JPS6385546A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enable quick processing of a photosensitive material and to reduce the recoloring defect by processing the material with a color-developing soln. contg. a specified preservative, and processing further with a processing soln. contg. a specified bleaching accelerator. CONSTITUTION:An imagewise exposed sensitive material is processed with a color developing soln. contg. a preservative expressed by the formula I and a processing soln. contg. >=on kind of bleaching accelerator expressed by the formulas II-IV. R1 and R2 are H, alkyl, etc. In the formulas II-IV, Q is atom groups necessary for forming an N-contg. heterocyclic ring; R1 is H, 1-6C alkyl, aryl, etc.; R2, R3 are H, 1-6C alkyl, hydroxy, etc.; A is a n1-valent heterocyclic residue, etc; X is =S, =O, etc.; n1 is 1-6; R6, R7 are H, 1-6C alkyl, carboxy, etc.; Y1 is =N-, =CH-,; B1 is 1-6C alkylene; Z1 is H, alkali metal, amino, etc.; n7 is 1-6.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for processing silver halide color photographic materials. More specifically, the present invention relates to a method for processing silver halide color photographic materials having rapid silver bleaching ability.

[Background of the Invention] As a recent trend, there has been a shift from a centralized processing type in which market demands are processed in a few large laboratories to a distributed processing type in which the market demands are processed in a large number of small labs.

In such small-sized laboratories, there is a growing demand for more compact processing machines and faster processing that can accommodate short-time services. In particular, high-sensitivity silver halide color photographic materials for photography take a long time to process. There is a strong need to reduce film processing time. Among these, the desilvering process occupies nearly half of the total processing time, and speeding up the desilvering process is an important issue.

In order to speed up the desilvering process, methods have been proposed in which, for example, various bleach accelerators are added to bleach baths, bleach-fixing baths, or their pre-baths.

As a bleach accelerator, for example, U.S. Patent No. 3.893.8
No. 58, British Patent No. 1,138,842, JP-A-53
No.-141623, No. 54-52534, JP-A No. 1973
Various mercapto compounds described in JP-A-95631, etc., compounds having disulfide bonds as described in JP-A-53-95630, thiazolidine derivatives as described in JP-A-53-9854, and thiazolidine derivatives as described in JP-A-53-94927. Isothiourea derivatives, Japanese Patent Publication No. 45-8506, No. 49-26
Thiourea derivatives described in No. 586, JP-A-49-423
Thioamide compound described in No. 49, JP-A-55-265
Dithiocarbamate salts described in No. 06 are known.

Some of these bleach accelerators do have a bleach accelerating effect, but the effect is not necessarily sufficient, and in particular, when the color developer mixes with the bleach solution or bleach-fix solution, the accelerating effect is significantly reduced. In addition to deterioration, the use of such bleach accelerators also tends to promote so-called defective color restoration due to leuco formation of cyan dyes. It has become clear that the effect becomes even more pronounced when mixed with

Therefore, efforts have been made to develop a processing method for silver halide color photographic materials that speeds up the desilvering process of the silver halide color photographic materials and does not deteriorate the recoloring properties of cyan dyes.

[Objective of the Invention] An object of the present invention is to provide a processing method using a processing solution having bleaching ability that enables rapid processing of silver halide color photographic light-sensitive materials and that causes extremely little deterioration of recoloring property of cyan dye. be.

[Structure of the Invention] The above object of the present invention is to remove at least a color developing solution and bleaching ability after exposing a silver halide color photographic material having at least one silver halide emulsion layer on a support. In the method of processing a silver halide color photographic light-sensitive material, the color developing solution contains at least one compound represented by the following general formula [A] and has the bleaching ability. This was achieved by a method for processing a silver halide color photographic light-sensitive material, in which processing with a processing liquid is carried out in the presence of at least one compound selected from compounds represented by the following general formulas [I] to [IX].

General Formula [A] In the formula, R1 and R2 each represent an alkyl group or a hydrogen atom. However, both R1 and R2 are not hydrogen atoms at the same time. Further, R1 and R2 may form a ring.

General formula [I] R3 In the formula, Q represents an atomic group necessary to form a nitrogen-containing heterocycle (including one in which 5- to 6-membered unsaturated rings are condensed), R1 is a hydrogen atom, Alkyl group having 1 to 6 carbon atoms, cycloalkyl group, aryl group, heterocyclic group (5 to 6
(including those with fused unsaturated rings) or amine groups.

General formula [■] In the formula, R2 and R3 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amine group, an acyl group having 1 to 3 carbon atoms, an aryl group, or an alkenyl group. represents.

A represents an or n1-valent heterocyclic residue (including those in which 5- to 6-membered unsaturated rings are condensed), and X represents -S, -0 or -NR''.Here, R and R' are R
2 and R3, X' is synonymous with X, Z is a hydrogen atom,
Represents an alkali metal atom, ammonium group, amine group, nitrogen-containing heterocyclic residue, alkyl group, or atom, Rn is a hydrogen atom, a carbon atom rX! 1-6
01 to n6 and m1 to l
15 each represents an integer from 1 to 6. B represents an alkylene group having 1 to 6 carbon atoms, and Y is -N or -C
R4 and R5 are R2 and R, respectively.
It is synonymous with 3. However, R4 and R5 are each -B
-8z may also be represented, and R2 and R3, R and R'
, R4 and R5 may each be combined to form a ring.

Note that the compound represented by the formula also includes enolated products and salts thereof.

General formula [■] 7 In the formula, R6 and R7 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amine group, an acyl group having 1 to 3 carbon atoms, an aryl group, Represents an alkenyl group or -8+ -3-Zl. However, R6 and R7 may be combined to form a ring. Yl represents ゝN- or ゝCH-, and B1 has 1 to 6 carbon atoms.
represents an alkylene group, and Zl does not represent a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue, or an integer of.

In the general formula EIV, R8 and Rs represent each, and Rho represents an alkyl group or (CH2)*t S 03e . (However, R
+.

f:p (CH2)718 S O30 Notoki 1,
2G; represents to, and represents 1 when it is an alkyl group. )
Ge represents an anion. O8 represents an integer from 1 to 6.

General formula [Vl Q7'''', where Ql 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). , R++ represents a hydrogen atom or an alkyl group. However, Q' has the same meaning as Ql.

General formula [Vl] In the formula, D+, O2, Da J5 and B4 each represent a simple bond, an alkylene group or vinylene group having 1 to 8 carbon atoms, and ql, O2, O3 and O4 each represent O% 1 zE+t Represents 2.

Further, the ring formed with the sulfur atom may be further fused with a 5- to 6-membered saturated or unsaturated ring.

General formula [VI] In the formula, X 2 bar COOM', -0H1-80
3M', -CONH2, -302NH2, -NH2,
-8H, -CN, -Ge2Rho, -5O2R+s,
-OR+s, -N R+s R17, -S R+6, -
8○3R16, -N HCOR+s, -NH3O2R+
6, -00 represents OR16 or -3O2R+s, Y
2 represents a hydrogen atom, In2 and O9 each represent an integer of 1 to 10, R11, R12, RI3, R
I4, R15, R+7 and Rho each represent a hydrogen atom, a lower alkyl group, an acyl group or an R++ group, and Rho represents -NR2oR2+, -0R2
2 or -5R22, R20 and R2+ each represent a hydrogen atom or a lower alkyl group, and R22
represents an atomic group necessary to combine with Rho to form a ring. R20 or R++ may be combined with Rho to form a ring. M' does not represent a hydrogen atom or a cation.

General formula [■Co(G')z In the formula, Ar is 2 which is a combination of two aryl groups or an aryl group and an oxygen atom and/or an alkylene group.
B2 and R3 each represent a lower alkylene group, R23, R2+, R25 and R
26 each represents a hydroxy-substituted lower alkyl group, and X and y each represent 0 or 1. G' represents an anion, and 2 represents 0.1 or 2.

General Formula [IX] In the formula, R29 and R3o each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, R3+ represents a hydrogen atom or an alkyl group, and R32 represents a hydrogen atom or a carboxy group.

[Specific Structure of the Invention] In the present invention, the color developing solution contains at least one compound represented by the general formula [A].

Hereinafter, the compound represented by the general formula [A] will be referred to as the compound of the present invention.

In general formula [A], R1 and R2 each represent an alkyl group or a hydrogen atom that is not a hydrogen atom, but the alkyl groups represented by R1 and R2 may be the same or different, and each has 1 to 3 carbon atoms. Alkyl groups are preferred. The alkyl groups of R1 and R2 include those having substituents, and R1 and R2 may be combined to form a ring, for example, a heterocyclic ring such as piperidine or morpholine.

Specific compounds of the hydroxyamine compound represented by the general formula [A] are described in U.S. Patent No. 3.287.125, U.S. Pat. However, particularly preferred specific exemplary compounds are shown below.

These compounds of the present invention are usually used as free amines, hydrochlorides,
It is used in the form of sulfate, p-toluenesulfonate, oxalate, phosphate, acetate, etc.

The concentration of the compound represented by the general formula [A] of the present invention in the color developing solution is usually 0.10/ffi to 50 g/l, preferably 1 g/72 to 30 g/4. Preferably 3g/j! ~20o#! It is.

The compound represented by the general formula [A] of the present invention can be used in place of hydroxylamine sulfate, which has been widely used as a preservative in color developing solutions for conventional silver halide color photographic light-sensitive materials. However, among the compounds of the present invention, for example, N,N-diethylhydroxylamine is known to be used as a preservative for a black and white developing agent in a color developer containing a black and white developing agent. In the so-called external color development method, in which a color photographic material is developed by a reversal method using a color developing solution containing a coupler, there is a technique in which it is used together with phenidone. (Tokuko Showa 4
5-22198).

Further, as another example of using the compound of the present invention such as N,N-diethylhydroxylamine as a preservative for a black and white developing agent added to a color developing solution, in an internal color developing solution, A technique for preserving phenidone derivatives added thereto (see JP-A No. 53-32035) and a technique for preserving phenidone derivatives together with hydroquinones (see JP-A-52-153437). Can be done.

However, after processing with a color developing solution containing the compound represented by the general formula [A] as a preservative, the general formula [A]
By treating with a processing solution having bleaching ability in the presence of bleach accelerators shown in [I] to [IX], not only can a remarkable bleaching accelerating effect be obtained, but also it can improve The fact that almost no color recovery defects occur is completely unpredictable.

In the present invention, the term "processing liquid having bleaching ability" refers to a processing liquid that at least bleaches a photosensitive material, and specifically refers to a bleaching bath or a bleach-fixing bath.

In the present invention, the treatment liquid having bleaching ability contains at least one compound selected from the compounds represented by the general formulas [I] to [TX].

The compounds represented by the general formulas [I] to [rX] used in the present invention are compounds generally used as bleach accelerators, and are hereinafter referred to as bleach accelerators of the present invention.

Typical specific examples of the bleaching accelerator of the present invention represented by the general formulas [I] to [rX] include, but are not limited to, the following.

Exemplary compound (I-1) (I-2) CH,C
H,SO,K CH2C'00H(I'
-3) (I -4) (T-5)
(I-6) CH, CH2CH, CH
, So, Na (I-7) (I-8) S Os
Na (I-9) (I-10) (I-
11) (I-12) CH,
CH, C00H (1-13) (I-14)
(I-15) (I-16)
(I-17) (Tl-1)
(n-2) (II-
3) (II-4) (n-5) (II-6) (n-7) (II-8) HIN-C8NHNHC3-NH.

(II-9) H, N-C3NH (CHt), NHO2-NH.

(I[-10) (IT-11) (II-12) (II-13) (II-14) (n-15) (n-16) (II-17) (II-18) (IT-19 ) (TI-20) (I[-21) (II-22) ([-23) (n-24) ([-25) (n-30) ([-31) (n-32) (n- 33) (n-34')(I
I-35) (II-36) (n
-37) (n-38) (n-39) (TT, -40) H (n-41) (II-42) (n-43) (II-44) (n-45) (III-1) H,N-N-CH2CH2- 8H(2”) (m-3) (III-4) HOOC-CH,CH,-8H (m-5'I (III-6)(
III-7) (III-8)
C&CH25K (II[-9) (m-10)(m
-11) (nI-12) (II
I-13) (T[l-44)(
III-15) f-λ H8CHICH2CH2CH2N N CPh(
JbCHzCL-3K℃-) (ffl-16) CH,-8H (u-17) CIII-18) ([-19) (III-20) ---〇-to (IV-4> (rV-5 )?CH.

(V-1) (V-2) (V-3
) (V-4) (V-ri)
(V-6) (V-7)
(V-8) (V-9) (V-10) (V-11
)(V-12) (V-13)(
V-14) (V-15)
(V-16) (V-17)N
H.

(v-18) (V-19) C,H.

(V-20) (V-21) (V-22) (V-23) (V-24) (V-25) (V-26) (V
-27) (V-28) (V-29
) (V-30) (V-31)
(V-32) (V-33)
(V-34))r] (V-35) H (■-1) (Vl-2)
(Vl-3) (Ml-4) (Vl-5)
(Vl-6) (Vl-7)
(Vl-8) (Ml-9) (■-10)
(Vl-11) (Vl-12)(
Vl-13) (Vl-14)
(■-15) (Vt-16) (■
-17) (■-18) (Vl-19)
(Vl-20) (Vl-21) (Vl
-22) (VII-1) (■-2) (■-3) 1+s cH,CHt NHCHz CHt CHt
S Os H) t(■-4) (VII-5) (Vll-6) cH blasphemy (■-7) (■-8) (■-9) (■-10) (■-11) (■ -12) (VI[-13) (■-14) (■-15) (■-16) IsCHzCHtNCHtCHtCONHtCH.

(VfI-17) HSCH, CH, NHCH, CH, OHC 1 83CH2CH,NCH2CHtOH C, H.

(Vll-19) HSCH,CH,NCHtCH,N(CH,)tCH.

(■-20) HSCH, CH2NCH2CH, OCH, CH, OCH
.

C0CH.

rn-g ω VTH-'7 ``2''('''H)'H20F()2■ llX
-2 In addition to the bleaching accelerator of the present invention exemplified above,
Exemplary compounds No. 26'3568, pages 51 to 115, I-2, I-4 to 7, ■-10,
11, l-13, knee 16, ■-18, ■-20, 21
, l-23, l-26, 27, ■-30 to 33, ■-3
5, ■-38, ll-2~5, IF-7~10, ll-
12, 13, ■-15 to 20, ■-22, n-24, 2
5,■-27,■-29~33,ll-35,36,■
-38~41, ll-43, l-45~52, ll-5
4,55, ■-57, ll-59,60, ■-62~6
4, ■-67~70, ■-73~76, ll-78,7
9,■-81~84,I[-86,87,ll-90゜91,I[-93,94,■-96,l-98゜99,
[-101,102, [-104, ll-106~10
8, [-110, IF-112, ■-1ia~119,
■=121~124, [-126, ll-128~13
1, ■-133~135, [-137~144, l[-
146, ■-148, I[-15<1~153, [-1
55, ■-157, ■-4, l1l-6~8, lll-
10, 11, lll-13, ■-15, I[[-17,
18, ■-20, ■-25, ■-27, I! 1-29,
II! -31, l-35, 36, ■-3~6, ■-8~
14, V-16~20. V-22~25, ■-27~2
1, v-31~33, V-35~38, ■-40~42
, V-44~46, V-48~56, ■-58, V-6
0~66, ■-68~70, ■-72~74, ■-76
~79, V-81, 82, ■-84 ~ 100, V-1
02~10B, V-110, V-112, 113, ■
-116~119, V-121~123, V-126
~ 130, V 132, V-134 ~ 138,
V-140~144, ■-146~156, V-158
~ 162, V-164 ~ 171, V-173, 17
4, V-177~184, Vl-4, ■-7, ■-1
3, Vl-16, Vl-19, ■-21, ■-25,
Compounds ①-27, ②-29, Vl-31 to 34, and VI-36 can also be used in the same manner.

The bleaching accelerator of the present invention only needs to be present when bleaching the silver image obtained by development, and is preferably added to the bleaching and/or bleach-fixing bath. It can also be incorporated into a bleaching and/or bleach-fixing bath by adding it to a bath (pretreatment solution) and bringing it into the silver halide color photographic light-sensitive material. Alternatively, it may be contained in a silver halide color photographic light-sensitive material.

These bleach accelerators of the present invention may be used alone or in combination.
More than one species may be used in combination, and the amount is preferably 0.03 to 10 g per 12 bleaching solutions, more preferably 0.05 to 2 g per 12 processing solutions.

When adding the bleach accelerator of the present invention to a bleach bath, a bleach-fix bath, and/or a bath (pretreatment bath) prior to the bleach-fix bath,
Although it may be added and dissolved as is, it is common to dissolve it in water, alkali, organic acid, etc. before adding it, and if necessary, dissolve it in an organic solvent such as methanol, ethanol, acetone, etc. before adding it. However, it has no effect on its bleaching promotion effect.

The processing solution having bleaching ability used in the present invention means a bleaching or bleach-fixing solution as mentioned above, and any bleaching agent can be used in these bleaching or bleach-fixing solutions. For example, red blood salt, iron chloride (described in British Patent No. 736.881 and Japanese Patent Publication No. 56-44424), persulfuric acid (described in German Patent No. 2, No. 141.199), hydrogen peroxide (described in Japanese Patent Publication No. 2, No. 141.199), No. 58-11617, 58
-11618), organic ferric complex salts such as ethylenediaminetetraacetic acid ferric complex salts are used.

A particularly preferred example is a ferric complex salt of a tiric acid shown below.

(1) Diethylenetriaminepentaacetic acid (2) Diethylenetriaminepentamethylphosphonic acid (3) Cyclohexanediaminetetraacetic acid (4) Ethylenediaminetetraacetic acid (5) Methyliminodiacetic acid (6) Probyliminodiacetic acid (7) Butyliminodiacetic acid (8) Cyclohexanediaminetetramethylenephosphonic acid Acid (9) Triethylenetetraminehexaacetic acid (10) Triethylenetetraminehexamethylenephosphonic acid (11) Glycol ether diamine tetraacetic acid (12) Glycol ether diamine tetramethylene phosphonic acid (13) 1,2-diaminopropane tetraacetic acid (14) )1.
2-Diaminopropane tetramethylenephosphonic acid (15) 1.3-diaminopropan-2-ol tetraacetic acid (16) 1.3-diaminopropane-2-ol tetramethylenephosphonic acid (17) Ethylenediamine diorthohydroxyphenyl acetic acid (18) ethylenediamine diorthohydroxyphenyl methylene phosphonic acid (19) ethylenediamine tetramethylene phosphonic acid (20
) N-Hydroxyethyliminodiacetic acid (21) 1.3-
Diaminopropane tetraacetic acid (22) 1,3-Diaminopropane tetramethylene phosphonic acid ferric complex salts of similar acids are free acid hydrogen salts), alkali metal salts such as sodium salts, potassium salts, lithium salts,
Alternatively, it may be used as an ammonium salt, or a water-soluble amine salt such as a triethanolamine salt, but potassium salt, sodium salt, and ammonium salt 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 used can be arbitrarily selected and must be selected depending on the amount of silver and silver halide composition of the photosensitive material to be processed, but it is generally used at a lower concentration than other aminopolycarboxylate salts because of its high oxidizing power. can. For example, the processing liquid 12 having bleaching ability
It can be used in an amount of 0.01 mol or more, preferably 0.05 mol per
~0.6 mol is used. 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.

Bleach and bleach-fix solutions can be used with I) H0.2 to 9.5, preferably 4 to 9, more preferably 5.5 to 8.
Used in 5. The treatment temperature is used at 80° C. or lower, preferably 55° C. or lower, most preferably 45° C. or lower to suppress evaporation.

The bleaching solution can contain various additives together with the organic acid ferric complex salt as a bleaching agent as described above. As additives, it is particularly desirable to include alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, and the like.

Also, the pH of borates, oxalates, acetates, carbonates, phosphates, etc.
Buffers, solubilizers such as triethanolamine, acetylacetone, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids, polycarboxylic acids, alkylamines, polyethylene oxides, etc. can be added to ordinary bleaching solutions. Those that are known can be added as appropriate.

The bleach-fix solution may include a bleach-fix solution with a slight addition of a halogen compound such as potassium bromide, or conversely a bleach-fix solution with a composition containing a halogen compound such as potassium bromide or ammonium bromide. Furthermore, a special bleach-fixing solution having a composition consisting of a combination of a bleaching agent and a halogen compound such as potassium bromide in multiple cans can also be used.

As the halogen compound mentioned above, in addition to potassium bromide, hydrogen chloride, hydrobromic acid, lithium bromide, sodium bromide, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, etc. can also be used. .

Silver halide fixing agents to be included in the bleach-fixing solution include compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, potassium thiocyanate, and ammonium thiosulfate, which are used in ordinary fixing processes. Typical examples thereof include thiosulfates such as potassium thiocyanate, thiocyanates such as sodium thiocyanate, ammonium thiocyanate, thioureas, thioethers, and high concentrations of bromides and iodides. These fixatives are 5
It can be used in an amount that can dissolve 1 g/f1 or more, preferably 50 g/ffi or more, more preferably 70 a/f1 or more.

As in the case of the above bleaching solution, the bleach-fix solution contains boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate,
pH buffering agents consisting of various salts such as acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, surfactants, and antifungal agents can be contained. In addition, preservatives such as hydroxyamine, hydrazine, sulfites, isomeric bisulfites, bisulfite adducts of aldehydes and ketone compounds, acetylacetone,
Organic chelating agents such as phosphonocarboxylic acid, polyphosphoric acid, organic phosphonic acid, oxycarboxylic acid, polycarboxylic acid, dicarboxylic acid and aminopolycarboxylic acid; stabilizers such as nitro alcohol and nitrate; solubilizers such as alkanolamine; Anti-stinting agents such as organic amines, other additives, and organic solvents such as methanol, dimethylformamide, and dimethyl sulfoxide may be appropriately contained.

In the present invention, when a fixer is used, the fixer is, for example, Thio1iii! Acid (Unexamined Japanese Patent Publication No. 57)
-185435), thiocyanic acid i! ! (British Patent No. 565.135, JP 54-137143
Descriptions in each publication, halides (Japanese Unexamined Patent Publication No. 52-1306
39), thioether (Belgian Patent No. 6), thioether (Belgian Patent No. 6)
26,970), thiourea (British Patent No. 1,
189,416@publication) etc. can be used.

In addition to these fixing agents, the fixing solution contains boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, pH buffering agents consisting of various salts such as sodium acetate and ammonium hydroxide may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, surfactants, and antifungal agents can be contained. Also hydroxyamine, hydrazine, sulfite, isomeric bisulfite,
Preservatives such as bisulfite adducts of aldehydes and ketone compounds; organic chelating agents such as acetylacetone, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, oxycafflebonic acids, polycarboxylic acids, dicarboxylic acids, and aminopolycarboxylic acids; Stabilizers such as alcohols and nitrates, solubilizers such as alkanolamines, stain inhibitors such as organic amines, other additives, and organic solvents such as methanol, dimethylformamide, and dimethyl sulfoxide may be appropriately contained.

In the treatment of the present invention, silver may be recovered by a known method from processing solutions containing soluble silver complexes such as fixing solutions and bleach-fixing solutions as well as washing substitute stabilizers. In this case, for example, electrolysis method (described in French Patent No. 2,299,667), precipitation method (described in Japanese Patent Application Laid-open No. 52-73037 and German Patent No. 2,331,220), ion exchange Japanese Patent Publication No. 51-17114, German Patent No. 2, 548.
No. 237) and metal substitution method (British Patent No. 1.
353.805) etc. can be effectively used.

The processing method of the present invention is particularly effective when bleaching or bleach-fixing is performed immediately after color development. In such a processing method,
Due to continuous processing of light-sensitive materials, the color developing solution is bleached or mixed into the bleach-fix solution and accumulated.

If the mixing rate of the color developer into the bleach or bleach-fix solution is 3% or more, especially 5% or more, the bleaching accelerating effect of the bleaching accelerator will decrease and poor color recovery will become noticeable. The treatment method of the invention can be used particularly effectively.

In the present invention, bleaching and fixing may be performed after color development, or bleaching and fixing may be performed after color development.

Also, as shown in Japanese Patent Application Laid-Open No. 61-75353,
After color development, bleaching treatment may be performed, followed by bleach-fixing treatment. In this case, the overflow of the bleaching bath may be introduced into the bleach-fixing bath as shown in Japanese Patent Laid-Open No. 61-75352. Furthermore, as shown in JP-A-58-105148, bleaching may be performed after pre-fixing.
As shown in Japanese Patent Application Laid-Open No. 61-51148, bleach-fixing may be performed after pre-fixing.

In this case, as shown in JP-A No. 61-51143, the overflow of the pre-fixing bath is introduced into the bleach-fixing bath,
But that's fine.

Typical specific examples of the treatment steps used in the treatment method of the present invention are shown below, and among the treatment steps below, the steps enclosed by the opening are the steps containing the bleach accelerator of the present invention.

(1) Color development → I Wataru 11 → Water washing (2) Color development → m → Sho is water washing → Water washing (3) Color development → m-m - washing room stable) Color development → U → Stable (5) Color development → [] → 1st stable → 2nd stability (6) color development → water washing → m → water washing (7) color development → I II-+ [Tile U → stable (8) color development → m-m- water washing ( 9) Color development → Q-+ I ■ II → Stable (10) Color development → Dance] - [Tile → Stable (11) Color development → Box 1 → Washing with water → Fixing → Washing with water → An (12) Color development → 0 → Fixing → Washing → Stable (13) Color development → 11 → Serving → 1st stable → 2nd
Stable (14) Color development → [n → Slightly washed with water → Fixation → Slightly washed with water →
Water washing → Stable (15) Color development → Il-+lI■I → 1st stable → 2nd
Stable (16) Color development → I10■1-'IIn → Fixation → 1st
Stability → 2nd stabilization 17) Color development → washing with a small amount of water → [1 → washing with a small amount of water → fixation →
[Small] Water washing → Water washing → Stable (18) Color development → [-"t-' Small amount of water washing → Fixation → Small amount of water washing → Water washing → Stable (19) Black and white development → Water washing (or stable) → Reversal → Color development - In constant Wear → Wash with water (or omit) → Stable (20) Black and white development → Wash with water (or stabilize) → Reverse → Color development → 匡■■I-++−+ Fix → Wash with water (or omit) → Stable (21) Black and white development → Wash with water (or stable) → reversal → color development → W → water washing (or omitted) → stable (22) black and white development → water washing (or stable) → reversal → color development → lllll- + field III → water washing (or omitted) → stable , Bleaching acceleration in the above step is a pre-bath containing a bleaching accelerator.

The compound of the present invention represented by the general formula [A] may be used in combination with other preservatives, and examples of preservatives that can be used in combination include potassium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, etc. and bisulfite adducts of aldehydes or ketones, such as formaldehyde bisulfite adducts, glutaraldehyde bisulfite adducts, and the like.

The color developing solution used in the color developing solution of the present invention immediately after color development includes various types that are widely used in various color photographic processes. These developers include amine phenol and p-phenylene diamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, because they are more stable in the transparent state.

Further, these compounds are generally preferably used in a concentration of about 0.10 to about 50 g per color developer 1r, more preferably about 1 g to about 30 g per 1f.

Examples of amine phenol developers include 〇-amine phenol, p-amine phenol, 5-amino-2-
Hydroxytoluene, 2-amino-3-hydroxytoluene, 2-hydroxy-3-amino-1,4-dimethylbenzene and the like are included.

Particularly useful color developers are N,N-dialkyl-p-phenylenediamine compounds, in which the alkyl and phenyl groups may be substituted or unsubstituted. Among them, particularly useful compounds include N, N-
Diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N-dimethyl-
p-phenylenediamine hydrochloride, 2-amino-5-(N
, -ethyl-N-dodecylamine)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amine aniline sulfate, N-ethyl-N-β-
Hydroxyethylamine aniline sulfate, 4-amino-
Examples include 3-methyl-N,N-diethylaniline sulfate and 4-amino-N-(methoxyethyl)-N-ethyl-3-methylaniline-11-toluenesulfonate.

The color developing agent may be used alone or in combination of two or more, and if desired, a black and white developing agent such as phenidone,
4-hydroxymethyl-4-methyl-1-phenyl-3
- May be used in combination with pyrazolidone, metol, etc.

Further, instead of using the above-mentioned color developing agent in the color developing solution, a color developing agent can be added to the light-sensitive material, and the color developing agent used in this case includes a dye precursor. A typical dye precursor is JP-A No. 5
Those described in No. 8-65429 and No. 58-24137 are used, and specifically, for example, 2',4'-bismethanesulfonamide-4-diethylaminodiphenylamine, 2'-methanesulfonamide-4' −(2
,4,6-doliisobrobyl)benzenesulfonamide-2-methyl-4-N-(2-methanesulfonamidoethyl)ethylaminodiphenylamine, 2'-methanesulfonamide-4'-(2,4,6- doliisobrovir)benzenesulfonamido-4-(hydroxytrisethoxy)diphenylamine, 4-N-(2-methanesulfonamidoethyl)ethylamino-2-methyl-2'
, 4'-bis(2,4゜6-doliisobrobyl)benzenesulfonamide diphenylamine, 2,4'-bismethanesulfonamide-4-N, N-diethylaminodiphenylamine, 4-n-hexyloxy-2'~ Methanesulfonamide-4'-(2,4,6-doliisobrobyl)benzenesulfonamide diphenylamine, 4
-Me1~Xy2'-Methanesulfonamide-4'-
(2,4,6-dolyisobrobyl)benzenesulfonamide diphenylamine, 4-diethylamino-4'-
(2,4,6-1-lyisopropylbenzenesulfonamide)diphenylamine, 4-n-hexyloxy-3
'-Methyl-4'-(2,4,6-dolyisobrobylbenzenesulfonamido)diphenylamine, 4-N.

N-diethylamino-4'-(2,4,6-doliisobrobylbenzenesulfonamido)diphenylamine,
Examples include 4-N,N-dimethylamino-2-phenylsulfonyl-4'-(2,4,6-doliisobrobylbenzenesulfonamide)diphenylamine.

The total amount of the dye precursor added to the photosensitive material is preferably 0.5 to 22 mg, more preferably 4 to 12 mg, per 100 ci2 of the photosensitive material.

The color developer may contain the following developer components in addition to the above components.

Examples of alkaline agents include sodium hydroxide, potassium hydroxide, silicates, sodium carbonate, potassium carbonate,
Sodium metaborate, potassium metaborate, phosphoric acid 3
Sodium, tripotassium phosphate, borax, etc. can be used alone or in combination with coarse gold. For general pharmaceutical needs or to increase ionic strength, disodium hydrogen phosphate, dipotassium hydrogen phosphate,
Various salts can be used, such as sodium bicarbonate, potassium bicarbonate, and borates.

Further, an organic antifoggant may be added as required.

Furthermore, a development accelerator can also be used if necessary.

As a development accelerator, U.S. Pat. No. 2,648,604;
3,671,247 and Japanese Patent Publication No. 44-9503, other cationic compounds, cationic dyes such as phenosafranin, neutral salts such as thallium nitrate, Patent No. 2.5
No. 33.990, No. 2,531,832, No. 2,
950,970, No. 2,577.127, and nonionic compounds such as polyethylene glycol and its derivatives, polythioethers, etc. described in Japanese Patent Publication No. 44-9504, and compounds described in Japanese Patent Publication No. 44-9509. These include solvents, organic amines, ethanolamine, ethylenediamine, jetanolamine, triethanolamine, etc. In addition to benzyl alcohol and phenethyl alcohol described in U.S. Patent No. 2□304.925□, acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine, amines, etc. can be mentioned. .

Furthermore, the color developing solution of the present invention may contain ethylene glycol, methylrerosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and others as required.
The compounds described in the publications can be used as organic solvents to increase the solubility of developing agents.

In addition, as a chelating agent, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, oxycarboxylic acids such as citric acid and gluconic acid,
Organic phosphonic acids such as 1-hydroxyethylidene-1,1-diphosphonic acid, aminopolyphosphonic acids such as aminotri(methylenephosphonic acid), polyhydroxy compounds such as 1,2-dihydroxybenzene-3゜5-disulfonic acid, etc. It can contain.

Other compounds that can be added to the color developer of the present invention include:
Examples include optical brighteners, especially triadylstilbene optical brighteners, and alkanolamines such as polyethyleneimine.

Furthermore, auxiliary developers can also be used with the developing agents. These auxiliary developers include, for example, N-methyl-p-aminophenol hexulfate (methol).
, phenidone, N,N'-diethyl-p-aminephenol hydrochloride, N,N.

N',N'-tetramethyl-p-phenylenediamine hydrochloride and the like are known, and the amount added is usually preferably 0.01 (] to 1.0 g/lj. In addition, if necessary, Competitive couplers, fogging agents, colored couplers, development inhibitor-releasing couplers (so-called DI
R coupler) or a development inhibitor-releasing compound can also be added.

Furthermore, other anti-stain agents, anti-sludge agents,
Various additives such as a multilayer effect accelerator can be used.

Each component of the above color developing solution can be prepared by sequentially adding and stirring a certain amount of water - in this case, components with low solubility in water are mixed with the above organic solvent such as triethanolamine and added. can do. More generally, the color developing solution of the present invention is prepared by adding a concentrated aqueous solution or a solid state of a plurality of components that can coexist stably in a small container into water and stirring. Obtainable.

In the present invention, the above color developing solution can be used at any pHI! However, from the viewpoint of rapid processing, I) H9,5-13
It is preferably pH 0, more preferably pH 9.8.
~13.0.

In the present invention, the processing temperature for color development is 30°C.
As mentioned above, the higher the temperature is 50°C or lower, the more preferable it is because it enables rapid processing in a short time, but from the viewpoint of image storage stability, it is better not to be too high, and it is preferable to process at a temperature of 33°C or higher and 45°C or lower.

In the present invention, washing with water or a stabilization treatment as an alternative to washing with water is performed.

Hereinafter, a washing substitute stabilizing liquid that can be applied to the present invention will be explained.

The pH of the water washing alternative stabilizer that can be applied to the present invention is preferably in the range of 5.5 to 10.0, more preferably pa
l ranges from 6.3 to 9.5, particularly preferably pH
It ranges from 7.0 to 9.0. As the (1) H adjuster that can be contained in the water-washing alternative stabilizing solution applicable to the present invention, any commonly known alkaline agents or acid agents can be used.

The treatment temperature for the stabilization treatment is preferably in the range of 15°C to 60°C, preferably 20°C to 45°C. In addition, from the viewpoint of rapid processing, it is preferable that the processing time be as short as possible, but it is usually 20 seconds or more.
The treatment time is 10 minutes, most preferably 1 to 3 minutes, and in the case of multiple tank stabilization treatment, it is preferable that the first stage tank be treated for a short time and the second stage tank be treated for a long time. Especially from 20% of Maebashi
It is desirable to process sequentially with 50% more processing time.

After the stabilization treatment applicable to the present invention, no water washing treatment is required at all, but rinsing with a small amount of water within an extremely short period of time, surface cleaning, etc. can be optionally performed as necessary.

As for the method of supplying the water-washing substitute stabilizing solution in the stabilization treatment step that can be applied to the present invention, when a multi-tank countercurrent system is used, it is preferable to supply it to the after bath and overflow from the front bath. Of course, it can also be treated in a single tank. The above compounds can be added as a concentrated solution to the stabilization tank, or the above compounds and other additives may be added to the washing alternative stabilizing solution supplied to the stabilizing tank, and then added to the washing alternative stabilizing replenishment solution. Although there are various methods such as using it as a supply liquid, it may be added by any method.

In this way, in the present invention, the treatment with a water-washing substitute stabilizing solution refers to a stabilization treatment that does not substantially involve water-washing, and the treatment solution used for the stabilization treatment is referred to as a water-washing substitute stabilizing solution. The tank is called a stabilization bath or stabilization tank.

The number of stabilization tanks in the stabilization treatment that can be applied to the present invention is 1 to 5.
The effect of the present invention is large when the product is 1, particularly preferably 1
-3 tanks, preferably 9 tanks or less at most.

Silver halide emulsions that can be used in the light-sensitive material applicable to the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide. Any silver halide may be used. However, the processing method of the present invention is particularly suitable for processing silver halide color photographic light-sensitive materials containing at least 0.5 mol% or more, especially 2 mol% to 20 mol%, of silver iodide grains.

Each of the silver halide emulsion layers according to the present invention can contain a coupler, that is, a compound capable of reacting with an oxidized product of a color developing agent to form a dye.

As the couplers that can be used in the present invention, various yellow couplers, magenta couplers, and cyan couplers can be used without any particular limitations. These couplers may be so-called 2-equivalent type couplers or 4-equivalent type couplers, and in combination with these couplers, it is also possible to use diffusible dye-releasing type couplers.

Cyan couplers useful in the present invention include, for example, phenolic and naphthol couplers. Specific examples of cyan couplers include U.S. Patent Nos. 2,369,929, 2,434,272, and
2.474.293, 2,521,908, 2.895.826, 3,034,892,
3,311,476, 3,458.315,
3.476, 563, 3.583.971, 3,591,383, 3,767.411,
No. 3.772.002, No. 3,933,494, No. 4.004.929, West German Patent Application (OLS) 2゜4
No. 14,830, No. 2.454.329, Japanese Unexamined Patent Publication No. 1973
-59838, 51-26034, 48-50
No. 55, No. 51-146827, No. 52-6962
No. 4, No. 52-90932, No. 5a-9s34s4,
ff public 'fa49-11572j% etc. can be mentioned.

As the magenta coupler, compounds such as pyrazolone type, pyrazolotriazole type, pyrazolinobenzimidazole type, and indacylon type are used. Examples of pyrazolone magenta couplers include U.S. Patent No. 2.600.788, U.S. Pat.
3,311,476, 3,419.391, 3,519.429, 3,558,318, 3,684,514, 3.8813.680, JP No. 49-29639, No. 49-111631@
, No. 49-129538, No. 50-13041, Special Publication No. 53-47167, No. 54-10491, No. 5
The compound described in US Pat. No. 5-30615, pyrazolotriazole magenta coupler, is
247,493 and Belgian Patent No. 792,525, and as a diffusion-resistant colored magenta coupler, a compound having an arylazo substitution at the coupling position of a colorless magenta coupler is generally used. For example, U.S. Patent No. 2,801,171;
, No. 983.608, No. 3.005.712, No. 3,
684,514, British Patent No. 937.621, and JP-A-49-123625 and JP-A-49-31448.

Furthermore, a colored magenta coupler of the type described in US Pat. No. 3,419,391, in which the dye flows out into the processing solution by reaction with an oxidized product of a developing agent, can also be used.

As the yellow coupler, an open chain ketomethylene compound has conventionally been used, and the generally widely used benzoylacetanilide type yellow coupler and pivaloylacetanilide type yellow coupler can be used. Furthermore, the carbon atom at the coupling position is substituted with a substituent that can be decoupled during the coupling reaction 2
Yellow couplers of the same type have also been used to advantage. Examples of these are U.S. Pat. No. 2,875,057;
．． No. 506, No. 3,664,841, No. 3,408.
No. 194, No. 3,277.155, No. 3.447.9
No. 28, No. 3,415,652, Special Publication No. 49-135
No. 76, JP-A-48-29432, JP-A No. 48-6883
No. 4, No. 49-10736, No. 49-122335, No. 50-28834, No. 50-132926, etc., together with the synthesis method.

The amount of the diffusion-resistant coupler used in the present invention is generally 0.0 per mole of silver in the light-sensitive silver halide emulsion layer.
It is 5 to 2.0 moles.

In the present invention, DIR compounds are preferably used in addition to the above-mentioned diffusion-resistant couplers.

In addition to DIR compounds, compounds that release development inhibitors during development are also included in the present invention, such as those disclosed in U.S. Pat. No. 3,297,445, U.S. Pat. 2,417,914, JP-A No. 52-15271, JP-A No. 53-9116, JP-A No. 53-9116,
Examples include those described in No. 59-123838 and No. 59-127038.

The silver halide color photographic light-sensitive material used in the present invention may contain various other photographic additives. For example, Research Disclosure Magazine 17643
Antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, optical brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, and wetting agents listed in the No. etc. can be used.

In the silver halide color photographic light-sensitive material used in the present invention, hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graph 1 of gelatin and other polymers - polymers, albumin, casein, etc. proteins, hydroxyethyl cellulose derivatives, cellulose derivatives such as carboxymethyl cellulose, starch derivatives, polyvinyl alcohol, polyvinylimidazole,
Any single or copolymer synthetic hydrophilic polymer such as polyacrylamide is included.

Examples of the support for the silver halide color photographic light-sensitive material used in the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer or a reflective material, such as a glass plate, Examples include polyester films such as cellulose acetate, cellulose nitrate, and polyethylene terephthalate, polyamide films, polycarbonate films, and polystyrene films, and other usual transparent supports may be used. These supports are appropriately selected depending on the intended use of the photosensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used to coat the halogen warm emulsion layer and other photographic constituent layers used in the present invention. Also in the US time rf2.76
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 1.791 and No. 2,941,898.

In the present invention, the coating position of each emulsion layer can be determined arbitrarily.

In the photosensitive material of the present invention, it is optional to provide an intermediate layer having an appropriate thickness depending on the purpose, and a filter layer,
Various layers such as an anti-curl layer, a protective 1G layer, and an antihalation layer can be used in appropriate combinations as constituent layers.

Hydrophilic colloids that can be used in the emulsion layers as described above can be used as binders in these constituent layers, and various types of colloids that can be contained in the emulsion layers as described above can be used in these layers. Photographic additives may be included.

In the method for processing a silver halide color photographic light-sensitive material of the present invention, if the silver halide color photographic light-sensitive material is a light-sensitive material that contains a coupler in the light-sensitive material and is processed by a so-called internal development method, color It can be applied to any silver halide color photographic material such as paper, color negative film, color positive film, color reversal film for slides, color reversal film for movies, color reversal film for TV, and reversal color vapor.

[Specific Effects of the Invention] As explained above, the present invention provides an excellent silver halide color photographic light-sensitive material that has rapid silver bleaching ability and exhibits extremely little deterioration in recoloring property of cyan dye. A processing method can be provided.

[Specific Practical Examples of the Invention] Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments of the present invention are not limited to these.

Example 1 Following the layer structure adopted in the industry for high-sensitivity silver halide color photographic light-sensitive materials, an antihalation layer, a red-sensitive silver halide layer, and a red-sensitive silver halide layer were coated from the support with various auxiliary layers interposed. They were an emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer, and a monodisperse high-sensitivity silver halide emulsion layer was disposed on the outermost side of the blue-sensitive silver halide emulsion layer.

The amount of coated silver is approximately 13+ for the blue-sensitive silver halide emulsion layer.
11 (J/dtz), the green-sensitive silver halide emulsion layer was approximately 18 m (+/d, =), and the red-sensitive silver halide emulsion layer was approximately 13 mg/d1'.

Layer 1: A dispersion of 0.8 g of black colloidal silver, which is highly absorbent to light in the wavelength range of 400 to 700 nm by reducing silver nitrate with hydroquinone as a reducing agent, is prepared in 3 g of gelatin, and an antihalation layer is applied. did.

Layer 2: Intermediate layer made of gelatin (dry thickness 0.8 μm) Layer 3: 15 g of low-sensitivity red-sensitive silver iodobromide emulsion (Ag
I: 6 mol%), 1.9 g of gelatin and 0.96 (
l of 1-hydroxy-4-(β-methoxyethylaminocarbonylmethoxy”)-N-[δ-(2,4-di[
-amylphenoxy)butylco-2-naphthamide (hereinafter referred to as cyan coupler (C-1>), 0.028 (
l of 1-hydroxy-4-[4-(1-hydroxy-8
-acetamido-3,6-disulfo-2-naphthylazo)phenoxy] -N-[δ-(2,4-Z-amylphenoxy)butyl]-2-naphthamide disodium (hereinafter referred to as colored cyan coupler (CC- 0.40 tricresyl phosphate (referred to as
(hereinafter referred to as TCP).

Layer 4 - Highly sensitive red-sensitive silver iodobromide emulsion (A
gI: 8 mol%) 1.2 (l of gelatin and 0.
4IQ cyan coupler (C-1>, 0.0269 colored cyan coupler (CC-1) dissolved in 0, 1
A highly sensitive red-sensitive silver halide emulsion layer containing 59 TCPs.

Layer 5: 2,5-di-t-octylhydroquinone (hereinafter referred to as antifouling agent (HQ-1)) of o, oag
0.04 g of dibutyl phthalate (hereinafter referred to as
DBP) and 1.2 g of gelatin.

Layer 6...1.6 (+ low sensitivity green photosensitive iodobromide limiting agent (AVI: 15 mol?6>, 1.7'J of gelatin and 0.3 og of 1- (2,4 ,6-trichlorophenyl)-3-[3-(2,4-di-t-amylphenoxyacetamide)benzenamide]-5-pyrazolone (hereinafter referred to as magenta coupler (M-1)), 0,2
0(l of 4.4-methylenebis-11-(2,4,6-
Dolichlorophenyl)-3-[3-(2,4-di-t-
amylphenoxyacetamide)benzenamide]-5
-pyrazolone (hereinafter referred to as magenta coupler (M-2)), 0.066 CI of 1-(2°4.6-1-lichlorophenyl)-4-(1-naphthylazo)-3-(2-
Chloro-5-octadecenyl succinimide anilino)
-5-pyrazolone (hereinafter referred to as colored magenta coupler)
0, 3 in which three types of couplers (referred to as CM-1) were dissolved
A low-sensitivity green-sensitive silver halide emulsion layer containing g of TCP.

Layer 7: Highly sensitive green-sensitive silver iodobromide emulsion (ACII:1
1 mol %), 1.9 g of gelatin and 0.093 (+
Magenta coupler (M-1), 0,094 (l) magenta coupler (M-2), 0,049Q colored magenta coupler (CM-1) dissolved in 1.2 g of TCP
A high-sensitivity green-sensitive silver halide emulsion layer containing.

Layer 8...0.2(l yellow colloidal silver, 0.11(l DBP) dissolved in 0.2g antifouling agent (HQ-1)
and a yellow filter layer containing 2.19 gelatin.

Layer 9...0.95g of low-sensitivity blue-sensitive silver iodobromide emulsion (
AoI: 6 mol%), 1.9 g of gelatin and 1,
84(] α-[:4-(1-benzyl-2-phenyl-3,5-dioxo-1°2.4-doriazolidinyl)
]-]α-pivaloyru2-chloro5[γ-(2,4
-di-t-amylphenoxy)butanamide]acetanilide (hereinafter referred to as yellow coupler (Y-1)) is dissolved in a low-sensitivity green-sensitive silver halide emulsion layer containing DBP of 0,93(1).

Layer 10: 1.2 g of high-sensitivity monodisperse blue-sensitive silver iodobromide emulsion (ACII; 7 mol %), 2. A high-sensitivity blue-sensitive silver halide emulsion layer containing gelatin of Og and DBP of 0.23() in which a yellow coupler (Y-1) of 0.46() was dissolved.

Layer 11: Second protective layer made of gelatin.

Layer 12: first protective layer containing 2.3 g of gelatin.

The sample obtained above was subjected to 20 CMS wedge exposure using a tungsten light source and adjusting the color temperature to 4800°K with a filter.

The exposed photosensitive material was subjected to the following treatments.

The processing steps included color development for 3 minutes and 15 seconds, bleaching for 2 minutes and 30 seconds, fixing for 3 minutes and 15 seconds, first stabilization for 2 minutes, and second stabilization for 30 seconds.

Each treatment was carried out at 37.8°C, and each treatment liquid was prepared according to the following formulation.

[Color developer] [Carbonic power 30 g1
Sodium hydrogen carbonate 2.5g [Bleach solution] [Fixer] [Second stabilizing solution] r Formalin (37% solution) 7.0.1
The bleaching acceleration effect was evaluated by determining the residual silver m in the maximum dye density part of the sample after treatment by fluorescence X-ray method. Furthermore, after measuring the maximum transmission density of the cyan dye using an optical densitometer PDA-65 (manufactured by Konishi Roku Photo Industry Co., Ltd.), the cyan dye was treated for 3 minutes at 35°C in an oxidation bath containing 3% red blood salt. The maximum transmittance density of the cyan dye of the sample in which 11 colors of dye were sufficiently added was measured again, and the color recovery property was evaluated by determining the difference ΔDa from the cyan dye concentration before color recovery.

The results are shown in Table 1.

As is clear from Table 1 on page 7, even if hydroxylamine b bleaching accelerators other than those of the present invention are used, silver remains in the photosensitive material without being sufficiently bleached within the bleaching time of this practical example. Although the amount is large, it can be seen that a good bleaching accelerating effect can be obtained by using the hydroxylamines of the present invention.

Furthermore, when a hydroxylamine sulfur M salt other than the present invention is used, poor color restoration occurs when the bleaching accelerator of the present invention is used; It can be seen that this almost never occurs.

In addition, when each hydroxylamine is used in a color developing solution, as a bleaching accelerator (I-6>, (
I-13>, (II-23>, (■-29), (II-
40), (II-45), (I[[-3), (TV-1
), (V-17), (■-20), (Vl-17> and (■-2)) were further processed.
Almost similar results were obtained using the bleach accelerators listed in Table 1.

Example 2 Using the photosensitive material used in Example 1, bleach-fixing was performed for 3 minutes and 15 seconds using a bleach-fixing solution having the following composition in place of the bleaching and fixing in Example 1.

As for the hydroxylamines in the color developing solution, those listed in Table 2 were used, and only 1 listed in Table 2 was used.

[Bleach-fixing solution] The bleach-accelerating effect and color restoration properties of the treated samples were evaluated in the same manner as in Example 1.

The results are shown in Table 2.

It is clear from Table 2', t J: Sea urchin, even in systems using bleach-fixing baths, hydroxylamine sulfates other than those of the present invention
Even if the bleach accelerator of the present invention is used,
Although there is a large amount of silver remaining in the photoreceptor R1 due to insufficient bleach-fixing within the bleach-fixing time of this example, the use of the hydroxylamines of the present invention provides a good bleaching accelerating effect. Recognize.

Moreover, human 1-coxylamine lii! other than the present invention! When I salts are used, poor color recovery occurs when the bleaching accelerator of the present invention is used, but poor color recovery hardly occurs when the hydroxylamines of the present invention are used. Recognize.

In addition, when each hydroxylamine is used in a color developing solution, as a bleaching accelerator (I-6>, (
I-13), (II-123), (I[-29), (I
I-40), (I-45), (III-3), (IV-
1>, (V-17), (Vl-20), (Vl-17
＞, and (■-2) were further carried out, and almost the same results were obtained as when using the bleach accelerators listed in Table 2.

Example 3 Using the photosensitive material used in Example 1, in place of the bleaching and fixing treatment in Example 1, a bleaching solution and a bleach-fixing solution having the following composition were used, and after bleaching was performed for 40 seconds. A bleach-fixing process was performed for 3 minutes and 15 seconds.

As for the hydroxylamines in the color developing solution, those listed in Table 3 were used, and only the amounts listed in Table 3 were used.

[Bleach solution] [The bleach-accelerating effect and color reversibility were evaluated in the same manner as in Example 1 for the sample treated with the bleach-fix solution.

The results are shown in Table 3.

As is clear from Table 3, when hydroxylamine sulfates other than those of the present invention are used, the effect of promoting bleaching is small;
Color recovery is also poor, especially when the color developer is mixed into the bleaching solution.
% or more, especially 5% or more, the bleaching accelerating effect becomes significantly smaller and the recoloring property deteriorates significantly, but by using the hydroxylamines of the present invention, the mixing rate of the color developing solution in the bleaching solution increases. However, it can be seen that both the bleaching accelerating effect and the recoloring property are good. In addition, as hydroxylamines, exemplary compounds of the present invention (A-3>, (A-8), (
A-9), (A-12>, (A-22) and (A-24
) was used, but similar good results were obtained.

Patent applicant Konishiroku Photo Industry Co., Ltd. Wow

Claims (1)

Scope of Claims: (1) After imagewise exposing a silver halide color photographic material having at least one silver halide emulsion layer on a support, at least a color developing solution and a processing solution having bleaching ability. In the method for processing a silver halide color photographic light-sensitive material, the color developing solution has the following general formula [A]
The treatment with the treatment solution containing at least one of the compounds represented by the following formula [I
] - [IX] A method for processing a silver halide color photographic material, characterized in that it is carried out in the presence of at least one compound selected from the compounds represented by [IX]. General formula [A] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 and R_2 each represent an alkyl group or a hydrogen atom. However, R_1 and R_2 cannot both be hydrogen atoms at the same time. Also, R_1 and R_2 may form a ring.) General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. R_1 represents the atomic group necessary to form a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic group (including
(including those in which six-membered unsaturated rings are condensed) or an amino group. ] General formula [II] ▲Mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_2 and R_3 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amino group, and a number of carbon atoms. Represents 1 to 3 acyl, aryl, or alkenyl groups. A has ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, -SZ or n_1 represents a heterocyclic residue (including those in which 5- to 6-membered unsaturated rings are fused), and X = S, =O or =NR''. Here, R and R' are synonymous with R_2 and R_3, respectively, X' is synonymous with X, and Z is a hydrogen atom, an alkali metal atom, an ammonium group, an amino group,
Represents a nitrogen-containing heterocyclic residue, an alkyl group, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, M represents a divalent metal atom, R″ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, Represents a cycloalkyl group, an aryl group, a heterocyclic residue (including those in which 5- to 6-membered unsaturated rings are condensed), or an amino group, and represents n_1 to n_6 and m_1 to
m_5 each represents an integer from 1 to 6. B represents an alkylene group having 1 to 6 carbon atoms, and Y represents -N< or -
CH<, and R_4 and R_5 are each R_2
and R_3. However, R_4 and R_5
may each represent -B-SZ, and R_2 and R_3, R and R', and R_4 and R_5 may each be combined to form a ring. Note that the compound represented by the formula also includes enolated products and salts thereof. ] General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_6 and R_7 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amino group, and the number of carbon atoms. Represents 1 to 3 acyl groups, aryl groups, alkenyl groups, or -B_1-S-Z_1. However, R_6 and R_7
may be combined to form a ring. Y_1 represents >N- or >CH-, B_1 represents an alkylene group having 1 to 6 carbon atoms, and Z_1 represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue, or a formula ▲ , chemical formula, table, etc. Represents ▼. n_7 represents an integer from 1 to 6. ] General formula [IV] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_8 and R_9 are respectively ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Numerical formulas, chemical formulas,
There are tables, etc. ▼ represents or, and R_1_0 represents an alkyl group or -(CH_2)_n_8SO_3^■. (However, when R_1_0 is -(CH_2)_n_8SO_3^■, l represents 0, and when it is an alkyl group, it represents 1.) G^■ represents an anion. n_8 represents an integer from 1 to 6. ] General formula [V] ▲ Numerical formulas, chemical formulas, tables, etc. R_1_1 represents a hydrogen atom, an alkali metal atom, a numerical formula, a chemical formula, a table, etc., or an alkyl group. However, Q' has the same meaning as Q_1. ] General formula [VI] ▲ Numerical formulas, chemical formulas, tables, etc. q_2, q_3 and q_4 represent 0, 1 or 2, respectively. Further, the ring formed together with the sulfur atom may be further condensed with a 5- to 6-membered saturated or unsaturated ring. ] General formula [VII] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X_2 is -COOM', -OH, -SO_3M', -CONH_2, -SO_2NH_2
, -NH_2, -SH, -CN, -CO_2R_1_6
, -SO_2R_1_6, -OR_1_6, -NR_1
_6R_1_7, -SR_1_6, -SO_3R_1_
6, -NHCOR_1_6, -NHSO_2R_1_6
, -OCOR_1_6 or -SO_2R_1_6, and Y_2 has ▲mathematical formula, chemical formula, table, etc.▼, ▲mathematical formula, chemical formula,
There are tables, etc. ▼ Or it represents a hydrogen atom, and m_9 and n_9 each represent an integer from 1 to 10. R_1_1, R_1_2,
R_1_3, R_1_4, R_1_5, R_1_7 and R_1_8 each represent a hydrogen atom, a lower alkyl group, an acyl group, or ▲a numerical formula, chemical formula, table, etc.▼, and R_1_
6 represents a lower alkyl group, R_1_9 is -NR_
2_0R_2_1, -OR_2_2 or -SR_2_
2, R_2_0 and R_2_1 each represent a hydrogen atom or a lower alkyl group, and R_2_2 represents R
Represents the atomic group necessary to combine with _1_8 to form a ring. R_2_0 or R_1_1 may be combined with R_1_8 to form a ring. M' represents a hydrogen atom or a cation. ] General formula [VIII] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Ar is a divalent aryl group or a combination of an aryl group and an oxygen atom and/or an alkylene group.
B_2 and B_3 each represent a lower alkylene group, R_2_3, R_2_4, R
_2_5 and R_2_6 each represent a hydroxy-substituted lower alkyl group, and x and y each represent 0 or 1. G' represents an anion, and z represents 0, 1 or 2. ] General formula [IX] ▲Mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_2_9 and R_3_0 each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R_3_1 represents a hydrogen atom or an alkyl group, R
_3_2 represents a hydrogen atom or a carboxy group. ](
2) The method for processing a silver halide color photographic light-sensitive material according to claim (1), wherein the processing solution having bleaching ability contains an organic acid ferric complex salt as a bleaching agent. (3) The content of the color developing solution in the processing solution having bleaching ability is 5% or more.
A method for processing a silver halide color photographic light-sensitive material according to item 1) or (2).