JPS6219851A - Treatment of silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance bleach-fixability of a photosensitive material capable of both attaining superhigh sensitivity and preventing waste of resources by processing the photosensitive material having the whole constituent layers specified in thickness and an emulsion layer containing silver iodide and a binder having a specified swelling speed. CONSTITUTION:The photographic constituent layers comprises blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layers, and contains the total coated silver in an amount of <=50mg/dm<2>, and at least one of the silver halide emulsion layers contains silver halide grains containing >=0.5mol% silver iodide. The total thickness of the photographic constituent layers if <=25mum, and the binder has a swelling speed T 1/2 of <=25sec. Such a silver halide color photographic sensitive material is imagewise exposed and developed, and processed in a bleach-fixing bath containing at least one of an organic acid ferric salts, thus permitting rapid processing of the photosensitive material to be attained.

Description

[Detailed description of the invention] [Industrial application field]

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 a silver halide color photographic material having rapid silver bleach-fixing ability.

[Prior art]

Generally, in order to obtain a color image by processing a silver halide color photographic light-sensitive material that has been imagewise exposed, a step is provided after the color development step to treat the generated metallic silver with a processing solution having bleaching ability. There is. Bleaching solutions and bleach-fixing solutions are known as processing solutions having bleaching ability. When a bleaching solution is used, a step of fixing silver halide with a fixing agent is usually added next to the bleaching step, but sometimes a bleach-fixing process is performed in which bleaching and fixing are performed in one step. Inorganic oxidizing agents such as red blood salts and dichromates are widely used as oxidizing agents for bleaching image silver in processing solutions that have bleaching ability in processing silver halide color photographic materials. . However, several serious drawbacks have been pointed out to processing solutions containing these inorganic oxidizing agents and having bleaching ability. For example, red blood salt and dichromate are relatively excellent in terms of bleaching blades for image silver, but there is a risk that they will decompose when exposed to light and produce cyanide ions and hexavalent chromium ions that are harmful to the human body. It has unfavorable properties in terms of pollution prevention. In addition, because these oxidizing agents have extremely strong oxidizing power, it is difficult to coexist silver halide solubilizers (fixing agents) such as thiosulfates in the same processing beneficial insects, and these oxidizing agents are not included in bleach-fix solutions. It is almost impossible to use agents,
This makes it difficult to achieve the objectives of speeding up processing and reducing the number of elements. Furthermore, treatment liquids containing these inorganic oxidizing agents have the disadvantage that it is difficult to reuse them without discarding the waste liquid after treatment. On the other hand, metal complex salts of organic acids, such as aminopolycarboxylic acid metal complex salts, are used as oxidizing agents, as they have fewer pollution problems and meet the demands of speeding up and simplifying treatment, and enabling recycling of waste liquid. In recent years, treatment solutions have come to be used. However, a processing solution using a metal complex salt of an organic acid has a weak oxidizing power, and therefore has the disadvantage that the bleaching speed (oxidation speed) of the image silver (metallic silver) formed in the development step is slow. For example, iron ethylenediaminetetraacetate (I[
I) Complex salts have been put to practical use in some parts as bleaching solutions and bleach-fixing solutions, but they can also be used in high-sensitivity silver halide color photographic materials based on silver bromide and silver iodobromide emulsions, especially silver halodendine. Color negative film and color reversal film containing silver iodide for photography lack bleaching blades,
Even after long-term processing, traces of image silver remain, resulting in poor desilvering. This tendency is particularly noticeable in a bleach-fix solution in which an oxidizing agent and thiosulfate and sulfite coexist because the redox potential is lowered. In particular, it has been found that in high-sensitivity silver iodide-containing silver halide color photographic light-sensitive materials for photographic use that contain black colloidal silver to prevent harene a, the desilvering properties are markedly deteriorated. Furthermore, the silver halide emulsion, which is the silver iodide-containing high-sensitivity emulsion, has fine grains, and effectively utilizes silver to meet the requirements for resource conservation; Recently, there is a core-shell emulsion that has been developed.This core-shell emulsion uses a preceding silver halide emulsion as a crystal nucleus, and successive precipitates are laminated on top of this, and the composition or environment of each precipitate is intentionally controlled. It is a monodisperse core-shell emulsion that is controlled and made. Among these, the core-shell type high-sensitivity emulsions containing silver iodide in the core and/or shell have extremely favorable photographic performance characteristics, but conventional bleach-fixing baths cannot be used for silver halide color photographic light-sensitive materials. When applied, it has been found that the bleach-fixing properties of developed silver and silver halide are extremely poor. That is, developed silver of a photographic silver halide emulsion containing 0.5 mol % or more of silver iodide is a core-shell emulsion in which halogen containing 0.5 mol % or more of silver iodide is used in the core and one shell. Developed silver made of silver oxide grains has excellent sensitivity, granularity, covering power, etc., but in color photographic materials that require bleaching of the developed silver, the form of the developed silver is different from conventional ones, so the bleaching properties are poor. It gets really bad. In particular, as an emulsion, JP-A Nos. 58-113930, 58-113934, and 5
8-127921 and 58-108532, etc., which use tabular silver halide grains, the number of photons captured by the silver halide grains increases. It is said that even if the amount of silver used increases, the amount of silver used will not increase, and the image quality will not deteriorate. However, even with these tabular silver halide grains, 1. Developed silver formed by development with a p-phenylenediamine color developing agent has a drawback of poor silver bleaching properties. Therefore, it is possible to quickly produce a silver halide color photographic light-sensitive material that is a core-shell emulsion and/or a tabular silver halide emulsion containing silver iodide, which is an excellent emulsion, as described above, and has an antihalation layer made of black colloidal silver. There is a particularly strong desire for the development of a processing solution that bleach-fixes.

[Problems to be solved by the invention]

The present invention has a technical object, firstly, to provide an excellent bleach-fixing method for highly sensitive fine-grain type, high-sensitivity silver iodide-containing silver halide color photographic light-sensitive materials that can achieve both resource conservation and ultra-high sensitivity. The second objective is to provide a processing method using a bleach-fix solution that enables rapid processing of high-sensitivity color photographic materials.

[Structure of the invention]

As a result of extensive research, the present inventor has found that the present inventor has a photographic constituent layer including blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers, and that the total coated silver amount is 50 aH/du+2 or less. At least one of the emulsion layers contains silver halide grains containing 0.5 mol% or more of silver iodide, and the total thickness of the photographic constituent layers is 25 μm or less, and the swelling rate of the baingu film of the photographic emulsion layer is A silver halide color photographic light-sensitive material having a T3A of 25 seconds or less is developed after imagewise exposure,
It has been found that the objects of the invention are achieved by treatment with a bleach-fix solution containing at least one ferric salt of an organic acid. Preferably, the organic acid ferric complex salt is selected from (,) to (q) described in claim 13. Here, the photographic constituent layer refers to the 7F photosensitive layer of the present invention,
Refers to all the wood-loving troid layers that participate in image formation and are located on the same side as the support surface coated with at least three silver halide emulsion layers, green-sensitive and red-sensitive, and include black colloidal silver halation. Particularly effective when there is a protective layer,
In addition to the silver halide emulsion layer, for example, a subbing layer, an intermediate layer (a simple intermediate layer, a single filter layer, an ultraviolet absorbing layer, etc.)
, a protective layer, etc. General formula []] General formula [■] General formula (In
) General formula [■] General formula CV) General formula (Vl) General formula [■] R11R14 In the above general formula, Q is a heterocycle containing one or more N atoms (5
- represents an atomic group necessary to form a group of atoms (including those in which at least one unsaturated ring of 6 shells is fused to it), and A is x''X''X/' or a 111-valent heterocyclic residue (including those in which at least one unsaturated ring of 5 to 6 shells is fused),
B represents an alkylene group having 1 to 6 carbon atoms, M represents a divalent metal atom, and X and X'' are =S, =O or =N
R" represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue (at least one unsaturated ring of 5 to 6 atoms is fused to this) or an alkyl group, R1 is a hydrogen atom,
Represents an alkyl group, cycloalkyl group, aryl group, heterocyclic residue having 1 to 6 carbon atoms (including those to which at least one unsaturated ring of 5 to 6 atoms is fused) or an ami7 group , R2, R3, R'', R5, R and R' are each
Hydrogen atom, alkyl group having 1 to 6 carbon atoms, hydroxy group,
Represents a carboxyl group, an amine 7 group, an acyl group having 1 to 3 carbon atoms, an aryl group, or an alkenyl group. However, R4 and R
5 may represent -B-8Z, or R, R', R2
and R3, R4 and R5 may each be cyclized with each other to form a heterocyclic residue (including one in which at least one unsaturated ring of 5 to 6 shells is fused thereto). R6 and R7 each represent an alkyl group or -(CH2)n, SO
, - However, when R8 is -(CH2)n, SO, -, q represents 0 or 1. ) G- is an anion, l11
1 to m and nl to R8 each represent an integer of 1 to 6, and +115 represents an integer of 0 to 6. R8 is a hydrogen atom,
Alkaline. However, Q' has the same meaning as Q above. D represents a simple bond, a fullylene group or a vinylene group having 1 to 8 monoprimes, and q represents an integer of 1 to 10. multiple D
may be the same or different, and the ring formed with the 1N sulfur atom may be further fused with 5 to 6 unsaturated rings. X′
is 1000M', -OH, -803M', -CONH2
, -8O2NH2, -NH2, -3H, -CN, -CO
2R", -S O2RIg, -OR", N
RI If RIf, -S RI G, -S
O3R", -NHCOR", -NHS O2R", -
00OR'6 or -S O2R'', Y' represents or a hydrogen atom, and m and n each represent an integer of 1 to 1o. Rth]: j I S , R
l and R'th represent a hydrogen atom, a lower alkyl group, an acyl group, or →ta-x'11'+, and R'G represents a lower alkyl group. R mouth is -N
R2° represents R21, -0R22 or -8R22, R2
0 and R'' represent a hydrogen atom or a lower alkyl group, R
22 represents an atomic group necessary to form a ring by bonding with R''. R20 or R'' and R18 may bond to form a ring. M' represents a hydrogen atom or a cation. In addition, the compounds represented by the general formulas [1] to (V) include di-/- and salts thereof. That is, the present inventors have developed a highly sensitive fine-grain silver halide color having black colloidal silver as an antihalation layer and having at least three layers of silver halide hole cuttings containing at least 0.5 mole percent silver iodide-containing emulsion. Focusing on the phenomenon of poor bleach-fixing properties of photographic light-sensitive materials, we have conducted intensive research and found that the total coating silver amount and emulsion layer thickness of silver halide color photographic light-sensitive materials are below a certain value, and that the binder It has been found that if the membrane swelling rate T3A is 25 seconds or less, even a bleach-fix solution containing an organic a-ferric complex salt can be sufficiently desilvered. Furthermore, it has been found that when processed with a bleach-fix solution containing a combination of specific compounds according to the present invention, the time required to complete bleach-fixing of a silver iodide-containing silver halide color photographic light-sensitive material is further shortened. In particular, when the photographic constituent layer of a photographic material made of a silver helodenide emulsion is thinned below a certain value according to the present invention, the bleach-fixing properties are significantly improved.
It was discovered that desilvering defects can be improved. Furthermore, the present inventor has found that the larger the molecular weight of the organic acid in the ferric organic acid complex salt, the smaller the swelling rate T of the binder film of the photographic constituent layer (gelatin film), which increases the bleaching promoting effect. They discovered that the opening time was significantly shortened during bleaching. On the other hand, it has also been discovered that the smaller the molecular weight of the organic acid in the organic acid ferric salt, the better the reduction in the thickness of the photographic constituent layer (gelatin g). In other words, in general, the larger the molecular weight of the organic acid in the organic acid 12 iron salt, the greater the oxidizing power of silver, but the more the effect of hardening the photographic constituent layers increases, the more the diffusion and permeation of bleach-fixing components is significantly reduced. This inhibition occurs and is large compared to the thickness of the photographic constituent layers, but this inhibition does not occur when gelatin has a property that the membrane swelling rate is extremely fast. On the other hand, it has a small molecular weight, 811ill! The fjtJ2 iron complex salt has a slightly weak oxidizing power for silver (although it does not inhibit bleach-fixing), so if the thickness of the photographic constituent layer is below a certain value according to the present invention, or if the gelatin film swelling rate is high as described above, it can be effectively used. It was found that a sufficient bleaching edge could be obtained.Furthermore, as the thickness of the N4 film in the photographic hη layer of a silver iodide-containing silver halide color photographic light-sensitive material increases, the black colloidal silver-containing antihalation layer and the silver iodide-containing antihalation layer Bleach-fixing inhibition, which is accentuated due to significant desilvering failure occurring at the boundaries of silver halide emulsion layers containing silver halide, is also caused by the photographic constituent layers +--!finnl injection *-
6j*l? 1-1M Nora←! We have found that this can be reduced by increasing the swelling rate of the gelatin membrane beyond a certain value. Therefore, according to the present invention, an innovative rapid bleach-fixing method has been discovered in which the bleach-fixing properties are not impaired even when a ferric acid complex salt of any molecular weight is used. According to a preferred embodiment of the present invention, the film thickness of the photographic constituent layer of the silver halide color photographic light-sensitive material is 22 μm or less, particularly preferably 20 μm or less, and the Bainggu film swelling rate T is 20 seconds or less, particularly preferably is 15 seconds or less, most preferably 10 seconds or less, and the bleach-fixing accelerator and the organic acid forming the ferric acid complex salt may be the following compounds. It has been found that the objects of the present invention can be effectively achieved by these methods. Margin below (3) H2N CNHNHCNt12 (4)
HOCH2CI CH25H(5) Its Ct12
Ct12Coo) 11l (15) C2H5>NC,, □CH2C) i2Ntl
CNHSH2o5II (16)0H')NCH2Cl2SH-C-5CH3
CH3II (17)”1>NCH2Cl2S CNHC[1aCI
I3 11 “”)”” >NCH2Cll2S CNIICI(a
CH3II (19)”13)NCH7C1l, N11-C-5CH
3coa II VS CI+. CH. CH CH (28) ll5cH2CH2NHCII2CH2
0H(29) 1IsclI2cH2NCH2CI
I□OH1, H5 or (a) diethylenetriaminepentaacetic acid (b) cyclohexanecyaminotetraacetic acid (c) triethylenetetraminehexaacetic acid (d) glycol ether diamine (e) 1,2-noaminopropane acetic acid (f) 1 .3-
Diaminopropan-2-ol acetic acid (g) ethylenecyamine di-0-hydroxyphenylacetic acid (11) ethylenenoamine acetic acid (i) nitrilotriacetic acid (j) iminodiacetic acid (k) methyliminodiacetic acid (1) hydroxy Ethyliminodiacetic acid (1) Ethylenenoaminetetraprobionic acid (n) Dihydroxyethylglycine (0) Nitrilotripropionic acid (1)) Ethylenediaminediacetic acid (q) Ethylenediaminedipropionic acid In the most effective embodiment, It has been found that the above objects of the present invention can be most effectively achieved by a processing method in which a fixing process is performed after the color development process and as a preprocessing step of the bleach-fixing process. Hereinafter, this fixing treatment will be referred to as a pre-fixing treatment or pre-fixing, and the processing liquid used in the pre-fixing treatment will be referred to as a pre-fixing treatment liquid or pre-fixing solution, or a pre-fixing treatment bath or a pre-fixing bath. The present invention will be explained in more detail below. The hydrophilic binder used to coat silver halide in silver halide color photographic light-sensitive materials is usually gelatin, but high molecular weight polymers may also be used, and if the film swelling rate TX is less than 25 seconds. No. The swelling rate T of the binder can be measured according to any method known in this technical field, for example, as described by Green et al.
t. Sci. Eng. ), Vol. 19, No. 2, pp. 124-129, it can be measured by using a swellometer (swell meter) of the type described, and T3A is reached when treated with a color developer at 30°C for 3 minutes and 15 seconds. Maximum swelling #i Saturation of 90% of thickness m
The film thickness is defined as the time required to reach this film thickness. The membrane swelling rate T% can be adjusted by adding a hardening agent to gelatin as a binder. Hardening agents include aldehyde-based, aziridine-based (for example, PB Report 19,921, U.S. Patent No. 2,950.197, U.S. Pat. No. 2,964,404, U.S. Pat. No. 2,983,6).
No. 11, 3,271. No. 175, Japanese Patent Publication No. 40898, Japanese Patent Publication No. 1973-
No. 91315, etc.), inoxacillium systems (e.g., those described in U.S. Pat. No. 3,321,323), and epoxy systems (e.g., U.S. Pat. No. 3,047,394).
No., West German Patent No. 1,085. No. 663, British Patent No. 1,033,518, Special Publication No. 1973
- those described in No. 35495, etc.), vinyl sulfones (e.g., PB Report 19,920, West German Patent 1,
No. 100,942, same 2. 337, 412, 2,545,722, 2,6
No. 35,518, same 2. No. 742,308, No. 2,749,260, British Patent No. 1,251,091, U.S. Patent No. 3,539,644, U.S. Patent No. 3,490.911, etc.), acryloyl type (for example, U.S. Pat. No. 3.640,720), carbodiimide series (
Example 9 Po, *National patent 2.938.892 bone, same 4,043
．． No. 818, No. 4, No. 081,499, Special Publication No. 1973-
38715, etc.), trianone series (for example, West German Patent Nos. 2, 410, 973, 2,
No. 553,915, U.S. Pat. No. 3,325,287, #
[Those described in Sho 52-12722, etc.], polymer type (
For example, British Patent No. 822,061, US Patent No. 3,62
3.878, same 3. No. 396, 029, No. 3,226,234, Special Publication No. 4
No. 7-18578, No. 18579, No. 47-48
896, etc.), maleimide-based, acetylene-based, methanesulfonic acid ester-based, and N-methylol-based hardeners can be used alone or in combination. As a useful combination technique, for example, West German patent 2,447,
No. 587, same 2. 505,746, US Patent No. 2,514.245, US Patent No. 4,047,957, US Patent No. 3,832.181, US Patent No. 3
, 840,370, JP-A No. 48-43319, JP-A No. 50-63082, JP-A No. 52-127329, and JP-A No. 48-32364. The binder of the photographic constituent layer used in the color photographic material of the present invention is the film! The IJ wetness speed T is 25 seconds or less, and the smaller the better, but the lower limit is too small, otherwise the film will not harden and problems such as scratches will easily occur, so it is less than 1 second.
is preferred. The time is more preferably 2 seconds or more and 20 seconds or less, particularly preferably 15 seconds or less, and most preferably 10 seconds or less. If it is longer than 25 seconds, the desilvering property, that is, the bleach-fixing performance will deteriorate, especially when a low molecular weight organic acid ferric complex salt is used, or even if a high molecular weight organic acid ferric complex salt is used, the concentration used may deteriorate. The deterioration is noticeable when the price is high.・ □ <=・The bleaching accelerator of the present invention is represented by the above general formulas (1) to [■], and representative examples thereof include the following. It is not limited to this. [Exemplary compounds] (1-1) (+-2) (1-3)
'(r-4)(1-5>
(1-6) (I-9) N
-10) (111) (r 12) (I
-13> (1-14)Ct
12 r C) 12C! 12cH2s038a
(I-17) (1
-18>(I -19)
(1-20) Cll2CH2COOH H2C: UυHCH2CH (1-25>(1-26>
Cll2CH2COOH HH (+ -31) (I -32
)(1-33) '(1-:3
4) (1-37) (1-
38>(II-1) (I
[-2) (ff -3) (II
-4) (II -5> (I
I-6) (IT-7) (I
I-8>(I[-9) (If
-10) (II -11)'
(It-12) SS
bb(n-13)
(If -14) (II -15)
(II-16) (II-17)
(II-18) (II-19) (II-20) S (TI-21) (II-22> (II-23) (It-24) ゛(II-25) (IT-26) S 11 II H3C-NH-C-Nil-NH-C-NH-CH3
(n-271 (U-28) +(2N-CSNIINHCS-N)+2(n-29
) (II-30) (U-31) (II-32)
([1-(II-33) (IT- H2N C3NH(C)12)2NHCS Nll
□ (n-(lI-35) H2N-CSNII(CI+□)4NIICS-NH
2([l- H2N-CSN)l(CI□)sNllCS-Nt1
2 (Ir=37)
(■-・38) S (II-43) (II-44) (II-45) (II-46'> (It-47) ([-48> (U -49) (II-50) (II -51) (II-52) (II-53) (TI -54) (n-55) (n-56) (II-57) (II-58) (II-59) (n-60) (If -61) (TI-82) (IT-63) S (II-64) (II-65) H2N-C-5-S-C-Nl2 (IT-67) CII3-N=C-S-C= N-Cl1311i Na Na (ff-68) Na Na (II-69) (ff-70) (II-71) δ (IT-72) (U-73) (n-74) (IT 75) C113NllCH□CH2N11CSCH2C1l □
Cll2COOH (U-76) (ff-77) (IT-78) (n-82) (TI-83) (n-84> (n-85) (TI-86> (II-87) (II-88) ) (II -89) (IT -90) (IT-91) (n -92) (II-93) (II-94) (II-95) . (If -96) (■ -97) (II- 98) (I[-99) (II-100) (If-101) ([-102) (II-103) ([-104) (ff-105) (ff-106) (II-107) (II -109) (ll -110) (II -111) (IT
-112) (H-113),
(I[-114>(TI-115)
(II-116) (II-117)
(It -118) (n -119)
(II-120)(I[-1
21) (ll -122)(
n −123> (II
-124) (II -125>
(If-126) (II-127>
(TI-128>(n
-129) (■-13
0)S (II-131) (I
[-132)S (II -133) (
TI-134) (II-135)
(II-136) (II-137)
(U-138)(n
-139) (I[-14
0) (II-141)
(II-142>(If-143) (U-144) H (II-145) (n-146) u (II-147) H (]l-148) (TI-149) (II-150) ( ■-151) (■-152) (II-153) (II-154) (If-155) (It-156) (II-157) (rt-158) H2N-C)12CH□-5)I ( nT-2> (III-3) (III-4) (III-5) HOOC-CH2Cl1□・5it (III-(3) (II[-7>([1-8> (I[I-9)
(III-10> (III-11) CIt3CH3(III-
12) -A Q N-C112Cll□-S11℃-ノ([IT -13) (III-14) CII□CI+2-3H (III -15) (III
-16) (III -17) (
III-1,8) (III-19)
(m-20) (III-21)
(II-22) C1bCIl□-5ll (III-23) (III
-24) (III-25) (
III-26) (III-27) (III-28) (1-29> (III-3
0) (I [[-31> (I
[I -32>(I[[-33) (III-34) (III-35> (I[[-36) (III-37) (IV-1) l3 (IV-2) H3 H3 (IV- 3) (■-4) (IV-5) l3 (V-1) (V-2)++ (V-3) (V-4) (V-5)
(V-6) (V-7)
(V-8) (V-9)
(V-10) [V-11)
(V −12) (V −13>
(V -14) (y -15)
(V-16) (V-17)
(V-18) (V-19)
(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) (V-35)
(V-36) (V-37
) (V-38)(
V-39) (V -40) (V -41) (V-42) (V -43> (V -
44) (V -45) (
V-46) (V-47)
(V-48) (V-49>
(V-50) (V-51>
(V-52) (V-53)
(v-54>H3 (V-55) (V-56
) (V-57) (V-58)
(V-59) (V-6
0) (V-61> (V-6
2) (V-63) (V-6
4) (V-65) (V-6
6) (V −67) (V −
68) (V-69) (y-70) (V-71) (y 72
) (V-73) (V-74
) (V-75)
(V-76) (V-77) (
V-78) (V-79) (
V-80) (V-81) (
V-82) (V-83)
(V-84) (V-85)
(V-86>(V-87)
(V-88>(V-89)
(V −90>(V −91>
(V-92)L:H2L:H2Nt12
((:H2) 3 hearing 2 (V -93)
(V-94) (V-95)
(V −961NH2Nl
(2 (V-97) (V-98
)CH2NH2C)H2C)12NH2 (V -99) (V -
100) (V-101)
(V -102>■ 2H5 (V -103> (V -
104) (V -105) (
V-106>(V-107) H2 (V-108) (V-109) (y-tto> (V-111) (V-112) (V-113) (V-114) (V-115) (V -116) (V -117) (V -118> (V -119) (y -120) (V -121) (V -122) (V -123) (V -1
24) (V -125> (V
-126) (V -127)
(V-128) (V-129)
(V-130) (V-1:111)
(V-132) (V-133>
(V -134) (V, +13
5) (V-136) SOYOH
a (V-137) (V-138)
(V −139) (V −1
40) (V -141) (
V-142) (V-143)
(V-144) (V-145)
(V -146) (V -147>
(V-148) (V-149)
(V -150) (V -151
) (V -152) (V
-153) (V -154>(
V -155) (V -15
6) Song SH5H (V -157) (V -
158>(V-159)
(V -160) (V -161>
(V -162) (V -163>
(V -164>(V -165)
(V-166) (V-167
) (V-168)SHN
l2 (V -169) (V -17
0) (V -171> (V-
172) SH (V -173) S (V -174) (V -1
75) SHSH (V -176) SH (V -177) (V -1
78) (V -179) SH (V -180) (V -18
1) (V -182) (V -
183) (V -184) N = N I SH (Vl-1) (Vl-2) (V
l-3) (Vl-4) (V
l-5>(W-6) (VI-7>
(Vl-8) (Vl-9)
(VI-10) (Vl-11)
(■-12) (Vl -13) (VI
-14) (■-15)
(Vl -16) (Vl-17) (Vl
-18) (VI-19) (VI-20)
(Vl-21) (VI
-22) (VI-23> (Vl -24)
(Vl-25>(Vl-26)
(Vl-27) (Vl-28) (Vl
-29) (Vl-30) (V
I-31) (fi-32) (Vl-33
> (VI -34)11+1 (Vl -35) (Vl
-36>l-+h Cll3 C113 +1SCII2C11,NCH2CII□C0NI+□
■ CHl HSCH2Ct12NIICII□CH2011+1s
c112ell□NCII□C1+□011C211°11sc112cII. NC1t2CI□N(CI,h
CH. HSCI12C112NCI□CI+20CI□CII
□0CII. C0CH. The above compounds are described, for example, in British Patent 1, 138.84.
No. 2, JP-A-52-20832, JP-A No. 53-28426
No. 53-95630, No. 53-104232,
No. 53-141632, No. 55-17123, No. 6
No. 0-95540, U.S. Pat. No. 3,232°936, U.S. Pat. No. 3,772,020, U.S. Pat.
, 893° 858, etc., and can be easily synthesized by known techniques. 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 a bleach-fixing bath.
It is also preferable to add Y to a pre-fixing treatment bath and bring it into the bleach-fixing bath by bringing it into the silver halide color photographic light-sensitive material. Most preferably it is present in the pretreatment solution, especially both the prefix treatment solution and the bleach-fix solution. In this case, it may be present in the pre-processing solution and brought into the bleach-fixing solution depending on the photographic material to be processed, or alternatively, it may be included in the silver halide color photographic light-sensitive material in advance during production, and it may be added to the pre-processing bath or bleach-fixing solution. When processing with a bath

[7 Exist 7 "I'm going to put it in. These bleaching steps of the present invention may be used alone,
Two or more types may be used in combination, and the bleach accelerator)
I ft, or the bath () pretreatment solution prior to one of them, especially the moe fixing place! l! The amount added to +(!) is generally about 0.01 to 1 oo per treatment e and IQ.
Good results can be obtained within the range of . However, in general, if the amount added is too small, the effect of promoting bleaching will be small, and if the amount added is too large, precipitation may occur and contaminate the silver halide color photographic material being processed. The amount is preferably 0.05 to 50 g per 1Q, and more preferably 0.05 to 15 g per 1q of treatment liquid. When the bleach-fixing agent of the present invention is added to the bleach-fixing effect V/or to a bath (pretreatment bath, especially prefixing treatment bath) prior to the bleach-fixing bath, it may be added and dissolved as is, but water, alkali, Generally, it is added by dissolving it in an organic acid, etc., but if necessary, it can also be added by dissolving it in a solvent such as methanol, ethanol, acetone, etc. to prevent bleaching. There is no effect on the retention effect. It is desirable that metal ions are supplied to the bleach-fixing solution of the present invention by any method in order to improve the bleach-fixing properties. For example, 710 can be supplied in any form such as denide, hydroxide, sulfate, phosphate, acetate, etc., but it is preferable to supply it as a complex salt of a chelating agent using the following compounds (hereinafter, The metal compound that supplies these metal ions is referred to as the metal compound of the present invention.) but,
However, the chelating agent is not limited to these feeding methods, and any chelating agent such as organic polyphosphoric acid or ami-7-boroborboxylic acid may be used. [Exemplary compounds] (A-1) Nickel chloride (A-2) Nickel nitrate (A-3) Nickel sulfate (A-4) Nickel acetate (A-5) Nickel bromide (A-6) Nickel iodide (A -7) Nickel phosphate (A-8) Bismuth chloride (A-9) Bismuth nitrate (A-10) Bismuth sulfate (A-11) Bismuth acetate (A-12) Zinc chloride (A-13) Zinc bromide ( A-14) Zinc sulfate (A-15) Zinc nitrate (A-16) Cobalt chloride (A-17) Cobalt nitrate (A-18> Cobalt sulfate (A-19) Cobalt acetate (A-20) Cerium sulfate (A-14) -21) Magnesium chloride (A-22) Magnesium sulfate (A-23) Magnesium acetate (A-24) Calcium chloride (A-25) Calcium nitrate (A-26) Barium chloride (A-27) Barium acetate (A-21) 28> Barium nitrate (A-29) Strontium chloride (A-30) Strontium acetate (A-31) Strontium nitrate (A-32) Manganese chloride (A-33) Manganese sulfate (A-34) Manganese acetate (, ~- 35) Lead acetate (A, -36>Lead nitrate (A-37) Titanium chloride (A-38) ml tin chloride (A-39) Zirconium sulfate (A-40) Zirconium nitrate (A-41) Ammonium vananoate ( A-42) Ammonium metavananoate (A-43)
Sodium tungstate (A-44) Ammonium tungstate (A-45) Aluminum chloride (A-46) Aluminum sulfate (A-47) Aluminum nitrate (A-48) Yttrium sulfate (A-49) Indritum nitrate (A-50 ) Yttrium chloride (A-51) Samarium chloride (A-52) Samarium bromide <A-53) Samarium sulfate (A-54) Samarium acetate (A-55) Ruthenium sulfate (A-56) Ruthenium chloride The metal compound may be used alone, or two
More than one species can also be used together. The amount used is preferably 0.0001 mol to 2 mol, particularly preferably 0.001 mol to 1 mol O', per 1 g of the liquid used as metal ions. The bleaching accelerator of the present invention is represented by the general formulas (1) to [■], among which R1, R2, R3, R4, R5, R
6, R9, ASI3. D, Z, Z', R1R', and a heterocyclic residue formed by R and R', R2 and R3, R4 and R5, and Q, Q', an ami7 group, an aryl group, an alkenyl The group and the alkylene group may each be substituted. Substituents include alkyl groups, aryl groups, alkenyl groups, cyclic alkyl groups, aralkyl groups,
Cyclic alkenyl group, halogen atom, nitro group, cyano group, alkoxy group, aryloxy group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group,
Sulfo group, sulfamoyl group, carbamoyl group, acylami/group, heterocyclic residue, arylsulfonyl group, alkylsulfonyl group, alkylami 7 group, noalkylamino group, anilino group, N-furkylanilino group, N-aryloxy group, N -acylanily7 group, hydroxy group, etc. can be mentioned. Moreover, the above R1 to R5, R1],
The alkyl group represented by R9, Z', R, and R' may also have a substituent, and examples of the substituent include all of those listed above except for the alkyl group. The bleach-fix solution of the present invention contains an organic acid ferric complex salt (hereinafter referred to as the organic acid ferric complex salt of the present invention) as a bleaching agent. The following are representative examples of the organic acids that form the organic acid ferric complex salt of the present invention. (1) Diethylenetriaminepentaacetic acid (MW = 393.
27) (2) Noethylenetriaminepentamethylenephosphonic acid (MW = 573.12) (3) Cyclohexanenomittetraacetic acid (MW = 364
．． 35) (4) Cyclohexaneamine tetramethylenephosphonic acid (MW = 58.23) (5) Triethylenetetraminehexaacetic acid (MW = 364
．． 35) (6) ) Liethylenetetramine hexamethylenephosphonic acid (MW = 710.72) (7) Glycol ethernoamine tetraacetic acid (MW = 3
80° (8) Glyfur ethernoamine tetramethylene phosphonic acid (M = 524.23) (9) 1,2-noaminopropane tetraacetic acid (MW = 30
6.27) (10) 1.2-Diaminopropane tetramethylenephosphonic acid (B = 450.15) (11) 1.3-Noaminopropan-2-ol tetraacetic acid (M o = 322.27) (12 ) 1.3-Noaminopropan-2-ol tetramethylenephosphonic acid (MW = 466.15) (13) Ethylenediamine diorthohydroxyphenylacetic acid (MW =
360.37) (14) Ethylenediaminenoorthohydroxyphenylmethylenephosphonic acid (M=432.31) (15)
Ethylenenoamine tetramethylene phosphonic acid (MW = 43
6.13) (16) Ethylenediaminetetraacetic acid (H = 292.25
) (17) Nitrilotriacetic acid (MW = 191.14) (
18) Nitrilotrimethylenephosphone I'll (MW
= 299° (19) 4-minodiacetic acid (H = 1.33.
10) (20) Iminonomethylenephosphonic acid (MW=
205.04) (21) Methyliminodiacetic acid (MW='
147.13) (22) Methyliminodimethylenephosphonic acid (MW = 219° (23) Hydroxyethyliminodiacetic acid (MW = 177.16) (24) Hydroxyethyliminodimethylenephosphonic acid (MW = 219°)
9IQ TIN (25) Ethyleneamine tetrabrobionic acid (H = 348.35) (26) Hydroxyethylglidinone (Mw = 163
．． 17) (27) Nitrilotripropionic acid (HW=
233.22) (28) Ethylenenoamine diacetic acid (MW
= 176, 17) (29) Ethylenediamine-propionic acid (MW = 277°) The organic acid ferric complex salt of the present invention is not limited to these, but one type can be arbitrarily selected from these. , or two or more types can be used in combination if necessary.Among the organic acids forming the organic acid ferric salt of the present invention, the following are particularly preferable: (1) diethylenetriamine pentate; Acetic acid (H = 393.2
7) (3) Cyclohexanoaminotetraacetic acid (Ma=
364. :15) (5) Triethylenetetraminehexaacetic acid (MW = 494.45) (7) Glycol ethernoaminehydroacetic acid (MW = 380° (9) 1,2-Noaminopropanetetraacetic acid (MW = 306.27) )(11)1
．． 3-diaminopropan-2-oltetraacetic acid (MW =
322.27 ) (13) Ethylenediamine diorthohydroxyphenyl acid! [1 (MW = 360.37) (16) Ethylenenoaminetetraacetic acid (MW = 292.
25) (19) Imi/Nizu M (MW=133.10)
(21) Methyliminoniacetic acid (N corpse = 147.13)
(23) Hydroxyethyliminodiacetic acid (MW = 17
7,16) (25) Ethylenediaminetetrapropionic acid (MW = 348.35) (26) Hydroxyethylglycidine (MW = 163
．． 17) (27) Nitrilotripropionic acid (MW=
233.22) (28) Ethylenediaminediacetic acid (MW
= 176.17) (29) Ethylenenoamine diprobionic acid (101 = 277°) The organic acid ferric complex salt of the present invention is an alkali such as a 7 Li acid (hydrogen salt), sodium salt, potassium salt, lithium salt, etc. Metal salts, ammonium salts, or water-soluble amine salts such as triethanolamine are used, preferably potassium salts, sodium salts and ammonium salts.
At least one type of iron complex salt may be used, but two or more types can also be used in combination. The amount of melon used can be arbitrarily selected, and the amount of silver in the photosensitive material to be processed and the silver halide group I
It is necessary to select by & etc. That is, it is preferably used in an amount of 0.01 mol or more, more preferably 0.05 to 1.0 mol, per IQ of the working liquid. In addition, in order to make the replenisher more concentrated and less replenishing, it is desirable to use the replenisher as a concentrated solution with the highest solubility. The bleach-fix solution of the present invention is preferably used at pi (2.0 to 10.0, more preferably pf (3.0 to 9.0).
5. Most preferably used at pH 4.0 to 9.0. It is preferable that the treatment temperature is 80°C or lower.
It is more preferably used at a temperature of 55°C or lower, most preferably 45°C or lower to prevent evaporation. The bleach-fixing treatment time is preferably within 8 minutes, more preferably within 6 minutes. The bleach-fix solution of the present invention can contain various additives together with the organic acid ferric complex salt of the present invention as a bleaching agent. As an additive that contributes to bleach-fixing properties, an alkali halide or an ammonium halide such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, ammonium iodide, sodium iodide, potassium iodide, etc. may be included. is desirable. Also, solubilizers such as triethanolamine, acetylacetone, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids, polycarboxylic acids, alkylamisos, polyethylene oxides, etc. can be added to the aM bleach solution. It is possible to add materials that are known as appropriate. The bleach-fix solution of the present invention includes a bleach-fix solution containing a small amount of a halide such as potassium bromide, or conversely, a bleach-fix solution containing a small amount of a halide such as potassium bromide, ammonium bromide and/or ammonium iodide, or a halogen such as potassium iodide. A bleach-fix solution having a composition in which a large amount of a compound is added, and a Vf special bleach-fix 1ff1 having a composition consisting of a combination of the bleach of the present invention and a large amount of potassium bromide fIrJ% halide may also be used. I can do it. The silver heroodide fixing agent to be included in the bleach-fixing solution of the present invention is a compound that reacts with silver herodenide to form a water-soluble complex salt, such as potassium thiosulfate, thiosulfate, etc., which is used in ordinary fixing processes. Typical examples include periosulfates such as sodium sulfate and ammonium periosulfate, thiocyanates such as potassium thiocyanate, sodium periosocyanate, and ammonium thiocyanate, thiourea, thioethers, and high concentrations of bromide and iodide. It is. These fixing agents have a weight ratio of 5g/11 or more, preferably 50g/Q or more, more preferably 70g/Q or more! It can be used in an amount within a range that allows one or more to be dissolved. The bleach-fix solution of the present invention may contain various types of l1H4! such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. It is also possible to contain an impacting agent alone or in combination of two or more kinds.6 Furthermore, it is also possible to contain various optical brighteners, foaming agents, or anti-foaming agents. In addition, preservatives such as hyproxylamine, hydranone, sulfites, yIS bisulfites, bisulfite adducts of aldehydes and ketone compounds, and other additives, methanol, trimethylformamide, trimethylsulfoxy An organic solvent such as V may be appropriately contained. Furthermore, patent application 1977-518
It is desirable to add a polymer or copolymer having a vinylpyrrolilene core, such as that found in the specification of No. 03. Other desirable compounds added to the bleach-fix solution of the present invention to promote bleach-fixing properties include tetramethylurea, trismethylamide phosphate, ε-caprolactam, N-methylpyrrolidone, N-methylmorpholine, and tetraethylene glycol. Flumo7 phenyl ether, acetonitrile, glycol monomethyl ether, etc. In the processing method of the present invention, it is preferable to perform the bleach-fixing of the present invention immediately after color development, but washing or rinsing with water after color development is preferred. Or after performing F11 such as suspension,
It may be subjected to the bleaching and fixing treatment of the present invention. Most preferably, the bleach-fixing treatment of the present invention is performed after the pre-fixing treatment after color development as described above, and in this case, the bleach accelerator of the present invention may be included in the pre-fixing treatment. . In the bleach-fixing treatment of the present invention, a stable treatment may be performed without washing with water, or a washing treatment with water may be performed and then a stabilization treatment may be performed. In addition to the above steps, various auxiliary steps may be added as necessary, such as hardening, neutralization, black and white development, reversal, and washing with a small amount of water. Typical specific examples of preferred treatment methods include:
The following steps are included. (1) Color development → bleach fixing → water washing (2) color development → bleach fixing → small amount of water washing → water washing (3) color development → bleach fixing → water washing → stable (4) color development → bleach fixing → stable (5 ) Color development → bleach fixing → first stability → second stability (6)
Color development → washing with water (or stable) → bleach-fixing → washing with water (or stable) (7) Color development → pre-printing → bleach-fixing → washing with water (8) color development → pre-printing → bleach-fixing → stable (9) color development →Moe establishment→
Photoconductivity → first stability - second stability (10) Color development → stop → bleach-fix → water washing → stabilization: Among these processing steps, the effect of the present invention is more noticeable, so (3) (4), (5), (8) and (
The treatment step 9) is more preferably used in the present invention. And most preferably (4), (5), (8) and (
This is the processing step 9). It is preferable to add various inorganic metal salts to the bleach-fix solution of the present invention. It is also a preferable method to add these inorganic metal salts after forming genus complex salts together with various chelating agents. The bleach-fix solution of the present invention contains a chelating agent other than the present invention and/or
Alternatively, a ferric complex salt thereof may be added. however,
The ferric complex salt other than the present invention is preferably used in an amount of 0.45 mol % or less based on the organic acid 12 iron complex salt of the present invention. As mentioned above, it is preferable that the pre-fixing solution contains the bleach accelerator of the present invention, and the most preferred method is to also include the bleach accelerator in the bleach-fixing solution. However, it may also be contained in only one of them. When a bleach accelerator is added only to the m7 fixer, the bleach accelerator is brought into the bleach-fixing process from the preceding 3'f solution by the halogen-arsenic color photographic light-sensitive material and exerts its effect. ) In the white paper fixer, it is preferable that an oxidation treatment is performed to return the reduced form of the raw iron complex salt in the white white fixer to the oxidized form, and the oxidation treatment includes, for example, air oxidation treatment. The air oxidation process refers to a forced oxidation process in which air bubbles are forcibly mixed into the processing liquid in the bleach-release tank or bleach-fix tank of an automatic processor to bring them into contact with each other to carry out oxidation treatment. This means that it is naturally oxidized by contact with air on the surface, and this means is usually called effregicin.
Air sent out from a device such as a compressor,
In order to increase the oxidation efficiency, a diffuser with fine holes such as an air distributor is used to make the diameter of the air as small as possible - increasing the contact area with liquid C, and treating the air bubbles sent into the liquid from the bottom of the tank. It is preferable that the oxidation be carried out by contacting the liquid, as this provides high oxidation efficiency. This aeration tank is mainly carried out within the processing tank, but it may also be carried out in batches in a separate tank, or it may be carried out in a secondary tank for the aeration tank attached to the side of the tank. In particular, when regenerating the bleaching solution or the bleach-fixing solution, it is preferable to perform the regeneration outside the tank bottom. In the present invention, there is usually no need to consider over-aeration, so the process may be carried out throughout the processing time, strong aeration may be carried out intermittently, and any method may be used. I can do it. However, the smaller the diameter of the air bubbles, the better the efficiency, and this is a preferable method because it prevents the air from mixing with other liquids due to splashing or the like. In the present invention, it is also preferable to carry out processing while the automatic processing machine is stopped and to stop the aeration tank during processing. Alternatively, the aeration tank may be conducted separately by leading the liquid outside the processing tank. The above airage tank is disclosed in Japanese Patent Application Laid-open Nos. 49-55336 and 51-98.
31, No. 54-95234, etc. can be used in combination with the shower type, spray type, jet spray type, etc., as well as the West German patent (OLS) 2,113,65.
The method described in No. 1 can also be used. The total amount of silver coated in the silver lodenide color photographic light-sensitive material used in the present invention is the value including one colloidal Wi filter layer and the colloidal silver antihalation layer, and is 80+ng.
/ dm2 or less (I), the effects of the present invention are exhibited. It is effective when it is preferably 60+++g/d+2, most preferably 50+ag/dm2 or less. From the viewpoint of photographic performance, a silver content of 20+og/den2 or more is preferable, and exhibits the effects of the present invention. Photographic structure of the silver halide color photographic material of the present invention/
riJ film thickness (gelatin film thickness) refers to all hydrophilic photographic constituent layers excluding the support, i.e., subbing layer, anti-reaction layer, intermediate layer, at least three emulsion layers, one filter layer, protective layer, etc. This is the total thickness of the sexual colloid layer, and the thickness of the dried photographic constituent layer. The thickness is measured using a micrometer, but in the present invention, the total thickness of the photographic constituent layers is 25 mm.
μII+ or less, preferably 22 μII+ or less, particularly 20 μIff or less, and most preferably 18 μm0 or less. From the point of view of photographic performance, 8μIfi or more is preferable.
The effects of the present invention are exhibited. The silver halide of the silver halide emulsion layer of the present invention contains at least 0.5 mol% of silver iodide grains, but the sensitivity and photographic properties of the silver halide color photographic light-sensitive material and the bleach-fixability of the present invention are In order to maximize the effects of silver iodide on photographic properties and bleach-fixing properties, the amount of silver iodide is preferably 0.5 mol % to 25 mol % from α. In the present invention, if the content exceeds 25 mol%, the photographic properties are more preferable, but the bleach-fixing properties are severely degraded. In the present invention, more preferably 2 mol% to 2
It contains 0 mol% silver iodide. The black colloidal silver dispersion layer of the antihalation layer used in the present invention has sufficient resistance to visible light (especially red light) for incident light from the support surface or emulsion surface of the silver halide color photographic light-sensitive material. It has high optical density. It also has a sufficiently low reflectance for light incident on the emulsion surface of the silver halide color photographic light-sensitive material. The black colloidal silver dispersion layer is desirably made of sufficiently fine colloidal silver particles from the viewpoint of reflectance and bleach-fixing properties, but if the colloidal silver particles are sufficiently finely divided, the absorption will be yellow to yellowish brown and the optical density against red light will be low. Because the grains do not increase, the grains must become coarse to some extent, and as a result, physical development using these silver grains as nuclei is likely to occur, resulting in poor white paper fixation (at the boundary with the silver halide emulsion layer). it is conceivable that. In particular, when the silver halide emulsion layer contains at least 0.5 mol % silver iodide grains, the silver halide emulsion layer closest to the support has a small amount (both contain 0.5 mol % silver iodide grains). When containing silver iodide, the phenomenon of deterioration of bleach-fixing properties becomes noticeable, and this becomes noticeable in multilayer silver halide color photographic light-sensitive materials having three or more silver iodide-containing emulsion layers. It is estimated that the effect of the present invention is particularly effective when processing a light-sensitive material containing a core-shell emulsion.
Some of the core-shell fL agents used are described in detail in JP-A-57-154232, etc., but a preferred silver lodenide color photographic light-sensitive material is one in which silver halide 11 in the core contains silver iodide. Silver halide containing 0.1 to 20 mol%, preferably 0.5 to 10 mol%, and the shell is made of silver bromide, silver chloride, silver iodobromide, silver chlorobromide, or a mixture thereof. It is. Particularly preferably, the shell is a silver halide emulsion comprising silver iodobromide or silver bromide. Further, in the present invention, preferable effects can be obtained by forming the core as substantially monodisperse silver halide grains and setting the shell thickness to 0.01 to 0.8 .mu.m. The silver halide color photographic light-sensitive material of the present invention is characterized by comprising silver lodenide grains containing at least 0.5 mol% silver iodide, and having an antihalation layer comprising black colloidal kite as the bottom layer; Total coated silver amount is 80B/c1m2 or less, preferably 60mg/d+a2, particularly preferably 5
0Ing/d+o2 or less, and the film thickness of the photographic constituent layers excluding the support (gelatin film thickness) is 25μIll
Below, preferably 22μ■0, more preferably 20μr
O1 is particularly 18 μIn or less. First, silver halide grains containing silver iodide in the core and/or shell are f! I! use,
By hiding the core of silver halide grains made of silver bromide, silver chloride, silver chlorobromide, silver iodobromide, or a mixture or mixture thereof using a shell having the specific thickness, silver iodide can be produced. The purpose is to take advantage of the ability of silver halide grains containing silver halide grains to increase sensitivity, while concealing disadvantageous characteristics of the grains. A silver halide emulsion having silver halide grains having a shell having the above-described specific thickness can be produced by coating the shells with silver halide grains contained in a monodisperse emulsion as a core. In addition, when the shell is silver iodobromide, the ratio of silver iodide to silver bromide is preferably 20 mol % or less. Core! In order to obtain gender-dispersible silver halide grains, (]A
Particles of a desired size can be obtained by the Guprnoet/T method while keeping g constant. Further, highly monodisperse silver halide emulsions can be produced by applying the method described in JP-A-54-48521. In a preferred embodiment of the method, a potassium iodobromide-gelatin aqueous solution and an ammonium silver nitrate aqueous 78 solution are used.
It is produced by a method of adding silver lodenide seed particles to an aqueous gelatin solution while changing the addition rate as a function of time. In this case, the time function of the addition rate, 1)
By appropriately selecting H, pAg, temperature, etc., a highly monodisperse silver halide emulsion can be obtained. Since the particle size distribution of a monodisperse emulsion is almost a normal distribution, the standard deviation can be easily determined. From this, if we define the width of the distribution (%) using the relational expression, the width of the distribution that can meaningfully regulate the absolute thickness of the coating should preferably have a monodispersity of 20% or less, and more preferably 10%.
% or less. Next, the thickness of the shell covering the core must be such that it does not hide the desirable qualities of the core, and on the contrary, it must be thick enough to hide the unfavorable qualities of the core. That is,
J7 is limited to such a narrow range bounded by the eye and the lower limit. Such a shell can be formed by depositing an H-type halogen compound solution and a soluble silver solution onto a monodisperse core by the double noet method. : Do it. For example, an average grain size of 1μ+ containing 2 mol% silver iodide in the core
nfl Using substantially monodisperse silver halide grains, 0
．． According to experiments in which the coating thickness was varied using 2 Morta 6 silver iodobromide as a shell, for example, 0.85μ+J7
Monodisperse silver halide grains produced by this method had low covering power when shells were prepared. This was treated with a physically developing processing solution containing a solvent that dissolves silver halide, and when observed under a scanning electron microscope, it was found that no developed silver filaments were present. This suggests that the optical density and even the covering power are reduced. Therefore, considering the filament form of developed silver, we thinned the thickness of the silver bromide shell on the surface while changing the average grain size of the core.As a result, the thickness of the shell was determined to be the absolute thickness regardless of the average grain size of the core. as 0.8μ
It has been found that a large number of well-developed silver filaments are produced at a diameter of 0 or less (preferably 0.5 μm) or less, resulting in sufficient optical density, and that the ability of the core to achieve high sensitivity is not impaired.On the other hand, the shell If the thickness of the toner is too thin, parts of the core material containing silver iodide will be exposed, and the effect of covering the surface with the shell, that is, the chemical sensitization effect, rapid development and quick fixing properties will be lost. Preferably, the limit of its thickness is 0.01μ0.Furthermore, as confirmed by a highly monodisperse core with a distribution width of 10% or less, the preferred shell Iq-sake is 0.01 to 0.0.
The thickness is 6 μm, and the most preferable thickness is 0.03 μCO or less. The above-mentioned development silver filaments are sufficiently generated to improve the optical density, the high-sensitivity properties of the core are utilized to produce a sensitizing effect, and rapid development and fixing properties are achieved due to the high This is due to the synergistic effect between the dispersible core, the shell whose thickness is regulated as described above, and the silver halide composition of the core and shell. As the silver halide constituting the shell, silver iodobromide, silver bromide, silver chloride, silver chlorobromide, or a mixture thereof can be used. Among these, silver bromide, silver iodobromide, or a combination thereof is preferred in terms of compatibility with the core, performance stability, and storage stability. The photosensitive silver halide emulsion used in the present invention may be doped with various metal salts or metal complex salts during the formation of silver halide precipitates of the core and shell, during grain growth, or after the completion of growth. For example, metal salts or complex salts such as gold, platinum, palladium, iridium, ronium, bismuth, cadmium, copper, etc., and combinations thereof can be applied.6 Also, excess halogen compounds or Salts and compounds such as nitrates and ammonium that are used or become unnecessary may be removed. As a method for removal, any of the Nudel water washing method, dialysis method, coagulation precipitation method, etc. commonly used in general emulsions can be used as appropriate. Further, the emulsion used in the present invention can be subjected to various chemical sensitization methods that are applied to general emulsions. Namely, activated gelatin; noble metal sensitizers such as water-soluble gold salts, water-soluble natural salts, water-soluble balanum salts, water-soluble rhodium salts, and water-soluble isonium salts; sulfur sensitizers; selenium sensitizers; polyamines, chloride Chemical sensitization can be carried out using chemical sensitizers such as reduction sensitizers such as stannous tin or the like alone or in combination. Furthermore, this silver halide can be optically sensitized to a desired wavelength range. There is no limit to the optical sensitization method for emulsions, and for example, optical sensitizers such as cyanine dyes such as zeromethine dyes, monomethine dyes, trimethine dyes, or merocyanine dyes are used alone or in combination (for example, supersensitization). can be sensitized. Regarding these technologies, see U.S. Patent No. 2,688.545, U.S. Pat.
No. 3,615,635, No. 3,628,964, British Patent No. 1,195.302, No. 1,242゜588, No. 1,293,862, West German Patent (OLS) No. 2,0
No. 30,326, No. 2,121,780, Special Publication No. 1973
-4936, No. 44-14030, etc. The selection is sensitized+$kmJF-j-+#spider&i
kt^1. s sea table 1ψ-blindness/r1MhhIT+261
-r? It is possible to set it arbitrarily. In the silver halide emulsion used in the present invention, a silver halide emulsion in which the core grains are substantially monodisperse halide grains is used to form the silver halide grains contained in the silver halide emulsion. By coating the particles with a shell, the F! However, even if such a substantially monodisperse silver halide emulsion is used as it is, the average particle size distribution is Two or more types of monodisperse emulsions having different grain sizes may be blended at any time after grain formation to obtain a predetermined gradation for use. The silver halide emulsion used in the present invention contains a substantially monodisperse core with a distribution width of 20% or less in a proportion equal to or higher than that of an emulsion obtained by coating a shell with a substantially monodisperse core. It is desirable that the silver halide grains of the present invention be included in all the silver halide grains. However, silver halide grains other than those according to the invention may also be included within a range that does not impede the effects of the invention. The silver halide other than those of the present invention may be of the core-shell type or may be of a type other than core-shell, and may be monodisperse or polydisperse. In the silver halide emulsion used in the present invention,
The emulsion contains at least 6 silver halide grains.
The silver halide emulsion of the present invention preferably has a silver halide grain size of at least 0.5 This includes cases in which the emulsion contains tabular silver halide grains containing mol% of silver iodide.That is, the emulsion of the present invention used in the silver halide 7L layer of the present invention contains silver halide grains containing mol% of silver iodide. ■ be the above-mentioned silver iodide core-shell grains, and ■ be iodide-containing tabular silver halide grains P (even if the iodide-containing tabular silver halide grains are core-shell type, (It may be of a different type.),■
Any of the embodiments, such as being a mixture of the above-mentioned (1) and (2), is included in the present invention. The silver iodide-containing tabular silver halide grains will be explained below. It is preferable that the tabular silver halide grains have a grain size of 5 times or more than the grain thickness.
No. 58-127921, No. 58-1.08532
No. 59-99433, No. 59-119350, etc., and in the present invention, from the viewpoint of effects on color staining and image quality, the particle diameter is determined by the particle thickness. 5 times or more, preferably 5 to 100 times, and even more preferably 7 to 30 times. Furthermore, the particle diameter is preferably 0.3 μm or more, and 0.5 to
G/Jm is particularly preferably used. These tabular silver halide grains more preferably exhibit the desired effects of the present invention when processing a sensitive material having one or more layers containing at least 50 to 60% by weight in at least one layer of silver halide emulsion. When all of the grains are the above-mentioned tabular silver halide grains, a particularly favorable effect is produced. It is particularly useful when the tabular silver halide grains are core-shell grains. In the case of core-shell particles, it is preferable that the requirements described above for the core-shell are also satisfied. In general, tabular silver halide grains are tabular with two parallel surfaces, and therefore, in the present invention, "J" is expressed as the distance between two parallel surfaces constituting the tabular silver halide grain. In addition, [grain diameter 1] refers to the diameter of the projection plane when the tabular silver halide grain is observed in the direction perpendicular to the flat surface, and if it is not circular, the best diameter is the diameter. The halogen composition of the tabular silver halide grains is preferably silver bromide and silver iodobromide, particularly those with a silver iodide content of 0.5 to 0.5. More preferably, it is silver iodobromide with a content of 10 mol %.Next, a method for producing tabular silver halide grains will be described.As a method for producing tabular silver halide grains, methods known in the art may be used as appropriate. This can be achieved by combining. Forming a seed crystal in which 40% or more of tabular silver halide grains are present in a layered manner in air, and growing the seed crystal while simultaneously adding silver and halogen solutions while keeping the pBr value at the same level. During this grain growth process, it is desirable to add a silver and halogen solution to prevent the generation of new crystal nuclei.The size of the tabular halogenated m grains is determined by temperature control and the type of solvent. By controlling the selection of silver salt and amount, the silver salt used during grain growth, the addition rate of halide, etc.
! ! ! can. When producing tabular silver halide grains, grain size, grain shape (diameter/F7-view ratio, etc.), grain size distribution, and grain growth rate can be controlled by using a silver halide solvent as necessary. can. The amount of silver halide solvent used is 1 x 10-3 of the reaction solution.
1.0% by weight is preferred, especially 1 x 10-2 to 1 x 10
-1% by weight is preferred. For example, with an increase in the amount of halogen solvent used, halogen
j/ ν Ire heart 1τ pot h ヱ 斗← no de
No sentry table 115t~ ~I le l
+I) You can speed up your speed. On the other hand, there is also a tendency for the thickness of silver halide grains to increase with the amount of silver halide solvent used. Examples of the halogenated kite solvent used include ammonia, thioethers, and thioureas. Regarding thioethers, U.S. Pat. No. 3,271,157;
No. 3,790,387, No. 3,574,628, etc. may be referred to. Silver salt solution (e.g. 8gNO. aqueous solution) and halide solution (e.g. K11r aqueous solution) added to accelerate grain growth during production of tabular silver halide grains.
A method of increasing the addition rate, amount, and concentration of addition is preferably used. These methods are described, for example, in British Patent 1, 335.
. No. 925, U.S. Pat. No. 3,672,900, U.S. Patent No. 3,65
No. 0,757, No. 4,242,445, Japanese Unexamined Patent Publication No. 1983-
Reference can be made to the descriptions in No. 142329, No. 55-158124, and the like. The tabular silver halide grains can be chemically sensitized if necessary. Regarding the chemical sensitization method, reference can be made to the description of the sensitization method explained for the core shell, but from the viewpoint of silver saving in particular, the tabular silver halide mercury of the present invention may be gold sensitized, sulfur sensitized, or It is preferable to use them together. In a layer containing tabular silver halide grains, it is preferable that the tabular silver halide grains are present in a weight ratio of 40% or more, particularly 60% or more, based on all the silver norodide grains in the layer. The thickness of the layer containing tabular silver halide grains is 0.5μ
III to 5.0μIll is preferable, and 1.0μfO to 3
．． More preferably, it is 0μ. Also, the coating amount of tabular silver halide grains (for one side)
is preferably 0.5g/m2 to 6g/ff12, and 1g/m2 to 6g/ff12.
It is more preferable that llI2 to 5 g/+112. Other configurations of the layer containing tabular silver halide grains,
For example, there are no particular restrictions on bindu, curing agents, antifoggants, silver halide stabilizers, surfactants, spectral sensitizing dyes, dyes, ultraviolet absorbers, etc.
arch D 1 closure volume 176, 22~
The description on page 28 (December 1978) can be referred to. Next, the structure of the silver lodenide emulsion layer (hereinafter referred to as upper silver halide emulsion layer) which is present outside (on the surface side) of the layer containing the above-mentioned tabular silver halide grains will be described. The silver lodenide grains used in the upper silver halide emulsion layer are preferably high-sensitivity silver halide grains used in ordinary direct X-ray films. The shape of the silver halide grains is preferably spherical, polyhedral, or a mixture of two or more thereof. In particular, it is preferable that spherical particles and/or polyhedral particles having a diameter/thickness ratio of 5 or less account for 60% or more (weight ratio) of the total. The average particle size is preferably 0.5 μIn to 3 μIff, and growth can be performed using a solvent such as ammonia, thioether, thiourea, etc., if necessary. Silver halide grains are made highly sensitive by gold sensitization, sensitization using other metals, reduction sensitization, sulfur sensitization, or a combination of two or more of these. Preferably. The other compositions of the upper emulsion layer are the same as those for the layer containing tabular (silver) silver grains, and there are no restrictions;
The description in csearch D 1 Closure volume 176 can be referred to. In addition, the emulsion used in the present invention is disclosed in JP-A-53-10372.
No. 5, No. 59-133540, No. 59-162540
It is also preferable to include epitaxially bonded 710 silver denride grains as described in No. 1, et al. The silver halide emulsion of the present invention can contain various commonly used additives depending on the purpose. For example, stabilizers and antifoggants such as azaindenes, triazoles, tetrazoles, imidazolithums, tetrazolium salts, polyhydroxy compounds; aldehydes,
Anoridine series, inoxazole series, vinyl sulfone series, acryloyl series, carboimide series, maleimide series,
Hardening agents such as methanesulfonic acid ester type and triacyl type; Development accelerators such as benzyl alcohol and polyoxyethylene type compounds; Image stabilizers such as Chroman type, Claman type, bisphenol type, and phosphite type; Wax,
There are lubricants such as glycerides of higher fatty acids and higher alcohol esters of higher fatty acids. In addition, anionic, cationic, and nonionic surfactants can be used as coating aids, permeability improvers for processing e, etc., antifoaming agents, and materials for controlling various physical properties of photosensitive materials. Alternatively, various species of both sexes can be used. In particular, it is preferable that these surfactants are eluted into a processing solution having bleaching ability. Effective antistatic agents include noacetyl cellulose, styrene perfluoroalkyl sodium maleate copolymers, and alkali salts of reaction products of styrene-maleic anhydride copolymers and 1]-aminobenzenesulfonic acid. Examples of matting agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers. It is also possible to use colloidal silicon oxide. Further, examples of the latex added to improve the physical properties of the film include copolymers of acrylic esters, vinyl esters, etc., and other monomers having ethylene groups. Examples of gelatin plasticizers include glycerin and glycol compounds, and examples of thickeners include styrene-maleic 117-g copolymer and alkyl vinyl ether-maleic acid copolymer. In the silver halide color photographic light-sensitive material of the present invention, the hydrophilic colloids used to prepare the emulsion and other hydrophilic colloid layer coating solutions include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, Proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose and carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinyl alcohol, and polyacrylamide, etc. Included. Examples of the support for the silver halide color photographic light-sensitive material of the present invention include a glass plate, a polyester film such as cellulose acetate, cellulose nitrate, or polyethylene terephthalate, a polyamide film, a polycarbonate film, and a polystyrene film. A reflective support (for example, baryta paper, polyethylene-covered paper, polypropylene synthetic paper, a transparent support provided with a reflective layer or combined with a reflective material) may be used, and these supports may be selected as appropriate depending on the intended use of the photosensitive material. selected. For coating the silver halide emulsion layer and other photographic constituent layers used in the present invention, tank coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used. Also, U.S. Patent No. 2,761,791, Z, 941,8
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 98. The silver halide emulsion of the present invention is a combination of cyan, magenta, and yellow couplers with the silver halide emulsion of the present invention, which has been color-sensitized and adjusted to have red sensitivity, green sensitivity, and blue sensitivity, in order to be applied to color light-sensitive materials. The method and material used for color photosensitive materials may be used, such as the method and material used for color photosensitive materials. Tai D [111 Me Tatsuhaku Yomidori Kumuta--11, Roshishi Ik
Sharp color photographic materials are produced using an internal development method (US Pat. No. 2,376.679,
2,801,171), as well as an external development method in which a coloring agent is contained in the developer (see U.S. Pat. No. 2,252,
No. 718, No. 2,592,243, No. 2,590,9
70) may be used. Further, as the coloring agent, any coloring agent generally known in the art can be used. For example, cyan coloring agents are those based on a naphthol or phenol structure and form indoaniline dyes through coupling, magenta coloring agents are those having a skeletal structure of a 5-pyrazolone ring with an active methylene group, and yellow coloring agents are As such, those having an acylacedoanilide structure such as benzoylacedoanilide and bivalylacetanilide having an active methylene chain, with or without a substituent at the coupling position can be used. In this way, as a coloring agent, so-called 2
Both equivalent couplers and 4-equivalent couplers can be applied. The black and white developer that can be used in the processing of the present invention is a commonly known black and white first developer used for processing silver halide color photographic materials, or a developer used for processing black and white photographic materials. It can contain various additives that are generally added to black and white developers. Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate; Inorganic or organic inhibitors such as potassium bromide, 2-methylbenlimigsol, methylbenzthiazole, hardening and water softening agents such as polyphosphates, and surface superfiltration consisting of trace amounts of iodide and mercapto compounds. Examples include development inhibitors. The aromatic primary amine color developing agent used in the color developing solution used before processing with the bleach-fix solution of the present invention is:
Various types widely used in various color photographic processes are included. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, because they are more stable than the free state. In addition, these compounds are generally used in color developer IQ.
It is preferred to use a concentration of about 0.1 g to about 30 g for IQ, and more preferably from about 1 g to about 15 g for IQ.
Use at a concentration of Examples of amino 7-el/-based developers include 0-7 minophenol, p-7 minophenol, 5-amino-2-
Hydroxytoluene, 2-7 minnow 3-hydroxytoluene, 2-hydroxy-3-7 minnow 1,4-methyl nightzene, etc. are included. A particularly useful aromatic primary amine color developer is N. It is an N-dialkyl-p-phenylenediamine compound, and the furkyl group and phenyl group may be substituted or unsubstituted. Among them, particularly useful compounds include N,N-diethyl-11-phenylenediamine hydrochloride, N-methyl'-p
-Phenylenediamine! fl[,N,N-dimethyl-9
-phenylenediamine hydrochloride, 2-7 minnow 5-(N-
Ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-
4-7 minoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline sulfate, 4-7 mino 3-
Examples include methyl-N,N-diethylaniline sulfate, 4-7minor N-(methoxyethyl)-N-ethyl-3-methylaniline-p-)luenesulfonate, and the like. Particularly useful color developing agents in the present invention are paraphenylenediamine color developing agents having at least one water-soluble group (hydrophilic group) on the amine 7 group, and representative examples of these color developing agents include: Examples include the following compounds, but the present invention is not limited thereto. (1) C2H, C2H, NHSO2CH31u NH. (3) C2)1. C211,0)1(6)C
H, Il? 211IOHNH□ H2 H2 NH□ (10) li I'112COO11N])2 H2 (12) C2H5(CH2C)I20LCLN1(
2 (13) C2H5 (CH2CH20), C2H5H
2 (14) C2H5(CH2CH2)2cJs Color developing agents that are particularly useful in the present invention include ami7 groups,
! :Lte(C1+2)IICI+2011. (CH
2CHs02(Cllz)nCH:+, (C112
)+n0(Ct12)ncI13, and specific examples include (1) and (
2), (3), (4), (6) and (7). However, Ill and I1 are integers of 0 to 6, preferably O to 5. The paraphenylenenoamine color developing agent is preferably mixed into the bleach-fix solution of the present invention. The alkaline color developer used before processing with the bleach-fix solution of the present invention contains, in addition to the aromatic primary amine color developer, various components that are usually added to color developers, such as Alkaline agents such as sodium hydroxide, sodium carbonate, potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal ocyanates,
Alkali metal helodenide, benzyl alcohol, noenonetriaminepentaacetic acid, 1-hydroxyethyl l-1,
A water softener such as 1-diphosphonic acid and a thickening agent may optionally be included. The l]H of this color developing solution is usually 7 or more, most commonly about 10 to about 13. The bleaching solution according to the present invention is a halogen-based bleaching solution containing the emulsion of the present invention, such as color paper, color negative film, color box film, color reversal film for slides, color reversal film for movies, color reversal film for TV, reversal color vapor, etc. It can be applied to silver oxide color photographic light-sensitive materials, especially when the total amount of coated silver is 20 mg/dm2 or more,
It is most suitable for processing high-sensitivity color photographic materials containing silver iodide of 80 mg/d+n2 or less. [Examples] Hereinafter, the present invention will be explained in detail with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 [Manufacture of emulsions] The following five types of monodisperse emulsions made of silver iodobromide containing 6.0 mol% of silver iodide were manufactured, each of which was subjected to gold sensitization and sulfur sensitization, and after completion of aging. , 4-hydroxy-6-methyl-1,3,
3a,7-chitrazaindene was added. Emulsion (^): Core-shell type silver iodobromide emulsion with an average grain size of 1.2 μm (shell is silver iodobromide with a thickness of 0.01 μm) Emulsion (B)
; core-shell type silver iodobromide emulsion with an average grain size of 1.2 μm (shell is silver iodobromide with a thickness of 0.05 μm) emulsion (C)
; core-shell type silver iodobromide emulsion with an average grain size of 1.2μ (shell is silver iodobromide with a thickness of 0.5μIn) emulsion (D)
; Core-shell type silver iodobromide emulsion with an average grain size of 2.6 μm (grain size is 10 times the grain thickness) Emulsion (E); Spherical silver iodobromide emulsion with an average grain size of 1.2 μm Emulsion (^) ~ (C) refers to the method described in JP-A-54-48521 and JP-A-58-49938; I) AI? t
l) Produced by controlling H, emulsion CD) was produced by the method described in JP-A-58-113934 and JP-A-59-99433, and emulsion (E) was produced by the method described in JP-A-58-49938. . [Manufacture of photosensitive material] The following compounds were added to the above emulsion to prepare a silver halide color photographic material. Anhydro-3,3'-no(
3-sulfopropyl)-5,5'-dichloro-9-ethylthiacarboxyanine hydroxide (dye p 1
) 285 mg/1 mole 8 g
'-Chu(3-sulfopropyl)-4,5,4',5
'Dibenzothi7carpocyanine hydroxide (dye p
-2) 38.5 g/1 mol^gX and anhydro-1
,3'-diethyl-3-(3-sulfopropyl)-5-
) Lichloromethyl-4',5'-benzobenzimidazoloti7 carpocyanine hydrakind (dye p-3) 11
Optical sensitization was performed using 6B/1 mol^gx. In this photographic emulsion, 2-(α. a, β, β, γ, γ, δ, δ-octafluorohexamide)-5-(2-(2,4-di-t-7mil) was added as a cyan coupler. 7eth/xy)hexanamide]phenol to tricresylphos7
A dispersion prepared by dissolving the coupler in alcohol and dispersing it in a conventional manner was added to the solution in an amount of 0.3 mol of coupler per 1 mol of gX. Furthermore, as a stabilizer, 4-hydroxy-6-
Methyl-1,3,3a,? - Tetrazaindene, poly-N-vinylpyrrolidone as a physical development inhibitor and 1-phenyl-5-flucaptotetrazole as an anti-capri agent, and the emulsion was coated in multiple layers on a polyethylene terephthalate film coated with a black colloidal silver coating. did. The coating was repeated several times with the average thickness of one layer being 4.2 μl and the thickness of the intermediate layer being 2 μl. Layered 6 times, film thickness 37゜2μ
A layer with a film thickness of 18.6 μm was created by layering it three times. The amount of silver is 96 g/d and 46 g/d, respectively.
It became dII2. The film swelling rate T of the binder was in the range of 9 seconds to 14 seconds. r ill m 74. ill 1 The silver halide color photographic light-sensitive material described above was exposed in a conventional manner and then subjected to the following development treatment. Color development for 3 minutes and 15 seconds, bleach-fixing for 1 to 30 minutes, washing with water for 2 minutes, and stabilization for 7 minutes are carried out in sequence, followed by drying. Each treatment was performed at 37.8°C, and each treatment liquid was prepared according to the following formulation. [Color developer] Potassium carbonate 30g Sodium sulfite 2.0g Hydroxylamine sulfate 2.0g Potassium bromide
1.2g sodium hydroxide
3.4 g N-ethyl-N-β-hydroxyethyl-3-methyl-4-7 minoaniline sulfate 4.6 g water was added to make one solution, and the pH was adjusted to 10.1 with sodium hydroxide. [Bleach-fix solution] Ethylenediaminetetraacetic acid diammonium salt 7.5g Ethylenediaminetetraacetic acid iron (III) ammonium salt 150.0g Ammonium sulfite (50% soluble n) 10.08
Ammonium 1,000 sulfate (70% solution 1) 200
．． OFI water was added to make IQ, and the mixture was adjusted to 1) H7.5 with ammonium hydroxide. This bleach-fix solution was treated as (1), and the bleach-fix solution to which 0.7 g/Q of bleach accelerator exemplified compound (a) was added was treated as (2). [Stabilizing solution] Formalin (37% solution) 7. Om
Add Q water to make IQ. The results are shown in Table 1. As is clear from the result that the sensitivity of sample (5) is 100 or more, samples (1) and (2) satisfy the preferable conditions of the present invention as light-sensitive materials. When (3) is used, even if a conventional bleach-fix solution is used, the developability is superior to that of other samples (4) and (5) that do not meet the conditions of the present invention, and the sensitizing effect is also excellent. ing. Furthermore, the results in Table 1 suggest that there is an optimum shell thickness. However, even with such excellent photographic materials, the coating film is thick and f! It can be seen that when the amount of A is large, the bleaching properties with conventional bleach-fix solutions are poor in any case. In addition, aW- is 18.6 μm and the amount of coated silver is 46+ag/
Even in the case of d+a2, when the bleach-fixing solution does not contain a bleaching accelerator, the time to complete skin silvering is not shortened much. Surprisingly, however, core-shell emulsions, which are the preferred emulsions of this invention, are found to be processed with particularly short desilvering completion times when containing bleach accelerators. Example 2 Following the layer structure adopted in the industry for high-sensitivity silver halide color photographic light-sensitive materials, various auxiliary layer prevention layers, a red-sensitive silver halide emulsion layer, and a green-sensitive silver halide emulsion layer were prepared. 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 μ blue-sensitive silver halide emulsion layer. That is, samples were prepared as described below, but the film thickness was adjusted by varying the amount of gelatin so as to keep the amount of coated silver constant, thereby creating samples in which the dry film thickness was varied. The amount of silver coated is approximately 100o+
It was adjusted to two types, g/d+++2 and 50+ag/den2. However, the following are standard coating conditions, and each formulation was adjusted by changing the amount of gelatin to accommodate changes in film thickness. Layer 1: A dispersion of 0.8 g of black colloidal silver, which is highly absorbent to light in the wavelength range 400 to 700 n+a, is prepared by reducing silver nitrate with hydroquinone as a reducing agent and 3 g of gelatin to form an antihalation layer. Painted. Layer 2: Middle layer made of gelatin. (Dry film thickness 0.8
μ+n) Layer 3: 1.5 g of low-sensitivity red-sensitive silver iodobromide emulsion (HgI; 6 mol%), 1.9 g of gelatin and 0.96 g of 1-hydroxy-4-(β-methoxy Ethylamide 7carbonylmethoxy1-N-rδ-t2.4-
di-amylphenoxy)butyl 1-2-su7amide (hereinafter referred to as cyan coupler (c-i)), 0.0
28 g of 1-hydroxy-4-[4-(1-hydroxy-8-7ceto7mido-3,6-cisulfo-2-su7tylazo)phenoxy]-N-[δ-(2,4-di-amylphenoxy) ) Low sensitivity containing 0.4 g of triphrenor phosphate (hereinafter referred to as TCP) in which butyl 1-2-su7 toamide nonodium (hereinafter referred to as colored cyan coupler (CC-1)) is dissolved. Red-sensitive silver halide emulsion layer. Layer 4...1.1g of highly sensitive red-sensitive silver iodobromide emulsion (^
g■; 8 mol%), 1.2 g of gelatin and 0.41
A highly sensitive red-sensitive silver halide emulsion layer containing 0.15 g of TCP in which g of cyan coupler (C-1) and 0.028 g of colored cyan coupler (CC-1) were dissolved. Layer 5: 0.04 g of dibutyl 7-talate (hereinafter referred to as DB
P) and an intermediate layer containing gelatin of i, zg. Layer 6: 1.6 g of low-sensitivity green-sensitive silver iodobromide emulsion (Hgl: 15 mol%), 1.7 g of gelatin and 0.3
0 g of 1-(2,4,6-)lichlorophenyl)-3-
[3-(2,4-di-t-amylphenoxyacetamide)benzenamide]-5-pyrazolone (hereinafter referred to as magenta coupler (M-1)), 0.208 4゜4
-methylenebis-11-(2,4,6-trichlorophenyl)-3-(3-(2,4-sheet t-7mil7enoxyacetamide)benzenamide J-5-pyrazolone (
Hereinafter referred to as magenta coupler (M-2)), o, oe
eg 1-(2,4,6-)lichlorophenyl)-4
-(1-su7tylazo)-3-<2-10 rho5-octadecenylsuccinimideanilino)-5-pyrazolone (hereinafter referred to as colored magenta coupler (CM-1)). Low-speed green-sensitive silver halide emulsion layer containing 0.3 g of dissolved TCP. Layer 7...1.5g of high-sensitivity green-sensitive silver iodobromide emulsion (3
81711 mol%), 1.9 g gelatin and 0.0
93g magenta coupler (M-1), 0.094g magenta coupler (M-2), 0.049. A high-sensitivity green-sensitive silver halide emulsion layer containing 0,12H TCP in which a colored magenta coupler (CM-1) is dissolved. Layer 8: One layer of yellow filter containing 0.2 g of yellow colloidal silver, 0.11 H DBP in which 2 g of antifouling agent (HQ-1) was dissolved, and 2.1 g of gelatin. Layer 9...0.9511 of a low-speed blue-sensitive silver iodobromide emulsion (HgI; 6 mol %), 1.9 g of gelatin and 1.
84g of α-[4-(1-benzene2-7enyl3
,5-dioxo-1°,2,4-tri7zolidinyl)1
-a-pivaloyl-2-chloro-5-[γ-(2,4-
A low-sensitivity blue-sensitive silver halide emulsion layer containing 0.93 g of DBP in which not-t-amylphenoxy)butanamide]acetanili V (hereinafter referred to as yellow coupler (Y-1)) was dissolved. Layer 10...1.2 g of high-sensitivity monodisperse blue-sensitive silver iodobromide emulsion (8[1:7 mol%), 2-Ogf) Cera+
#11 I41'l ARg yellow coupler (
High-sensitivity blue-sensitive/silver lodenide emulsion layer containing 0.23 g of DBP in which Y-1) was dissolved. Scrap 11: tJX&2 protective layer made of gelatin. Layer 12: first protective layer containing 2.3 g of gelatin. The dry film thickness of the photographic constituent layers of the finished sample was 35 μt each.
*, 30μm, 27μm, 25μ+a, 22μ beats, 20
There were seven types: μ+a, 18 μm. This is sample N
011-7. However, the film thickness and black colloidal silver content of the antihalation layer and the i-thickness of the gelatin intermediate layer and yellow filter layer were not changed at all. Another sample was prepared by coating the same emulsion on a transparent polyethylene terephthalate film base without the colloidal silver ray-inhibiting layer as the bottom layer. The samples are numbered in descending order of film thickness. It was set as 8 to 14. Furthermore, 14 samples were prepared using emulsions having the same compositions as Samples Nos. 1 to 14, but with a reduced amount of hardening agent and an increased film swelling rate T as shown in Table 2-2. (Sample No. 15-28) The processing steps were color development for 3 minutes and 15 seconds, bleach-fixing for 1 to 30 minutes, first stabilization for 2 minutes, and second stabilization for 30 seconds. Each treatment was performed at 37.8°C, and each treatment liquid was prepared according to the following formulation. [Color developer] Potassium carbonate 30g Sodium sulfite 2.0g Hydroxylamine sulfate 2,0g 1-hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 1.0g Potassium bromide 1.2g Magnesium chloride 0.6g Water Sodium oxide 3.4gN-ethyl-N-β-
Hydroxyethyl-3-methyl-4-7mi77niline sulfate 4.6g was added to make IQ, and the pH was adjusted to 10.0 with sodium hydroxide.
! ! I arranged it. [)Nth fixer] Ethylenenoaminetetraacetic acid diammonium salt 7.5g/
Polycarboxylic acid ferric complex salt (added according to Table 2) Ammonium sulfite (50% solution) 10,0
gAmmonium thiosulfate (70% solution) ZO
0.0g water was added to give IQ, and the mixture was adjusted to +)H7.5 with ammonium hydroxide. [First stable solution] 1-Hydroxyethylidene 1,1-diphosphonic acid 3.085-chloro-2-methyl-4-isothiazolin-3-one 1.0g ethylene glycol 1.0g Add water]Q
and adjusted to pi-(7.1) with potassium hydroxide. [Second stabilizing solution] Formalin (37% solution) 7.0 m
Add Q water to make IQ. was processed using ethylenediaminetetraacetic acid ferric complex salt as the 7-polycarboxylic acid in the eighth fixer. As a bleach accelerator, exemplified compound (a) was used and added at a rate of 0.78 per IQ. The bleach-fixing completion time at that time was measured. The results are shown in Table 2. 7 or less margin (, 7 ( \・, -・' It can be seen that when the bleaching accelerator (gelatin thickness) is large, the bleach-fixing completion time is extremely long, but it decreases rapidly as the thickness of the photographic constituent layer (gelatin film thickness) becomes thinner, and the change is greatest at around 25 μm. It can be seen that although the effect of (1) is not effective when the photographic constituent layer film f\ (gelatin film thickness) is large, a significantly large effect is exhibited in the case of a thin photographic constituent layer (gelatin film thickness). In addition, it can be seen that in the case of samples coated with a large amount of silver other than those of the present invention, a large bleaching promotion effect cannot be obtained regardless of the film thickness.On the other hand, silver halide without a black colloidal silver antihalation layer cannot be obtained. For color photographic materials, the thickness of the photographic constituent layers (
It can be seen that there is almost no effect on gelatin film thickness (gelatin film thickness) and that the time required to complete bleach-fixing is extremely short. As a high-sensitivity photographic material, it is difficult to put it into practical use because the sharpness deteriorates. Bleach accelerators (9) and (12) were also investigated, and the same effects as those described above could be obtained. Furthermore, when the swelling speed T is 10 seconds, compared to when the same speed is 35 seconds, the bleach-fixing completion time is sufficiently short even in the absence of a bleach accelerator, and the present invention provides the optimum amount of silver and film thickness. It can be seen that this can be achieved for the first time by a combination of 1 and 1 membrane swelling rate. Example 3 Film thicknesses of 36 μII+ and 19
Samples of μ duck were coated with a silver amount of 120a+g/da each.
+', 100mg/dm2.70mg/d1112.5
0Ing/dm2.40mH/dm2.30mg/d
Ia2 and processed using the bleach-fixing solution of Example 2 (aminopolycarboxylic acid shown in Table 3). The bleach-fixing completion time at that time was measured and the results are shown in Table 3. In addition, the samples were prepared by changing the amount of hardening agent as in Example 2, and B'
The ltD water speed was changed. As is clear from Table 3 below, the film thickness, silver content, and film swelling rate T
If both are outside the scope of the present invention, a sufficient bleaching accelerating effect cannot be obtained in any case, and a remarkable bleaching accelerating effect is obtained in which the film thickness, silver content, and membrane swelling rate T are all below the values of the present invention. It turns out that you can get it. Example 4 Samples (brass film thickness: 19 μm) were prepared in accordance with the method of Example 3, with the amount of coated silver and film W adjustment rate T% changed as shown in Table 4, and these samples were treated in the same manner as described above. As the bleach-fix solution, 0.20 mol of the organic acid ferric complex salt shown in Table 4 was used, and 0.7 g/Q of the bleach accelerator shown in Table 4 was added. The bleach-fixing completion time at that time was measured. The results are shown in Table 4. , / Hereinafter, I warehouse, white ・ From the results in Table 4, if the film 17 is 19μ'n, desirable bleach-fixing promotion is shown when the coated silver amount and the film swelling rate T are below the values of the present invention.In particular, the film When the swelling rate T was large, the n-th promotion effect (due to the decrease in silver content) was significantly greater with the low molecular weight organic acid ferric complex salt than with the high molecular weight organic acid ferric complex salt, but when the swelling rate T was large, When the amount of silver is small, this does not occur, and both high molecular weight organic acid ferric complex salts and low molecular weight organic acid ferric complex salts show a good desilvering rate at the optimum silver amount.Example 5 Using the same method as in Example 2, coat an antihalation layer, a low-sensitivity red-sensitive silver halide emulsion layer, and a high-sensitivity red-sensitive silver halide emulsion layer from the support while interposing various auxiliary layers. However, in order to adjust the Il!2 thickness, red-sensitive silver halide emulsion layers were repeatedly coated.Also, the film swelling speed T3A was divided into two types, i1 to 35 seconds and 7 seconds.
! l! I arranged it. Layer 1: An antihalation layer containing black colloidal silver that is exactly the same as Layer 1 of Example 2. N2: Intermediate layer completely similar to layer 2 of Example 2. Layer 3: A low-sensitivity red-sensitive silver halide emulsion layer that is completely the same as JvI3 of Example 2, except that the silver iodide content was changed as shown in Table 5. Layer 4: A highly sensitive red-sensitive silver halide emulsion layer that is exactly the same as Layer 4 of Example 2, except that the silver iodide content was changed as shown in Table 5. Layer 5: An intermediate layer completely similar to layer 5 of Example 2. Layer 6.../[3 was applied again. Layer 7: Layer 4 was applied again. Layer 8: Layer 5 was applied again. /I9: Layer 3 was applied again. Layer 10.../I4 was applied again. Layer 11: Layer 5 was applied again. i12: A second protective layer completely similar to layer 11 of Example 2. Layer 13: A first protective layer completely similar to layer 12 of Example 2. The dry film thickness of the photographic constituent layer of the finished sample was approximately 20 μm. Exposure and development treatments were carried out according to Example 2. The results are shown in Table 5. /7'□-11, As is clear from the results in Table 5 below, when the silver iodide content is low, the removal of tIi is possible regardless of the membrane swelling rate T and the presence or absence of a bleaching accelerator. The speed is fast. However, as the silver iodide content increases, if the film swelling rate Ty2 is large, the bleaching rate becomes noticeably slow; It can be seen that there is almost no delay in the bleaching rate even when the silver iodide content is 0.5 mol % or more, particularly 1 mol % or more, which is preferable from the viewpoint of sharpness and sharpness. Example 6 A sample having a silver iodide content of 8 mol %, a film swelling rate T of 8 seconds, and an emulsion film thickness of 19 μIff was prepared in the same manner as in Example 5. However, the bleach-fix solution contains 15% of the ferric ammonium noethylenetriaminepentaacetate of wood 2 in Example 5 per IO.
0g was used, and one prepared based on Example 2 was used. Exposure and development treatments were performed in the same manner as in Example 5. The following bleach accelerators of the present invention were added to the bleach-fix solution in varying amounts. The desilvering completion time was measured and the results are shown in Table 6. (Bleach accelerator used) (4) IOCB2 CH-CH25H (5) II
s CH2CH2C0OHOH 0■ (28) HSCH2CI28HC112CH20
H(29) HSCJCH2NCHzCHzOH2
8S CH=CH. Table 6 As can be seen from the results in Table 6, all of the exemplary accelerators of the present invention exhibit a favorable bleaching accelerating effect in the samples in which the film swelling rate T, film thickness, and coated silver amount are within the range of the present invention. In yet another experiment, 160 g/Q of ferric ammonium ethylenenoaminetetraacetate was used as the bleaching agent in the bleach-fix solution, and ferric ammonium hydroxyethyliminodiacetic acid
Two types of) nth using iron ammonium 200g/Q
A similar experiment was conducted with a fixer to measure the time required to complete desilvering, and the results were substantially the same as with ferric ammonium diethylenetriaminepentaacetate. Applicant Konishiroku Photo Industry Co., Ltd.

Claims (1)

[Scope of Claims] (1) It has a photographic constituent layer including blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layers, and at least one silver halide emulsion layer contains 0.5 mol% or more. Contains silver iodide of
and the total thickness of all photographic constituent layers excluding the support is 25 μm
After imagewise exposure and development of a silver halide color photographic light-sensitive material in which the film swelling rate T1/2 of the binder in the photographic emulsion layer is 25 seconds or less, at least one of the organic acid ferric complex salts is added. 1. A method for processing a silver halide color photographic light-sensitive material, the method comprising processing with a bleach-fixing solution containing a silver halide color photographic material. (2) The method for processing a silver halide color photographic material according to claim 1, wherein the silver halide color photographic material has a black colloidal silver antihalation layer. (3) The silver halide color photographic light-sensitive material according to claim 1 or 2, characterized in that the total coating amount of silver in the silver halide color photographic light-sensitive material is 50 mg/dm^2 or less. Processing method. (4) Claim 1, characterized in that the membrane swelling rate T1/2 of the binder in the photographic emulsion layer is 20 seconds or less.
A method for processing a silver halide color photographic light-sensitive material according to item 1, 2 or 3. (5) The silver halide color photographic photosensitive material according to any one of claims 1 to 4, wherein the silver halide contains at least one layer of silver iodide in an amount of 2 mol % or more and 25 mol % or less. How materials are processed. (6) The silver halide color photographic light-sensitive material according to any one of claims 1 to 5, characterized in that a pre-fixing process having a fixing ability is performed immediately before the bleach-fix solution and after the development process. processing method. (7) The following general formula [
7. The method for processing a silver halide color photographic light-sensitive material according to claim 6, which comprises a compound selected from [I] to [VII]. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [IV] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [V] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [VI] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [VII] ▲ Mathematical formulas, chemical formulas, Tables etc. are available▼ [In the above general formula, Q is a heterocycle containing one or more N atoms (
Represents the atomic group necessary to form a 5- to 6-membered unsaturated ring (including those with at least one fused ring), and A is ▲Mathematical formula, chemical formula, table, etc.▼, ▲Mathematical formula, chemical formula ,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, 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. ▼, -SZ' or n_represents a monovalent heterocyclic residue (including those with at least one 5- to 6-membered unsaturated ring condensed to it), and B has 1 to 6 carbon atoms. M represents a divalent metal atom, X and X″ represent =S, =O or =NR″, 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 to which at least one 5- to 6-membered unsaturated ring is fused), or an amino group, and Y is >N- or >CH- represents Z
represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, Z′ represents Z or an alkyl group, and R^1 represents a hydrogen atom , carbon number 1
~6 alkyl groups, cycloalkyl groups, aryl groups,
Represents a heterocyclic residue (including those to which at least one 5- to 6-membered unsaturated ring is fused) or an amino group,
R^2, R^3, R^4, R^5, R and R' are each
Hydrogen atom, alkyl group having 1 to 6 carbon atoms, hydroxy group,
It represents a carboxyl group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group, or an alkenyl group. However, R^4 and R^5 may represent -B-SZ, or R, R', R
^2 and R^3, R^4 and R^5 each cyclize with each other to form a heterocyclic residue (including those to which at least one 5- to 6-membered unsaturated ring is fused). It's okay. R^6 and R^7 each represent ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R^9 is an alkyl group Or -(CH_2)n_8SO_3^- (however, R^
When 8 is -(CH_2)n_8SO_3^-, l is 0
Or represents 1. ) G^- is an anion, m_1 or m_
4 and n_1 to n_8 are each an integer of 1 to 6, m
_5 represents an integer from 0 to 6. R^8 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 above. D
represents a simple bond, an alkylene group or vinylene group having 1 to 8 monoprimes, and q represents an integer of 1 to 10. A plurality of D's may be the same or different, and the ring formed together with the sulfur atom may be further fused with a 5- to 6-membered unsaturated ring. X
' is -COOM', -OH, -SO_3M', -CON
H_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' is ▲mathematical formula, chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
or represents a hydrogen atom, and m and n each represent an integer of 1 to 10. R^1^1, R^1^2, R^1^4, R^
1^5, R^1^7 and R^1^8 represent a hydrogen atom, a lower alkyl group, an acyl group, or ▲a mathematical formula, a chemical formula, a table, etc.▼, and R^1^6 is a lower alkyl group represents. R^1
^9 represents -NR^2^0R^2^1, -OR^2^2 or -SR^2^2, and R^2^0 and R^2^1 represent a hydrogen atom or a lower alkyl group. Represents R^2^2 is R^
Represents an atomic group necessary to connect with 1^8 to form a ring. R^2^0 or R^2^1 and R^1^8 may be connected to form a ring. M' represents a hydrogen atom or a cation. The compounds represented by the above general formulas [I] to [V] include enolized compounds and salts thereof. (8) The silver halide color photographic light-sensitive material according to any one of claims 1 to 7, wherein the thickness of the photographic constituent layer of the silver halide color photographic light-sensitive material is 22 μm or less. processing method. (9) The method for processing a silver halide color photographic material according to claim 8, wherein the thickness of the photographic constituent layer of the silver halide color photographic material is 20 μm or less. (10) Each of the silver halide emulsion layers contains 4 mol % to 1 mol %
10. The method for processing a silver halide color photographic light-sensitive material according to claim 1, which comprises silver halide grains containing 0 mol % of silver iodide. (11) The method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 to 10, wherein the silver halide emulsion is a core/shell type silver halide emulsion. . (12) The silver halide color photographic light-sensitive material according to any one of claims 1 to 11, wherein the compounds represented by the general formulas [I] to [VII] are the following compounds: Processing method. (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (3) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (4) ▲ Numerical formulas, chemical formulas, tables, etc. Yes ▼ (5) HS-CH_2CH_2-COOH (6) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (7) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (8) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( 9) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (10) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (11) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (12) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (13) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (14) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (15) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (16) ▲ Mathematical formulas, chemical formulas, tables, etc. ▼ (17) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (18) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (19) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (20) ▲ Mathematical formulas, chemical formulas, There are tables, etc. ▼ (21) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (22) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (23) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (24) ▲ Mathematical formulas, There are chemical formulas, tables, etc. ▼ (25) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (26) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (27) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (28) HSCH_2CH_2NHCH_2CH_2O
H (29) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or (30) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (13) The bleach-fix solution is characterized by containing a ferric complex salt of the following organic acid. A method for processing a silver halide color photographic material according to any one of claims 1 to 12. (a) Diethylenetriaminepentaacetic acid (b) Cyclohexanediaminotetraacetic acid (c) Triethylenetetraminehexaacetic acid (d) Glycol etherdiaminetetraacetic acid (e) 1,2-diaminopropanetetraacetic acid (f) 1,3-diaminopropane- 2-oltetraacetic acid (g) ethylenediaminedi-o-hydroxyphenylacetic acid (h) ethylenediaminetetraacetic acid (i) nitrilotriacetic acid (j) iminodiacetic acid (k) methyliminodiacetic acid (l) hydroxyethyliminodiacetic acid (m ) Ethylenediaminetetrapropionic acid (n) Dihydroxyethylglycine (o) Nitrilotripropionic acid (p) Ethylenediaminediacetic acid (q) Ethylenediaminedipropionic acid