable, and the irradiation time is at least 1 second. In case of partial irradiation, it may be applied at any of the early, middle, and late stages of the treatment process. Further, the vibration processing method is a method in which vibration is applied to the photosensitive material between the upper roller and the lower roller in the processing liquid tank of an automatic processor to effectively perform immersion processing. As the vibrator for the vibration source, for example, V-2B and V-4B types manufactured by Shinko Electric Co., Ltd. are generally used. The method of installing the vibrator is to fix the vibrator to the upper part of the immersion processing tank of an automatic processor, and install it so that the vibrator is applied from the back side of the photosensitive material. The vibrator of the vibrator is 100 to 10
000 times/sin is preferred, and the most preferred range is 50
0 to 8000 times/sin. The amplitude of the photosensitive material to be processed is from 0.2 to 30 m5, preferably from 1 to 20 layers per layer. If it is lower than this, there is no effect, and if it is too large, the photosensitive material may be damaged. The number of vibrators to be installed varies depending on the size of the automatic processor, but if the processing tank is composed of multiple tanks, a preferable effect can be obtained by installing at least one vibrator in each processing tank. Preferred specific treatment steps of the treatment method according to the present invention are shown below. (1) Color development → bleaching → fixing → washing with water (2) color development → bleaching → fixing → washing → stabilization (3) color development → bleaching → fixing → stabilization (4) color development → bleaching → fixing → first stabilization → first stabilization 2 stable (5
) Color development → bleaching → bleach-fixing → washing (8) color development → bleaching → bleach-fixing → washing → stabilization (7) color development → bleaching → bleach-fixing → stable (8) color development → bleaching → bleach-fixing → first stabilization →Second stability Among these steps, especially (3), (4), (7),
(8) is preferred, particularly (3) and (4). Another preferred embodiment of the processing method of the present invention is a method in which part or all of the overflow solution of the color developing solution according to the present invention is allowed to flow into the bleaching solution that is the next step. This is because when a certain amount of the color developing solution according to the present invention is introduced into the bleaching solution, the generation of sludge in the bleaching solution is improved. The color developing solution according to the present invention includes alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide,
ammonium hydroxide, sodium carbonate, potassium carbonate,
It may contain sodium sulfate, sodium metaborate, borax, etc., and may further contain various additives such as benzyl alcohol, alkali metal silver halide 1 such as potassium bromide or potassium chloride, or a development regulator such as citradinic acid, etc. Hydroxylamine or sulfite or the like may be contained as a preservative. Furthermore, various antifoaming agents, surfactants, and organic solvents such as methanol, dimethylform 7mide, or dimethyl sulfoxide can be appropriately contained. Further, the pH of the developer according to the present invention is usually 7 or more, preferably about 9-13. The color developer used in the present invention may optionally contain antioxidants such as hydroxylamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, pentose, or Hexose, pyrogallol-1,3
-Dimethyl needle etc. may be contained. Further, in the color developing solution according to the present invention, various chelating agents can be used together as a metal ion sequestering agent. For example, the chelating agent may include ethylenediaminetetraacetic acid,
7-minopolycarboxylic acids such as diethylenetriaminepentaacetic acid; organic phosphonic acids such as 1-hydroxyethylidene-1,1-diphosphonic acid; 7minopolyphosphonic acid such as aminotri(methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acid such as citric acid or gluconic acid, phosphonocarboxylic acid such as 2-phosphonobutane-1,2,4-)licarponic acid, tripolyline Examples include acids and polyphosphoric acids such as hexametaphosphoric acid. In the present invention, a method in which treatment is performed with the bleaching solution of the present invention and immediately followed by treatment with a fixing solution or a bleach-fixing solution and a stabilizing solution is preferable in terms of the desired effects of the present invention, particularly in terms of speed, but additional effects may be obtained. As a result, the stability of the processing solution (stabilizing solution) is also improved. The amount of replenishment of the stabilizer according to the present invention is 1 of the amount brought in from the dust pre-bath per unit area of the color photographic light-sensitive material to be processed.
80 times, preferably 2 to 60 times. In the present invention, the concentration of the pre-bath component (bleach-fix solution or fixer) in the stabilizing solution is 17 times in the final stabilizing solution tank.
More preferably 500 or less, particularly preferably 17100
It is less than or equal to 0. Furthermore, from the viewpoint of low pollution and liquid storage stability, 17,500 to 17
100000 is preferable, more preferably 1/200
The processing tank of the stabilization tank is configured so that the number of cells becomes 0 to 1,150,000. The stabilization treatment tank is preferably composed of a plurality of tanks, and the number of the plurality of tanks is preferably 2 or more and 6 or less. The effect of the present invention is that there are cases where the number of stabilization treatment tanks is 2 or more and 6 or less, and that the countercurrent method (a method in which supply is supplied to the rear bath and overflows from the front bath) is used.
In particular, it is preferable to use 2 to 3 tanks, and more preferably 2 tanks, which is particularly preferable from the viewpoint of reducing pollution and improving image preservation. The amount brought in depends on the type of photosensitive material, the conveyance speed of the automatic processor,
Although it varies depending on the transportation method, squeezing method for the surface of the photosensitive material, etc., color photosensitive materials for photography usually use color film (
roll film). The usual carry-on amount is 50mu/rn' ~150m1
/ m'', and the replenishment amount at which the effect of the present invention is more remarkable on this amount brought in is 50 or / m'' ~ 4.01
/rrl, and the most effective supplementation amount is 20
It is in the range of 01 min/rn' to 1500 min/rrl. The treatment temperature for the treatment with the stabilizing solution is preferably in the range of 15 to 60°C, preferably 20 to 45°C. In addition, the stabilizer according to the present invention contains the following general formula [■'
It is preferable to include chelating agents represented by ] to [■'] in order to improve whiteness in unexposed areas and prevent yellow staining of dye images after storage. General formula [■'] (wherein, E is an alkylene group, a cycloalkylene group, a phenylene group, -Rs-0-Rs-1-R5-0-R5-0
-Rs- or -Rs-Z-Rs-, Z is〉GR5
-^5゜R3 each represents an alkylene group, ^1~A
3 represents -COO)1 or -PO3M2, respectively;
A4 and A5 are hydrogen atoms, hydroxyl groups, -COOM, respectively
or 0M representing -PO3M2 represents a hydrogen atom or an alkali metal atom) General formula [V1N'1 (wherein, R7 is an alkyl group, an aryl group, or a nitrogen-containing 6
represents a membered ring group, represents a hydrogen atom or an alkali metal atom) General formula [IX'1 (wherein, R8, R9 and RIO are each a hydrogen atom, a hydroxyl group, -coox, -PO3>12, or an alkyl group) , B l* B 2 and B3 are hydrogen atoms, respectively.
hydroxyl group. Atom, alkyl group, -C2840H or -PO: 1M
0M representing 2 represents a hydrogen atom or an alkali metal atom, and n and 0 represent O or 1, respectively. Below is the general formula [■′],

Some specific examples of chelating agents represented by [■'], [] CHs: )1,0.P-C-PO,)11 POJ. POsll* )IO-C-cn. 0OH OJt 0-C1 HOOCCTlt PO,1IIs )10-C-11 1100C-C-I+ PO,11° POsH* +10- C-C0OH 11- C-Cool POsH* HC-COOH HC-COOH C)I, C0OH" CI -C0OH CI -Coo)1 POJ. CH, C00I+ L HOOCC, +(, -C-C00II [Po3 is also CH. CHt C00H CIi, CD0B ■ cncu, coon CHPOslb ■ 0Jt ci, coon CD. C, B, -C-POJ. ■ CHy C0OH CH-C , Hs HOOC-C-C0OH CHsPOsHt C)l , Cool CEII. CTl-C00I+ Po, 11 attack C)l, C00I1 C)ICOOH C,lI-C-C00)! P.O.,)I. ' C) ltPOsHt C) IfP03Hz +1tosP CPOsHt 0) I C1,OH H,0,P-C-PO,Il. OH OH H, O, P-C-PO3H. Hy C)! . 0Jt CIltPOsl* C11-C0OH cm, coon CHt-C0OH Ht ++00c -C-PO,Il. 911°C)I I C00H OHO)l 0H The chelating agent preferably used in the above stabilizing solution is preferably used in an amount of 0.01 to 100 g, more preferably 0.05 to 50 g, and particularly Preferably 0.1-20. It is. Further, the pH value of the stabilizer preferably used in the present invention is preferably in the range of pn 4-0 to 9.0 for the purpose of improving the image storage stability of the effect of the present invention. More preferably the pH is in the range of 4-5 to 8.0, particularly preferably p)! It is in the range of 5.0 to 8.5. The stabilizing solution preferably used in the present invention may contain any of the generally known alkaline agents or acidic agents. Acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.),
pH adjusters (phosphates, borates, hydrochloric acid, sulfates, etc.)
, surfactant, preservative, Bi, Mg, Zn, Ni,
A1. Metal salts such as Sn, Ti, Zr, etc. can be added. The amount of these compounds to be added is necessary to maintain the pH of the stabilizing bath according to the present invention, and in any combination that does not adversely affect the stability of color photographic images during storage and the occurrence of precipitation. I don't mind. Anti-spill agents preferably used in the stabilizer of the present invention include hydroxybenzoic acid ester compounds, phenolic compounds,
Thiazole compounds, pyridine compounds, guanidine compounds, carbamate compounds 1 morpholine compounds,
These include quaternary phosphonium compounds, ammonium compounds, urea compounds, isoxazole compounds, propanolamine compounds, sulfamide compounds, amino acid compounds, active halogen-releasing compounds, and penttriazole compounds. The hydroxybenzoic acid ester compound includes methyl ester, ethyl ester, propyl ester, butyl ester, etc. of hydroxybenzoic acid, preferably n-butyl ester, isobutyl ester, propyl ester of hydroxybenzoic acid, and more preferably This is a mixture of the hydroxybenzoic acid esters 31a. The phenolic compound preferably used as anti-spike agent for Kimitsuaki is a compound that may have an alkyl group, a halogen atom, a nitro group, a hydroxyl group, a carboxylic acid group, an amino group, a phenyl group, etc. as a substituent, Preferably ortho phenylphenol and orthocyclohexyphenol,
These are phenol, nitrophenol, chlorophenol, cresol, guaiacol, and aminophenol. Particularly preferably, ortho-phenylphenol exhibits remarkable anti-spiking properties in combination with bisulfite adducts of aldehyde derivatives. The thiazole compound is a compound having a nitrogen atom and a sulfur atom in a five-membered ring, and is preferably 1,2-benzisothiazolin 3-one, 2-methyl-4-isothiazolin 3-one, or 2-octyl-4-yn. These are thiazolin 3-one, 5-chloro-2-methyl-4-thiazolin 3-one, and 2-chloro-4-thiazolyl-penzimidazole. Specifically, the pyridine-based compounds include 2,6-dimethylpyridine, 2,4.8-)limethylpyridine, and dimethylpyridine.
-Pyridinethiol-1-oxide and the like, preferably radium-2-pyridinethiol-1-oxide. Specifically, guanidine compounds include cyclohexidine,
Examples include polyhexamethylene biguanidine hydrochloride, dodecylguanidine hydrochloride, etc., and dodecylguanidine and its salts are preferred. Specifically, the carbamate compound is methyl-1-L/
Examples include tylcarbamoyl)-2-benzimidazole carbamate and methylimidazole carbamate. Specific examples of morpholine compounds include 4-(2-nitrobutyl)morpholine and 4-(3-nitrobutyl)morpholine. Quaternary phosphonium compounds include tetraalkylphosphonium mounds, tetraalkoxyphosphonium salts, etc.
Preferably, it is a tetraalkylphosphonium salt,
More specific preferred compounds are tri-n-butyl-tetradecylphosphonium chlorite and triphenyl nitrophenylphosphonium chloride. Specific examples of quaternary ammonium compounds include benzalkonium salts, benzethonium salts, tetraalkylammonium salts, alkylpyridium salts, and specific examples include dodecyldimethylbenzylammonium chloride, dodecyldimethylammonium chloride, and laurylpyridinium chloride. etc. Specifically, the nuclear compounds include N-(3,4-dichlorophenyl)-N'-(4-chlorophenyl) urine 1N-(
Examples include 3-)lifluoromethyl)-N'-(4-chlorophenyl)urea. Specific examples of isoxazole compounds include 3-hydroxy-5-methyl-isoxazole. Propatur amino compounds include *n-F'O ha/-ols and isopropatol, specifically 0L-2-benzylamino-2-propatol, 3-diethylamino-1-propatol, 2-dimethylamino-2-methyl-1-propanol, 3-amino-1-propanol,
Idopropaturamine, diisopropaturamine,
N, todimethyl-isobrobanolamine, etc. Examples of sulfamide compounds include O-nitrobenzenesulfamide, p-aminobenzenesulfamide, 4-chloro-3,5-dinitrobenzenesulfamide, and α-amino-p-toluenesulfamide. A specific example of the amino acid compound is N-lauryl-β-alanine. Active halogen-releasing compounds include sodium hypochlorite, chloramine T dichloroisocyanurate, chloramine B, dichlorodimethylhydantoin, and chlorobromodimethylhydantoin, including sodium hypochlorite, sodium dichloroisocyanurate, trichloroisocyanurate. Acids are preferred. Specific examples of penttriazole compounds include the following. (a) Penztriazole (h) Among the above anti-spill agents, compounds preferably used in the present invention include phenolic compounds, thiazole compounds, pyridine compounds, guanidine compounds, quaternary ammonium compounds, and active halogen-releasing compounds. , a penztriazole compound. Furthermore, from the viewpoint of liquid storage properties, phenolic compounds, thiazole compounds,
These are active halogen-releasing compounds and penztriazole compounds. If the amount of the anti-pie agent added to the stabilizer is less than 0.001 g per liter of the stabilizer, the desired effect of the present invention will not be achieved, and if the amount exceeds 50 g, it will be unfavorable in terms of cost, and the preservation of the dye image will be impaired. Since the stability deteriorates, Q, 0
Used in the range of 0.01 to 50 g, preferably 0.005
~10g is used. In the processing of the present invention, silver may be recovered by various methods from processing solutions containing soluble silver salts such as fixing solutions and bleach-fixing solutions as well as stabilizing solutions. (described in the specification), precipitation method (Japanese Unexamined Patent Publication No. 52
-Described in Publication No. 73037. Alternatively, any material may be used as long as the Ca and Mg ions are reduced to 5 PP layers or less.1 For example, it is preferable to use an ion exchange resin or a reverse osmosis membrane alone or in combination.Ion exchange resins and reverse osmosis membranes are not disclosed. Technical report 87
-1884, but preferably 1
It is preferable to use a strongly acidic H-type cation exchange resin and a strongly basic OH-type anion exchange resin. In the present invention, the salt concentration in the stabilizing solution is 11,000 ppm or less, preferably 800 ppm or less, which enhances the washing effect and is good for improving the white background and preventing pimples. The processing time for the stabilizing solution in the present invention is 2 minutes or less, preferably 1 minute and 30 seconds or less, particularly preferably 1 minute or less, in order to achieve the effects of the present invention, particularly for the processing stabilizing solution. In the method for processing a silver halide color photographic material of the present invention, the average silver iodide content of all the silver halide emulsions in the silver halide photographic material is preferably 0.1 to 15 mol%, More preferably 0.5 to 12 mol%, particularly preferably West German Patent No. 2,331,220
(described in the specification), ion exchange method (Japanese Patent Application Laid-Open No. 51-1711
The method described in Japanese Patent No. 4, the specification of Second Patent No. 2.548,237), the metal substitution method (described in the specification of British Patent No. 1,353,805), etc. can be effectively used. Furthermore, when recovering silver, the soluble silver salt may be collected from the overflow of the processing solution and silver may be recovered by the above method, and the remaining solution may be treated as a waste solution, or a regenerating agent may be added and used as a replenisher or tank processing solution. It is particularly preferred to mix the stabilizing solution, which may be used, with the fixing solution or bleach-fixing solution prior to silver recovery. Further, a treatment in which the stabilizer of the present invention is brought into contact with an ion exchange resin, an electrodialysis treatment (see Japanese Patent Application No. 59-96352), a reverse osmosis treatment (see Japanese Patent Application No. 59-98532), etc. can also be used. Furthermore, it is preferable to use water that has been previously deionized in the stabilizing solution of the present invention, since this improves the anti-piping properties of the stabilizing solution, the stability of the stabilizing solution, and the image storage stability. As a means for deionization treatment, the dielectric constant of the washing water after treatment is 50 p, s/cm or less, and 1 to 6 moles. In the method for processing a silver halide color photographic material of the present invention, the average ikJm diameter of the total silver halide emulsion in the silver halide color photographic material is 2. OILm or less is preferable,
More preferably 0.1 to 1.0 #L11 or less, particularly preferably 0.2 to (1.6 g+*). In the method for processing a silver halide color photographic light-sensitive material of the present invention, Total dry film thickness of all woody colloid layers of the material (hereinafter referred to as the film thickness on the emulsion side)
There is a lower limit to the lower limit depending on the silver halide emulsion, coupler, oil agent, additives, etc. contained, and the preferred film thickness on the emulsion side is 5 to 1.8 JLIl, more preferably 10 to 1.
This is 6 Iho. Further, the distance from the outermost surface of the emulsion surface to the lower end of the emulsion layer closest to the support is preferably 14 ILm or less, and the distance from the emulsion layer to the lower end of the emulsion layer that is different from the emulsion layer in color sensitivity and closest to the support is 10 ILm. End-less is preferred. The photosensitive material according to the present invention uses an internal development method (U.S. Pat. No. 2,376,579) in which a coupler is contained in the photosensitive material.
No. Z, No. 801,171), and any couplers generally known in the art can be used.For example, cyan couplers are based on naphthol or phenol structure, and indoanisine can be formed by coupling. Examples of the magenta couplers include those having a 5-pyrazolone ring having an active methylene group as a skeleton structure and pyrazoloazole-based ones.For example, yellow couplers include those having an active methylene ring. Those having a benzoylacetanilide, pivalylacetanilide, acylacedoanilite structure, etc., with or without a substituent at the coupling position can be used. Thus, as the coupler, both a so-called 2-equivalent type coupler and a 4-equivalent type coupler can be applied. Below, one coupler preferably used in the present invention will be explained in detail. As a cyan coupler, the following general formula [C-Al, [C-
B] and [C-C]. General 2 [C-Al H General formula [C-B] H (wherein, R8 represents an alkyl group, alkenyl group, cycloalkyl group, aryl group or heterocyclic group, and Y is a group represented by (However, R1 represents an alkyl group, alkenyl group, cycloalkyl group, aryl group, or heterocyclic group, R3 represents a hydrogen atom or a group represented by R2, R2 and R3 may be the same or different, and each other may be combined to form a 5- to 6-membered heterocycle), 2
represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized product of an aromatic primary amine color developing agent.)
General formula [C-C] H R1 is -CONR4R5, -NHCOR4, -NH(:
0ORa, -11HsOJ6, -NHCONRJs or -NH3O□NR4R, R2 is a monovalent group, R1 is a substituent, X is a hydrogen atom or a group that leaves by reaction with an oxidized aromatic primary amine developing agent. 0 or 1. Crow is 0~
3. R4 and Rs each represent a hydrogen atom, an aromatic group, an aliphatic group, or a heterocyclic group, R6 represents an aromatic group, an aliphatic group, or a heterocyclic group, and when ■ is 2 or 3, each R3 is the same or different. may be combined with each other to form a ring, and R
4 and Rs, Ra and Rff. R2 and X may be combined to form a ring, provided that i is O
The rise is 0. I'l-CONHR? "t' is present, and R7 represents an aromatic group. First, the above general formula [C-Al and general formula [C-B] will be explained. In the linear formula, Y is a group represented by. where R8 and R2 are each an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl,
7-butyl, dodecyl groups, etc.), alkenyl groups, preferably alkenyl groups having 2 to 20 carbon atoms (allyl groups, heptadecenyl groups, etc.), cycloalkyl groups, preferably 5 to 7 carbon atoms
membered rings (e.g. cyclohexyl), aryl groups (
For example, phenyl group, tolyl group, naphthyl group, etc.), heterocyclic group, preferably 5- to 6-membered ring group containing 1 to 4 nitrogen atoms, oxygen atoms, or sulfur atoms (for example, furyl group, thienyl group, benzothiazolyl group, etc.) ), R co represents a hydrogen atom or a group represented by R2, R3 and R may be combined with each other to form a 5- to 6-membered heterocycle, and R1 and R2 are Any substituent can be introduced, such as an alkyl group having 1 to 1 carbon atoms (e.g., methyl, i-propyl, i-butyl, t-butyl, t-octyl, etc.), an aryl group (e.g., phenyl, naphthyl, etc.). ), halogen atoms (fluorine, chlorine, bromine, etc.), cyano, nitro, sulfonamide groups (e.g. methanesulfonamide, butanesulfonamide, p-toluenesulfonamide, etc.), sulfamoyl groups (methylsulfamoyl, phenylsulfamoyl) etc.), sulfonyl group (
For example, methanesulfonyl, p-toluenesulfonyl, etc.)
, fluorosulfonyl group, carbamoyl group (e.g. dimethylcarbamoyl, phenylcarbamoyl, etc.), oxycarbonyl group (e.g. ethoxycarbonyl, phenoxycarbonyl, etc.), acyl group (e.g. acetyl, benzoyl, etc.), petero ring (e.g. pyridyl group, pyrazolyl group, etc.) ), an alkoxy group, an aryloxy group, an acyloxy group, and the like. In general formula [C-Al and general formula [C-B], R
3 represents a ballast group necessary for imparting diffusion resistance to the cyan coupler represented by the general formula [C-Al and the general formula [C-B] and the cyan dye formed from the cyan coupler, preferably An alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, or a heterocyclic group having 4 to 30 carbon atoms.
-butyl, n-octyl, t-octyl, n-dodecyl, etc.), 5-membered or 6-membered heterocyclic groups, and the like. In the general formula [C-Al and the general formula [C-B], 2 represents a hydrogen atom or a group that can be separated during the coupling reaction with the oxidized product of the tohytroxyalkyl-substituted -p-phenylenediamine derivative color developing agent 0 For example: 6 halogen atoms (
(e.g., chlorine, bromine, fluorine, etc.), substituted or unsubstituted alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, carbamoyloxy groups, sulfonyloxy groups, alkylthio groups, arylthio groups, heterocyclic thio groups, sulfonamides More specific examples include U.S. Pat. No. 3,741.51i3 and JP-A-47-3
No. 7425, Japanese Patent Publication No. 36894-1973, Japanese Patent Publication No. 1977-
No. 10135, No. 50-117422, No. 50-13
No. 0441, No. 51-108841, No. 50.120
No. 343, No. 52-18315, No. 53-10522
No. 6, No. 54-14736, No. 54-48237,
No. 55-32071, No. 55-65957, No. 56
-1938, 56-12643, 56-271
No. 47, No. 59-146050, No. 59-16695
No. 8, No. 60-24547, No. 80-35731,
In the present invention, cyan couplers represented by the general formula [C-D] are preferred. General formula [C-D] OH In the general formula [C-D], R4 is a substituted or unsubstituted aryl group (especially preferably a phenyl group), and when the aryl group has a substituent, the substituent is , -3O,
R,, halogen atom (fluorine, chlorine bromine, etc.), -C
F, t, -NOt, -CN, -COR,, -CO
ORs, 5OzORs. At least one substituent selected from is included. Here, R is an alkyl group, preferably having 1 to 20 carbon atoms.
alkyl groups (e.g. methyl, ethyl, 1-butyl,
dodecyl groups, etc.), alkenyl groups preferably having 2 carbon atoms
~20 alkenyl groups (allyl group, heptadecenyl group, etc.), cycloalkyl groups, preferably those with 5- to 7-membered rings (
R6 represents a hydrogen atom or a group represented by R5. A preferred compound of the cyan coupler of the present invention represented by the general formula [CD'] is one in which R4 is a substituted or unsubstituted phenyl group, and the substituent to the phenyl group is cyano, nitro, -3OJy (R7 is an alkyl group) halogen atom, trifluoromethyl. In the general formula [C-D], 2 and R are each -general formula [C
-A] and [C-B]. R.I.
A preferable example of the ballast group represented by the following general formula [C
-It is a group represented by El. General formula [C-El In the formula, J represents an oxygen atom, a sulfur atom, or a sulfonyl group, K represents an integer from 0 to 4, one sentence represents 0 or l, and when K is 2 or more, two or more are present. R9 may be the same or different, R6 is a straight chain or branched chain having 1 to 20 carbon atoms,
and represents a substituted alkylene group such as an aryl group, and R9
represents a monovalent group, preferably a hydrogen atom, a halogen atom (e.g. chromium, bromine), an alkyl group, preferably a linear or branched alkyl group having 1 to 20 carbon atoms (e.g. methyl, t-butyl, t- 6 groups such as pentyl, t-octyl, dodecyl, pentadecyl, benzyl, phenethyl, etc.),
Aryl groups (e.g., phenyl), heterocyclic groups (e.g., nitrogen-containing heterocyclic groups), alkoxy groups, preferably linear or branched alkoxy groups having 1 to 20 carbon atoms (e.g., methoxy, ethoxy, t-butyloxy, octyloxy) , decyloxy, dodecyloxy, etc.), aryloxy group (e.g. phenoxy group), hydroxy group, acyloxy group, preferably alkylcarbonyloxy group, arylcarbonyloxy group (e.g. acetoxy group, benzoyloxy group), carboxy, alkyl An oxycarbonyl group, preferably a straight or branched alkylcarbonyl group having 1 to 20 carbon atoms, preferably a phenoxycarbonyl group, an alkylthio group, preferably an acyl group having 1 to 20 carbon atoms, preferably a straight chain or branched alkylcarbonyl group having 1 to 20 carbon atoms. Chain or branched alkylcarbonyl group, acylamino group, preferably 1 carbon number
-20 linear or branched alkylcarboxamide group, benzenecarboxamide group, sulfonamide group, preferably a C1-C20 linear or branched alkylsulfonamide group or benzenesulfonamide group, carbamoyl group, preferably It represents a straight-chain or branched alkylaminocarbonyl group or phenylaminocarbonyl group having 1 to 20 carbon atoms, a sulfamoyl group, preferably a straight-chain or branched alkylaminosulfonyl group or phenylaminosulfonyl group having 1 to 20 carbon atoms. Next, specific examples of compounds of the cyan coupler of the present invention represented by the general formula [C-A] or [C-B] will be shown, but the invention is not limited thereto. [Exemplary compounds] tJ 1”ll4 (t) C-F1-R ○-5 C, Hs H H3 fJ 0H. C-13 OH OH (t) OsHu ○-22 OH OH OH. t C4) 1゜t- 6H13 I o4kl. L H 06H,. 0-3 B OR 00H, 0H200H. Next, the general formula [C-CF will be explained. The six groups represented by R3-R7 in the general formula [C-CF have no substituents. R6 is an aliphatic group having 1 to 30 carbon atoms, and 6 to 3 carbon atoms.
0 aromatic group and a heterocyclic group having 1 to 30 carbon atoms are preferred, and R4, R, and the hydrogen atoms and those listed as preferred as R6 are preferred. R2 is a hydrogen atom bonded to NH directly or via N)l, Go or S02, an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, a hetero group having 1 to 30 carbon atoms. cyclic group, -OR, -COR; -PO+0Rto)z, -PO+Rto)t,
-COtRto, -3OJx. or -9OtOR1° (Ra, Rs and Ro are the same as defined in R4, R% and R6 above, and Ra and R9 may be combined to form a petero ring) is preferred. R7 is preferably an aromatic group having 6 to 30 carbon atoms,
Typical examples of substituents for R7 include a halogen atom, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, a cyano group, an aromatic group, a heterocyclic group, a carbonamide group, a sulfonamide group, a carbamoyl group, and a sulfamoyl group. , ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic sulfonyl group, sulfamoylamino group, nitro group, imide group, aliphatic group, aliphatic oxycarbonyl group, etc. When substituted with a plurality of substituents, the plurality of substituents may be bonded to each other to form a ring, such as a dioxymethylene group. Typical examples of R3 include a herogen atom, hydroxy group, amino group, carboxyl group, sulfonic acid group, cyano group, aromatic group, heterocyclic group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, and ureido group. , acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic sulfonyl group, sulfamoylamino group. Examples of the cyclic R3 include a nitro group and an imide group, and the number of carbon atoms contained in R2 is preferably 0 to 30 when 0m=2. When the sentence is 1, R□ is particularly preferably -CONR4RII, 厖 is preferably 0, and R2 is directly bonded to N)l -
COR,,-GOOR,. , -9O,R,. , -CO
NR, R1, -8O□NF1. R@ is particularly preferred, and even more preferred is GOOR+o, which directly binds to Ni1.
, -C0Ra, -3OzRto, especially -COO
Rt. is most preferred. Also included in the present invention are those that form a dimer or more multimer via R, to R1, and X. Among the general formula [C-C], the case where l=o is preferable. Specific examples of couplers represented by the general formula [C-C] are JP-A-60-237448, JP-A No. 61-153640, JP-A No. 6
No. 1-145557, No. 62-85242, No. 4g-
No. 15529, No. 50-117422, No. 52-1
No. 8315, 52-! l [19co No. 2, 53-52
No. 423, No. 54-48237, No. 54-61i12
No. 9, No. 55-32071, No. M2S-65957,
Fil No. 55-10522, No. 56-1938, No. 56-12643, No. 5-27147, No. 56
-126832, US Pat. No. 58-95346, and US Pat. No. 3,488,193, etc., and can be synthesized by the methods described therein. To add a coupler to a light-sensitive material, an oil-in-water emulsion dispersion method using a water-insoluble high-boiling organic solvent can be used, depending on the physical properties (for example, solubility) of the coupler. Various methods can be used, such as an alkali dispersion method in which the material is added as an alkaline solution, a latex dispersion method, and a solid dispersion method in which it is directly added as a fine solid. The amount of coupler added is usually per mole of silver halide.1.
OX 10-” mol-1.0 mol, preferably 5.0
×101 mol~8. Ox is in the range of 10-" moles. Next, typical examples of couplers represented by the general formula [C-C] are shown, but the present invention is not limited thereto. [Exemplary Compound] CH3CO Death CR3SOJII C3F?CONIICQ C-55 C-56 C1Js*5OtllH 0■ [(i)CsHylJSOJH H H B C,H,0CO1lH C,jB□0CONH CHsOCONHCQ H (+)CJsOCONH C ll5O, NH c4o, ocON)l C- 750H CFsCONH0(CHJJCHCOJCItH1@BC,1lsOcON)lx:y-60:40 (molar ratio);
Bondage 0
Q\------------
1 CHtCHtSCH*CHtCOJ CO,H ■ CH*CHJH8O*CHs 0g COt II sHn C1,Cl6 U(niHe)S(υυi C+Jts CIJt+ αx■ C00)I HarukaCO" (molar ratio) Halogenation that can be used in the present invention The silver emulsion is preferably a tabular silver halide emulsion, but in addition to this,
Any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodide, silver iodobromide, and silver chloroiodobromide may be used; As the protective colloid for silver halide, in addition to natural products such as gelatin, various products obtained by synthesis can be used. Silver halide emulsions contain stabilizers, sensitizers, hardeners, and sensitizing dyes. Common photographic additives such as surfactants may also be included. As the photosensitive material used in the present invention, all of color negative films, color vapors, color reversal films, color reversal vapors, etc. can be used. [Effects of the Invention] According to the present invention, it is possible to provide a processing liquid that has excellent silver source white blade and improved stability of the processing liquid, and has excellent processing stability and improved precipitation generation during processing. It is possible to provide a method for processing a photosensitive material. [Example] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. Example 1 In all Examples, the amount added to the silver halide photographic light-sensitive material is expressed in grams per lrn' unless otherwise specified, and silver halide and colloidal silver are expressed in terms of silver. . on a triacetylcellulose film support. Sample 1 of a multilayer color photographic material was prepared by sequentially forming each layer having the composition shown below from the support side. Sample 1 (comparison) First layer dihalation prevention FJ (HC-1) Black colloidal silver -0,25 Ultraviolet 11 absorber (UV-1) -0,20 Colored coupler (CG-1)...0. 05 colored coupler (CM-2) -0,05 high boiling point solvent (oil
-1) ...-0,20 gelatin
...1.4 2nd R: Medium MR (IL-1) Ultraviolet absorber ([IV-1) -.-0,01 High boiling point solvent (oil-1) -0,01 Gelatin
-1,4 Third layer: low sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (E,,, -1) -1,0 Silver iodobromide emulsion (E, -2) ...O, S sensitizing dye (S
-1) -2,5xlO-' (dried/silver) Sensitizing dye (S, -2) ・-2,5x 10-
'(Dry l#I1 mole) Sensitizing dye (S-3)...-0,5Xl0-'
(mol 1 silver 1 mol) Cyan coupler (C-4)' -1,2 cyan coupler (C-2)' ... -o, oa Colored cyan coupler (CC-1) ... -O,0S DIR compound ( D-1) -[1,002 high boiling point solvent (oil-1) -0,5 gelatin
-1, 4 4th calendar: High sensitivity red-sensitive emulsion layer (R11) Silver iodobromide emulsion (
E, -3) -...2.0 sensitizing dye (S-1)
・-2, OX 10-' (mol/silver 1 mol) Sensitizing dye (S-2) ・-2, Oxl Rho 4 (
1 mole of silver) Sensitizing dye (S-3)...0. I Xl0-
'(mol/#11 mole) Cyan coupler (C-1)...0.15 cyan coupler (C-2) -0,018 cyan coupler (C-:l)'...1.15 colored cyan Coupler ((:C-1)-0,015 DIR compound (D-2) ...-0,05 high boiling point melt (oil-1) -O, S gelatin
...1.4 Fifth calendar: Intermediate layer (IL-2) Gelatin ・-O,S 6th layer: Low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (E,,,-1) ・・・1.0 sensitizing dye (S-4) ・−5,Ox 10−'(
Sensitizing dye (S-5) -1,OxlO-' (1 mole of silver) Magenta coupler (T1)...O,S colored magenta coupler (CM-1)...・0.05 DIR Compound (D-3) -0,015 DIR
Compound (D-4) -D, D2D high boiling point solvent (
oil-2) -0,5 gelatin
・-1,0 7th N: Intermediate N (IL-3) Gelatin ・・・0.8 High boiling point solvent (o
N-1) -0,2 8th layer: High-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (E, -3) -...1
．． 3 Sensitizing dye (S-6)...1.5 xl
G-' (1 mole of silver) Sensitizing dye (S-7) -2,5xlP' (mol/1 mole of silver) Sensitizing dye (S-a) -0,5xlO-' (
mole/1 mole of silver) Magenta coupler (T2), -0,06 magenta coupler (T3), -0,18 colored magenta coupler (C
M-2)...-O,0S DIR compound (D-3) ・0.01 High boiling point solvent (oil-3) -0.5 Gelatin
...1.0 9th calendar: yellow filter layer (y
c) Yellow colloidal silver...0.1 Color stain inhibitor (sc-i)...0.1 High boiling point solvent (of
f-3) ...0.1 gelatin
・-0,8 10th layer: Low sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (
E, -1) ...0.25 silver iodobromide emulsion (E,
-2) ...0.25 sensitizing dye (S-10)
・7. OXl0-' (mol l silver 1 mol) Yellow coupler (Y-1) -0,6 yellow coupler (Y-2) -0,12DIR compound (+1-
2) ...0. O11 high boiling solvent (oil-3
) = J, 15 gelatin -1,
0 11th layer: Highly sensitive blue-sensitive emulsion layer (OH) Silver iodobromide emulsion (
E, -4) ...0.50 silver iodobromide emulsion (E,
-1) -0,20 sensitizing dye (S-9)
-1,OX 10-' (mol/silver 1(l) Yellow coupler (Y-1)...0.36 Yellow coupler (y-z)...0.06 High boiling point solvent (
oN-3) ...0.07 gelatin
...1.1 12th layer: 1st protective layer (Pro-1
) Fine grain silver iodobromide emulsion...0.4 (average grain size 0.4)
08 Le Ion Agl 2 mol%) Ultraviolet absorber (UV-1)
-0,10 ultraviolet absorber (UV-2)
-0,05 High boiling point solvent (oil-1)...0
．． 1 High boiling point solvent (oil-4) -0,1 Formalin scavenger ()Is-2)...0.2 Gelatin...1, 13th Calendar:! 8
2 Protective layer (Pro-2) Surfactant (Su-1)
= J, 005 alkali-soluble matting agent (average particle size 2#L) -0,10 cyan dye (
Arc-1) ...-0,005 magenta dye (
AIM-1) ...0.01 Schheli agent (WAX-
1) -0,04 gelatin ・
-0,8 In addition to the above composition, each layer contains a coating aid 5u-2, a dispersing aid 5u-3, hardeners H-1 and H-2, and a preservative DI.
-1, stabilizer 5tab-1, antifoggant AP-1, A
F-2 was added. Em-1 Average grain size: 0.50Ls, average silver iodide content: 7.7% Monodisperse surface-lower-order silver-containing emulsion E-Oboro-2 Average grain size: 0j51Ls, average silver iodide content: 2 .2% monodisperse, uniform composition emulsion E Karasu-3 Average grain size 0.81 gm, average silver iodide content 6.0% monodisperse surface low silver iodide compound emulsion E layer-4 Average Grain size: 0.93μ■, average silver iodide content: 7.8%, monodisperse, surface-low silver iodide-containing emulsions E-1, E-yoku-3, and 8-layer-4 are JP-A-60-138.
The silver iodobromide emulsion is a silver iodobromide emulsion mainly composed of octahedrons and has a multilayer structure adjusted with reference to the publications of No. 538 and No. 61-245151. In addition, for all Em-1 to E■-4, the average value of particle size/particle thickness is 1. II], and the width of the distribution per particle was 4, 10, 12 and 12%, respectively. S-Tobi S-8 C-Atsushi'u RiQ Q rθ C-1 M-1 e D-1 Song 1T H ow V-2 ((CB*=CHSOmCHt)accHtsOt(C
H*)*)J(C1*)*SO! u-1 ■ 11aOsS-c-C00CHt(CF*CF*)JC
-COOC14m(CP-C-C00Cu-2 Na0sS-CC00CJ+t C1b-COOC-11+yu-3 c-1 0H H TC-J IM-1 Stat+-1 II AP-heavy AP-2 l-1 0i1-300-4 The sample thus prepared was exposed to wedge light using white light, and then subjected to the following development treatment. (Experimental treatment) Processing process Processing time Processing temperature Color development (1 tank) 3 minutes 15 seconds 38° C bleaching (1
38°C fixation (1 tank) 1 minute 45 seconds 38°C stabilization (3 tank cascade) 1 minute 38°C drying (40
The composition of the treatment solution used for 45 seconds (°C to 80°C) is as follows. [Color developer] Potassium carbonate 30g Sodium bicarbonate 2.5g Potassium sulfite 4g Sodium bromide
1.3g potassium iodide
1.2 g hydroxylamine sulfate
2.5g sodium chloride
0.6g4-amino-3-methyl-N-ethyl-N-
(β-hydroxylethyl)aniline sulfate 4.8g Potassium hydroxide 1.2g Add water to adjust to 11, adjust to pH 10 using potassium hydroxide or 50% sulfuric acid,
Adjust to 06. [Bleach solution] Organic acid ferric complex salt Listed in Table 1 Ethylenediamine disodium acetate 2g Ammonium bromide
150g glacial acetic acid
10m Compound of Fumiki invention Ammonium nitrate listed in Table 1 30g
Add water to make one part, and adjust the pH to 5.8 using aqueous ammonia or glacial acetic acid. [Fixer ammonium cothiosulfate 150g ammonium sulfite 20g disodium ethylenediaminetetraacetate 0.5g sodium carbonate 10g Add water and IJ
The pH was adjusted to 7.0 using acetic acid and aqueous ammonia. [Stabilizing solution] Formaldehyde (37% solution) 11 sentences 5-chloro-2
-Methyl-4-inchazolin-3-one 0.05g Emulgen 8101 Sodium formaldehyde bisulfite adduct 2g Hexamethylenetetramine 0.5g Add water to make one sentence, and add ammonia water and 50% sulfuric acid to p) l Adjusted to 7.0. As shown in Table 1 below, an experiment was conducted using an organic acid ferric complex salt of a bleaching solution and the compound of the present invention. The cyan stain in the unexposed area of the processed film sample was measured using a photodensitometer PDA-65A (
(manufactured by Konica). Furthermore, the amount of residual silver in the highest density area was measured using a fluorescent X-ray method. The results are summarized in Table 1 below. Table 1 In the table, EDTA4e is ethylenediaminetetraacetic acid ferric ammonium salt, (A-1)・Fe, (A-2)・Fe
, (^-4)・Fe, (A-7) 4e, is that (
It means the ferric ammonium salts of A-1), (A-2), (A-4), and (A-7). The following terms are synonymous. As is clear from the above-mentioned coating 1, it can be seen that by using the organic acid ferric complex salt of the present invention, the desilvering reaction is carried out quickly and the rapid processability is improved. However, it has the drawback of high bleaching fog, which can be significantly improved by using the compound of the present invention. Example 2 Using Experiment No. 1-5 of Example 1, a buffer was added to the bleaching solution in the amount shown in Table 2 to adjust the pH.
The same treatment as in Example 1 was carried out to evaluate the bleaching stain. The results are shown in Table 2. Table 2 As is clear from Table 2, adding acetic acid as a buffer to the bleaching solution lowers the bleaching stain, and adding 0.5 mol or more, especially 0.8 mol or more, the bleaching stain improves even more markedly. I know it will happen. Bleaching stains are also greatly improved by the addition of preferred buffering agents of the present invention other than acetic acid. Example 3 Table 3 shows the bleaching solution used in experiments 1-5 of Example 1.
An experiment was conducted in the same manner as in Example 1 except that 1.5 g/l of the bleaching accelerator shown in Figure 1 was added. The amount of residual silver and cyan stain in unexposed areas of the film samples after processing were measured. The results are summarized in Table 3. From Table 3, it can be seen that by using the bleaching solution of the present invention in combination with a specific accelerator, the suitability for rapid processing is further added, and at the same time, the cyan stain is also improved. Example 4 A running process was performed using the color negative film and processing solution prepared in Experiment No. I-4 of Example 1, and using the following replenisher. Processing liquid used! The II formation is as follows. [Color development replenisher co-potassium carbonate 40g sodium bicarbonate 3g potassium arouse
7g sodium bromide
0.5g hydroxylamine sulfate
3.1g 4-amino-3-methyltoethyl-
N-(β-hydroxylethyl)aniline sulfate 6.0g Potassium hydroxide 2g Add water to make one sentence, and adjust to pH 10.12 using potassium hydroxide or 20% sulfuric acid.
tJR will be adjusted. [Bleach replenisher mff [2 iron complex salt (listed in Table 4) 0.4 mol ethylenediamine vinegar 2 sodium 2 g ammonium bromide]
178g glacial acetic acid
21m ammonium nitrate
Add 35 g of water and adjust to pH 5.6 using 14Q water and aqueous ammonia or glacial acetic acid. [Fixer replenisher] Ammonium thiosulfate 200g Anhydrous sodium bisulfite 15g Sodium metabisulfite 3g Disodium ethylenediaminetetraacetate 0.8g Sodium carbonate 14g Water was added to make a monolayer, and the pH was adjusted to 1.5. As the stabilizing replenisher, the stabilizing solution of Example 1 was used. The processing steps, processing time, processing temperature, and replenishment amount of the running processing were as follows. (The amount of replenishment is the value per rn' of photosensitive material.) However, the fixing tank was a two-tank countercurrent (45 seconds, two tanks). The running process takes 240 days to reach 2 of the capacity of the bleach tank.
This was done until double the amount of bleach replenisher was refilled. The film sample after the running process was evaluated in the same manner as in Example 1, and the amount of bleached stain and residual silver in the highest density area was measured. After the running process was completed and left for 3 days, sedimentation in the bleach solution tank was observed. The sedimentation was observed by looking at the bottom of the tank, and was ranked as follows. 0 No precipitation △ Slight precipitation observed × Large amount of precipitation Next, a similar experiment was conducted by replacing the organic acid ferric complex salt in the bleach solution and bleach replenisher with the organic acid iron complex salt shown in Table 4 below. . The results are summarized in Table 4. Table 4 As shown in Table 4, the bleaching agent of the present invention is suitable for rapid processing. However, there are disadvantages in that bleaching stains are likely to occur and sludge is also likely to be generated, and it can be seen that the above problems can be greatly improved by using the compound of the present invention. Example 5 Replaced with cyan couplers (C-2)'' and (C-3)' used in Experiment No. 1-10 of Example 1. Same mole as (C-2)' and (C-3)' When the same treatment and evaluation as in Example 1 was performed except that the cyan coupler listed in Table 5 was used, almost the same results were obtained.However, bleaching fog (cyan fog) was also measured. The results are shown in Table 5. As is clear from Table 5, bleaching fog is reduced by changing the cyan coupler to a cyan coupler preferred for the present invention. Example 6 A vinyl chloride nozzle with a hole of 0.5 mm in diameter was installed in the bleaching tank and fixing tank of Experiment Nos. (1-5) to (1-10) of Example 1, and a magnet was placed on the emulsion surface of the photosensitive material. An experiment was conducted in the same manner as above, while spraying the treatment solution using pump MD-15. As a result, cyanstein was lowered by 0.02N2.02, and the amount of residual silver was reduced to Tsuba.Example 7 Stabilizing solution (first tank) after running in Example 4 at 30°
The liquid was stored at C for 2 weeks, and the appearance of the liquid after storage was evaluated. ○ No sulfurization △ Slight sulfurization × Sulfurization Table 6 As is clear from Table 6, it can be seen that by using the organic acid ferric complex salt of the present invention, the storage stability of the stabilizer is improved compared to EDT^.Fe. Patent applicant Nobuaki Sakaguchi, agent of Konica Co., Ltd., patent attorney

Claims (1)

[Scope of Claims] 1. A silver halide color photographic light-sensitive material containing a ferric complex salt of a compound represented by the general formula [A] and a compound represented by the general formula [S-I] or [S-II] processing liquid. General formula [A] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A_1 to A_4 may be the same or different, -CH_2OH, -COOM or -PO_3M_1
Represents M_2. M, M_1, M_2 are hydrogen atoms, sodium,
Represents potassium or ammonium. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms. ] General formula [S-
I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Z represents the atomic group necessary to form a heterocycle. General formula [S-II] Q-SM_1 In the formula, Q is -SO_3M_2, -COOM_2, -OH
and -NR_1R_2 represents a heterocyclic residue directly or indirectly bound to at least one selected from the group consisting of M
_1 and M_2 represent a hydrogen atom, an alkali metal, a quaternary ammonium, and a quaternary phosphonium, and R_1 and R_2 represent a hydrogen atom or a substituted or unsubstituted alkyl group. 2. In a method for processing a silver halide color photographic material, which immediately after color development is treated with a bleaching solution and subsequently treated with a processing solution having fixing ability, the bleaching solution is represented by the following general formula [A]. 1. A method for processing a silver halide color photographic light-sensitive material, characterized in that the processing liquid contains a ferric complex salt of a compound and a compound represented by the general formula [S-I] or [S-II]. General formula [A] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A_1 to A_4 may be the same or different, -CH_2OH, -COOM or -PO_3M_1
Represents M_2. M, M_1, M_2 are hydrogen atoms, sodium,
Represents potassium or ammonium. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms. ] General formula [S-
I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Z represents the atomic group necessary to form a heterocycle. General formula [S-II] Q-SM_1 In the formula, Q is -SO_3M_2, -COOM_2, -OH
and -NR_1R_2 represents a heterocyclic residue directly or indirectly bound to at least one selected from the group consisting of M
_1 and M_2 represent a hydrogen atom, an alkali metal, a quaternary ammonium, and a quaternary phosphonium, and R_1 and R_2 represent a hydrogen atom or a substituted or unsubstituted alkyl group.