JPS61269156A - Treatment of silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance storage stability of a magenta dye by incorporating silver halide grains contg. silver iodide in the layer nearest to an antihalation layer and processing an imagewise exposed and developed specified silver halide color photographic sensitive material with a processing solution capable of bleaching silver. CONSTITUTION:The photographic constituent layers comprising the antihalation layer contg. black colloid silver, and blue-sensitive, green-sensitive, and red- sensitive silver halide emulsion layers are formed on a support, and silver halide grains contg. silver iodide are contained in one of the silver halide emulsion layers nearest to the antihalation layer. The total thickness of the photographic constituent layers is <=25mum, and the photosensitive material contains a magenta coupler in the silver halide emulsion layer usually, in an amt. of 0.005-2mol, preferably, 0.01-1mol per mol of silver halide, and it is imagewise exposed and developed, and then, processed with a processing solution contg. peroxide as a bleaching agent, and capable of bleaching silver.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to the processing of silver halide color photographic materials (hereinafter referred to as color photographic materials), and more specifically relates to the processing of silver halide color photographic materials (hereinafter referred to as color photographic materials), and more specifically, to the processing of silver halide color photographic materials (hereinafter referred to as color photographic materials). The present invention relates to a processing method of processing with a processing solution containing peroxide after processing with a developer.

[Prior art]

Conventionally, the following methods have been generally used to process color photosensitive materials. After the color photosensitive material is subjected to imagewise exposure, it is treated with a color developing solution containing an aromatic primary amine developing agent, whereby the silver halide is reduced to metallic silver, and the aromatic primary amine is It is oxidized and undergoes a coupling reaction with a coupler to produce a dye image.

The metallic silver is oxidized to soluble silver halide by a bleaching agent (oxidizing agent) in a bleaching process. Thereafter, by treatment with a fixing solution (eg, thiosulfate, thionanate, etc.), the silver complex ions are converted into silver complex ions and removed from the photographic material, leaving only the color image. The actual development process includes the above-mentioned color development process and the basic processes of bleaching and fixing, as well as auxiliary processes for physical photographic image preservation and quality preservation. There is also a method of processing with bleaching constant NwL carried out in one bath.

As bleaching agents used in the bleaching process, red blood salts, ferric chloride, aminopolycarboxylic acid-metal complex salts, and peroxides are generally used.

Both red blood salt and ferric chloride have strong bleaching blades, and the bleaching speed (
It is a good bleaching agent because it has a fast oxidation rate.

However, since bleaching solutions using red blood salt liberate cyan ions through photolysis and cause environmental pollution, it is necessary to make the treated waste liquid harmless. Also, chloride chloride
Bleaching solutions that use iron have a very low pH and extremely high oxidizing power, so the processing equipment that contains them is easily corroded, and during the washing process after bleaching, hydroxylation occurs in the emulsion layer. Precipitating iron 1: However, there is a problem that causes so-called staining. This is no good,
A cleaning step using an organic chelating agent is required after the bleaching treatment, which is not suitable for the purpose of rapid processing and labor saving, and is also undesirable due to the risk of generating chlorine gas in terms of environmental pollution.

It has been proposed to use an aminopolycarboxylic acid-metal complex salt as a bleaching agent that causes less environmental pollution than the red blood salt and ferric chloride. However, the bleaching solution of the 7-mi/polycarboxylic acid-metal complex salt has low oxidizing power and has an insufficient bleaching edge. For example, when bleaching a low-sensitivity color light-sensitive material that is mainly composed of silver chlorobromide emulsion, the purpose can be achieved, but if the material is mainly composed of silver chloride iodide or silver iodobromide and the color When processing sensitized high-sensitivity color light-sensitive materials, especially color light-sensitive materials using high-silver emulsions, the bleaching effect may be insufficient, resulting in poor desilvering, or oxidation products of color developing agents and couplers may be mixed. Even after bleaching, the dye produced by the oxidative coupling of red blood salt remains in the state of a leuco dye, which is a reaction intermediate, and the dye is not completely formed, resulting in so-called poor color recovery6. Bleaching agents (oxidizing agents) such as ferric chloride salts or aminopolycarbon Wl metal complex salts pose problems such as environmental pollution due to the pollution burden of the waste liquid, so measures must be taken to completely render the treated waste liquid harmless. Of course, it is preferable to use a peroxide method that does not use metal ions, in particular a method that uses persulfate ions and/or hydrogen peroxide or a compound that releases hydrogen peroxide. Peroxide used as a bleaching agent decomposes into water and oxygen or sulfate, so it does not increase biological oxygen demand (BOD) or chemical oxygen demand (COD), making it advantageous in terms of pollution control. However, for example, persulfate ions are
It has stronger oxidizing power than metal complex salts of iron and organic acids, and has a high redox potential, but silver has a weak bleaching blade and takes a long time to bleach. For this purpose, it is known to use various bleach accelerators in combination, and two bleach accelerators are added to a solution containing persulfate ions or to a prebath prior to a bleach bath, for example, in US Pat. No. 3,707. , No. 374, 3,72
No. 2,020, No. 3.893.85111, Special Publication No. 5
No. 1-28227, 41F! No. 53-94927, No. 53-95631, No. 55-25064, No. 55-
No. 26506, Research Disclosure (Rcsea)
rcbD 1 closure) No. 15704 (197
A method using a bleaching accelerator such as a mercapto compound or a nootyl rubamate compound, as described in JP-A No. 149944/1986, JP-A No. 58-83
No. 52 and No. 58-95347, a method has been proposed in which a 7-mi compound is incorporated into a sensitive material, and this technique improves the bleaching blade and makes it possible to speed up the bleaching time.

However, even if these accelerators are used, there is no bleaching agent that uses peroxide as a bleaching agent. [! For liquids, high-sensitivity photographic materials that have a black colloidal silver antihalation layer and a silver halide layer containing 3 mol% or more of silver iodide in the closest layer have a large film thickness. It was found that desilvering failure suddenly occurred when continuous processing was performed.

Therefore, the inventor first determined that the total thickness of the photographic constituent layers was 25 μm.
It has been discovered and proposed that the desilvering property of the above photosensitive material can be significantly improved by reducing the amount to below m.

However, when the film thickness of the color photosensitive material is reduced in this way and it is processed with the processing solution having bleaching ability of the present invention,
An unexpected problem arose in that the storage stability of the magenta dye deteriorated. This was a completely unexpected phenomenon since it does not occur at all in ordinary color photosensitive materials in which the total thickness of the photographic constituent layers is 25 μm or more. 6. If the treatment time with a treatment solution that has whitening ability is 3 minutes or more,
It has been found that magenta dye deteriorates significantly under high temperature and high humidity storage conditions such as 0° C. and 80% relative humidity, and this is a serious problem for Tenkawa.

Therefore, in order to process color photosensitive materials with the processing solution having bleaching ability of the present invention, it is desired to develop a technique that prevents deterioration of the magenta dye due to storage and does not damage the silver source white blade.

[Purpose of the invention]

Accordingly, a first object of the present invention is to provide an excellent method for bleach-fixing high-sensitivity silver iodide-containing color light-sensitive materials in the processing of color light-sensitive materials.

A second object is to provide a method for processing color light-sensitive materials in which the storage stability of the produced magenta dye is improved.

The purpose of @3 is to provide a method for processing color photosensitive materials that has a low risk of environmental pollution and meets the requirements for pollution prevention.

[Structure of the invention]

As a result of extensive research, the present inventor has found that the present inventor has a photographic constituent layer on a support including an antihalation layer containing black colloidal silver and a blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layer. The layer closest to the antihalation layer among the silver emulsion layers contains silver halide grains containing silver iodide,
A color photosensitive material in which the total thickness of the photographic constituent layers is 25 μ(1) or less and contains a compound represented by the following general formula (1) is developed after imagewise exposure, and peroxide is used as a bleaching agent. The purpose of the present invention can be achieved by treatment with a treatment solution having silver bleaching ability containing the general formula (1
3 In the formula, Ar represents an optionally substituted phenyl group, and Y represents an aromatic ring 1ti! represents a group that leaves when a dye is formed by coupling with an oxidized product of an amine color developing agent. X represents a halogen atom, an alkoxy group or a furkyl group, R represents a group that can be substituted on a benzene ring, and n represents an integer of 1 or 2.

When summer 1 is 2, R may be the same or different.

Here, the photographic constituent layer refers to all the parent wood involved in image formation that is on the same side as the support surface coated with the black colloidal silver-containing antihalation layer of the present invention and the at least 3N silver halide emulsion layer. The colloid layer includes, in addition to the antihalation layer and the silver halide emulsion layer, a subbing layer, an intermediate layer (a simple intermediate layer, a single filter layer, an ultraviolet absorbing layer, etc.), a protective layer, and the like.

The most preferred embodiment of the present invention is the general formula (1) to [
The present inventor has found that the object of the present invention can be achieved more effectively by containing at least one of the compounds shown in (2).

General formula (1) General formula [II] General formula (II
) General formula [■] General formula (V) General formula [VI] In the above general formula, Q 1. t Represents a group of atoms necessary to form a heterocycle containing one or more N atoms (including those in which at least one unsaturated ring of 5 to 6 shells is condensed), A represents the group of atoms necessary to form a heterocycle containing one or more N atoms, X' or n1-valent heterocyclic residue (including those to 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
”, and 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 G shell is fused to this) an atom, an ammonium group, an amino group, a nitrogen-containing heterofulkyl group with 1 to 6 heteroaryl groups, a cycloalkyl group, a 7-aryl group, a heterocyclic residue (at least one unsaturated ring of 5 to 6 shells is attached to this) R2, R3, R, R%, R and R' are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, Represents an ami7 group, an acyl group, an aryl group, or an alkenyl group having 1 to 3 carbon atoms.However, R4 and R5
may represent -B-3Z (also R and R', R2 and R
3. R4 and R6 may each be cyclized with each other to form a heterocyclic residue (including one in which at least one unsaturated 5-6H ring is fused thereto).

Rs = R? represents each, R1 is an alkyl group or -(CH2)nIsO
represents 0, where R6 is -(CH2) n @ SO
s" f), Q represents 0 or 1.) GO is an anion, all to -4 and n+ to n are each 1
An integer of ~6 represents an integer of 0 to 6. R is a hydrogen atom or an alkali, provided that Q' has the same meaning as Q above. D
represents a simple bond, an alkylene group or a vinylene group having 1 to 8 monomers, q represents an integer of 1 to 10, multiple Ds may be the same or different, and the ring formed with the sulfur atom is Furthermore, the compound represented by the above general formula may be condensed with the unsaturated ring of the 5-G shellfish, and includes enolized compounds and salts thereof.

That is, the present inventor continuously processed a high-sensitivity fine-grain color light-sensitive material having black colloidal silver as an antihalation layer and at least three silver halide emulsion layers containing a silver iodide-containing emulsion adjacent to the black colloidal silver layer. We focused on the phenomenon that the desilvering properties deteriorate significantly in cases where J! ! ! It has been discovered that when processed with a solution, when the photographic constituent layers of the silver iodide-containing color light-sensitive material to be processed become thinner than a certain value, the bleach-fixing properties are significantly improved and desilvering defects are improved. It is.

Furthermore, this phenomenon shows that when the thickness of the photographic constituent layer of a silver iodide-containing color light-sensitive material increases, obvious desilvering defects occur at the boundary between the black colloidal silver-containing antihalation layer and the silver iodide-containing silver halide emulsion layer. It has been found that it increases significantly because of this.

Furthermore, the present inventor has found that when a specific bleach accelerator is added to a bleach-fix solution containing peroxide as a bleaching agent, the film thickness of the photographic constituent layers including the colloidal silver-containing antihalation layer and the silver halide emulsion layer (gelatin film If the thickness (thickness) exceeds a certain value, a good bleaching accelerating effect cannot be obtained, but if the thickness of the photographic constituent layer (gelatin film thickness) of the color photosensitive material is below a certain value, the bleaching accelerating effect of the specific bleaching accelerator will be improved. We have discovered the surprising fact that this can be significantly improved.

Preferred implementation of the invention! ? ! ! According to the above, the thickness of the photographic constituent layer of a color photographic light-sensitive material is 22 μm or less, more preferably 20 μm or less, particularly 18 μm or less. It has been found that the first object of the present invention can thereby be achieved more effectively.

Furthermore, the unexpected phenomenon of deterioration of storage stability of magenta dye that occurs when the film thickness of the photographic constituent layer becomes 25 μm or less can be solved by using a specific magenta coupler, which is the second object of the present invention. I achieved this and discovered the scales.

Next, the present invention will be specifically explained.

The magenta dye-forming coupler used in the present invention can be represented by the following general formula (CI').

General formula [C1] Ar A': A phenyl group, which is a previously substituted 7-enyl group.

Substituents include a halogen atom, an alkyl group, an alkoxy group, a 7-aryloxy group, an alkoxycarbonyl group, a Schiff 7 group, a carbamoyl group, a sulfonyl group, a sulfonyl group, a sulfonamido group, or an acylamino group, Q, Ar
The phenyl group represented by may have 2 or more substituents.

Specific examples of substituents are listed below.

Halogen atom: chlorine, bromine, fluorineFurkyl group: methyl group, ethyl group% 1So-propyl group, butyl group, t-butyl group, t-pentyl group, etc., but especially an alkyl group having 1 to 5 carbon atoms preferable.

Alkoxy group: methoxy group, ethoxy group, butoxy group,
Examples include 5eC-butoxy group and 1so-pentylokyne group, and particularly preferred is an alkoxy group having 1 to 5 carbon atoms.

Aryloxy group = phenoxy group, β-su7toxy group, etc., but this aryl moiety may further have the same substituents as listed for the phenyl group represented by Ar.

Alfkidicarbonyl group: The above-mentioned carbonyl group with an alkoxy group attached, and those having an alkyl moiety of 1 to 5 carbon atoms, such as a methoxycarbonyl group and a pentyloxycarbonyl group, are preferable.

Carbamoyl group: Furkylcarbamoyl group such as carbamoyl group, dimethylcarbamoyl group Sulfamoyl group Furkylsulfamoyl group such as Nislua T-moyl group, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group Sulfonyl group: Methanesulfonyl group, ethanesulfonyl group, butanesulfonyl group, etc., furkylsulfonamide group: notanesulfone 7 mido group, toluenesulfonamide group, etc., furkylsulfonamide group, arylsulfonamide group, etc. 7 sylamide group: 7 acetamide group Particularly preferred are halogen atoms such as , pivalyl 7-mi 7 group, and benz 7-mido group, among which chlorine is most preferred.

Y: represents a group that leaves when a dye is formed by coupling with an oxidized product of an aromatic primary amine color developing agent.

Specifically, it represents a group of atoms required to form a 5- or 6-shell ring with an atom selected from, for example, a halogen atom, an alkoxy group, or an atom. ) Specific examples are given below.

Halogen atom: chlorine, bromine, 77 alkoxy group: ethoxy group, penciloxy group, methoxyethylcarbamoylmethoxy group, tetradecylcarbamoylmethoxy group Calculation aryloxy group = 7e/oxy group, 4-methoxyphenoxy group, 4-2 Acyloxy groups such as trophenoxy group: acetoxy group, myristoyloxy group, benzoyloxy group 7-arylthio group: phenylthio group, 2-butoxy-5-
Alkylthio groups such as octylphenylthio group, 2.5-nohexyloctylphenylthio group: methylthio group, octylthio group, hexadecylthio group, pencylthio group, 2-(diethylamino)ethylthio group, ethoxycarbonylmethylthio group,
Nidoxyethylthio group, PhaeNZ: pyrazolyl group,
Imidazolyl group, triazolyl group, tetrazolyl group, etc. IX: Represents a halogen atom, an alkoxy group, or a fluorine group.

Specific examples are listed below.

Halogen atom: chlorine, bromine, fluorine Alkoxy group: 1 carbon atom such as methoxy group, ethoxy group, 5ee-butoxy group, 1so-pentyloxy group, etc.
~5 alkoxy groups are preferred.

Alkyl group: An alkyl group having 1 to 5 carbon atoms is preferable, such as a methyl group, ethyl group, 1so-propyl group, butyl group, t-butyl group, and pentyl group.

Particularly preferred is a halogen atom, with chlorine being particularly preferred.

R: represents a group that can be substituted on the benzene ring, and represents 1 or 2. When I+ is 2, R may be the same or different.

Groups that can be substituted on the benzene ring represented by R include a halogen atom, R'-, and R'0-.

etc.

R', R" and R"' may be the same or different and each represents a hydrogen atom or a fulkyl group, fulkenyl group or aryl group which may have a substituent.

Among these, preferably It is.

Specific examples of magenta couplers are shown below, but the invention is not limited thereto.

C! ll Examples of R in the above formula include the following.

M-1-NIICOC, 112゜ M-2-NHCOC,,11□.

Examples of Y in the above formula include the following.

M-8 M-11-SC, □H25 M 12 -SCH2COzCJsM-13-SC
H2C008 M-15-5CH2CONH.

M-16-SCHsCIIzOCJsM-17-S
SC112C112011-19-5C112CII□
NHSO□CH.

CH3 CH3 M-32 M-33 Q 4Q In the present invention, the magenta coupler represented by the general formula (Crl) can be used in combination with conventionally known magenta couplers within the scope of the purpose of the present invention. .

Furthermore, as colorless couplers that can be used in combination with the present invention, British Patent No. 861,138, British Patent No. 914.145, British Patent No. 1,1
No. 09°963, Japanese Patent Publication No. 45-14033, U.S. Pat.
Age 77 Rebel Cusen Volume 4 pp. 352-367 (
(1964) and others.

When a magenta coupler represented by general formula (CI) is contained in a silver halide emulsion layer, silver halide 1
per mole: 170.005 to 2 moles, preferably 0.0
It is used in a range of 1 to 1 mole.

The bleaching accelerator of the present invention has the general formula [l) or Vl)
Typical examples include, but are not limited to, the following:

[Exemplary compounds]

(1-3> (1-4) (1-7)
N-8) (1-9)
(1-10>(I-11
) (1-12)(f −1
3) (1-14) (1-1
5) (1-16>(r −
17) (I-18)N
-19) (1-20) CH2
C82COOH (1-2t>N,.

shio2shiuur+
CH2CH3(r-23)
(1-24)N-25)
(I-26)N-27)
(1-28)N
l(r-31)
(+ −32>N −33)
(1-34) (1-35)
(1-36>(1-37>(
r −38>(ff−1) (
II-2>,>b
SS(III-3)
(n -4) (n -5)
(II-6') (El-7)
(II-8) (II-9)
(II-10), (n
-11> (If -12) (1-1
3) (■-14) (II-
15) (n-16)(I[
-17) (II-18)(
II-19) 01(OH (II-20) (n-21) (n-22) (n-23) (■-24) (II-25) (n-26) S II II H3CNH-CNH-NH -CNH-CH3(n-28
> 112N-CSNHNHCS-Ni12(II-29) (II-30) (If-31) (IT-32) (II-33) (II-34) H2N C5NH(CH2)2NHCS-N13(I
T-35) H2N-CSNH(CH2)4NHCS N13(I
I-36) HJ-CSNH(CH2)sNHCS N13(II
-37) (II-38) (If-39) (■-40) (I[-41> (n -42) (II-43) (U-44) (n-45) (II-46) ( II-47) b 5 (IT-48) (n -49) (■-50) (Il-51) (U-52) (II-53) S (■-54) (■-55) (If- 56) (n-57) ([1-58) (U-59) (If-60> (II -611 (II-62) (II-63> (IT -64) (II-85> (tl- 66) (II-67) Na Na (U -68) (ff-69) (II-70) (II-71) (n-72) (IT-73) b (If-74) (If-75) CI3NFICHzC1hNtlCSCToCllzC
■2COOl1 (II -76) (If-77) (n-78) (I[-79) (n -80) (II-81) (n-82) (II-83) (If-84) (II -85> (n-86) (II-87>(n-88>(II-89> (II-90) (II-91) (II-92) S (II-93) (II-94> ( II-95) (n-96) ) □ (TI-97) (II-98) (n-99) (■ -too) (II-1ot) (II-102) (IT-103) (It-104 ) (IT-105) (n-106) (II-107)
1□ ↑ (II -108) (.

1-"09):・:1 1' (IT-110) (■-111) (Ill -
112>(If -113) (
■-1141b (IT-115) (II-1
16) (n -117) (■-
118>(II-119) (
II-120) (II-121>
(II-122) (II 123>
(H124) (It-125)
(II-126) (H-127
> (y 128) (]l
-129) (I[-130)
(II-131,) < ■
-132>(II -133>
(II-134) rI.

(IT -135) ([-13
6) (II-137) (I
I-138) (II-139)
(II-140) (IT-141>
(U -142) (II-143) (TI-144> H (If-145) (It-146) NH (■-147) N)l (II-148) (n-149) (II-151) ↓ (■-152) (n-153) (n-154> (II-155) (II-156) ([1-157) (It-158) H2N C)12cH25H (fir -2) (III-3 ) (III-4) (Ill -5) 1100c -C)I2CH2・5H ([11-7) ([[[-8) ([[[-9)
(I [I -10) Duck (III -11) (ll-12) f-1 ON-Cl1□CH2-5R \-1/ f'ilJ (III-14) CH2C) 12-SH (III - 15) (I[
I-16) (1-171 (III-18) CT.

113 (In-19) (I[l-
20) (III-21)
(III-22) CH2C1125N (III-23) (II-2
4) ([I[-251(III-26) (III-27) H (I[[-28) (I[[-29) (I[
-30) (III-31)
(1-32>(III-33) (III-34) (II-35) (I[l-36) (III-37) (■-1) CHyoCH3 HV-2) (■-3) ( IV-4) (IV-5) H3 ■ (V-1) (V-2) (V-
3) (V-4) (V-5)
tV-6) (V-7>
(V-8) (V-9)
(V-10) (V-11)
(V-12)υII
0H (V-13)
(V −14>(V −1,5>
(V-16) (V-17)
(V-18) (V-19
) (V-20) (V-21
) (V -22) (V -23
) (V-24>(V-25)
(V 26 ) (V 27
) (y zs>(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) Nawate (V-55> (V-56)
(V-57) (V-58
) (V -59) (V -6
0) (V-61) (V-62
)(V-63>(V-6
4) (V-65) (V-6
8) (V -67) (V -
as) (V-691(V-70> (V-71) (V-7
2) Amane (V -73) (V -
74) (V-75) (V
-76) (V-77>
(V-78) (V-79)
(V-80) (V-81)
(V-82)NH2Cl.

(V-83) (V-84
)(V-85>(V-8
6) (V-87> (V-8
8) (V -89) (V
-90) (V-91) (V
-92) and H2 and t12Nlh
(L; 11 December NH2 (V -93)
(V-94) (V-95)
(V-96) (V-97
) (V-98) (V-99
) (V -100) (V
-101) (V-102)(
V-103) (V-1
04) (V -105) (
V-106) Nl2 Nl
2 (V -107) Nl2 (V -108) (V -109) (V -110) (V -111) (V -112) (V -113) (V -114) (y -115) (V - 116) (V-117) (V -118) (V -119) SR5H (V -120) (V -121) (V -122) (V -123) (V -1
24>(V -125>(V
-126) (V -1,27)
(V-1281 (V-129)
(V-130) (V-131)
(V-132) (V-133)
(y + 134)N112sl( (V -135> (V -1
36) 03Na (V -1371 (V-138) (V -139) (V-140
) (V -141) (V -1
42) (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 −156)(I+ (V −157) (y −158
>(V-159) (V-16
0) (V -161) (V
-162>(V -1631 (V -164) (V -165) (V -1
66) (V -167) (V
-168):)11
8H2 (V-169)
(V-170) (V-171)
(V -172) HA H (V -173> K (V -174) (V-175
)1ISll (V -176) H (V -177) (V -17
8) (V -179) H (V -180> (V-181
) (V-182) (V-183
) (V -184) N = N I N,, N-CH2CIh5O,Ni1゜[H (Vl-1> (W-2)NT
-3) (Vl-4) (W
-5) (Vl-6) (■-7)
(■-8) (■-9) (Vl
-10) (W-11) (V[-12>
(W-13) (Vl-14) (
VI-15) (Vl-16) (Vl-1
7) (Vl-18> (Vl-
19) (Vr-20) (■-21>
(Vr-22) (■-26> (Vl
-27) (Vl-28), (
VI-29) (Vl-30)
(Vl-31) (Vl-32) (Vl-
33) (Vl-34)l (V[-351 (Vl -36>
No. 53-95830, No. 53-104232, No. 5
It can be easily synthesized by known techniques described in US Pat. No. 3-141623, US Pat. No. 55-17123, US Pat.

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 processing bath having bleaching ability, and is preferably added to a processing bath having bleaching ability. It is also preferable to add it to a pre-processing solution and bring it into the bleach-fixing bath by bringing it into the color photosensitive material, or to add it to the color photosensitive material in advance at the time of manufacture and elute it into the bleach-fixing bath. may also be used.

These bleach accelerators of the present invention may be used alone or in combination.
When the bleaching accelerator is added to a processing solution having bleaching ability or a bath (pretreatment solution) preceding those baths, the amount added is generally about 0.0 per IQ of the processing solution.
Good results are obtained in the range of 1 to 100 g. However, in general, when the amount added is too small, the bleaching promotion effect is small;
Also, if the amount added is too large than necessary, precipitation may occur and contaminate the color photosensitive material being processed.
It is preferably 0.05 to 50 g per treatment wLin, and more preferably 0.05 to 15 Fi per treatment liquid IQ.

When the bleach accelerator of the present invention is added to a treatment bath having bleaching ability and/or a bath (pretreatment bath) that precedes a treatment bath having bleaching ability, it may be added and dissolved as is, but water, Generally, it is added by dissolving it in an alkali, organic acid, etc., but if necessary, adding it by dissolving it in an organic solvent such as methanol, ethanol, acetone, etc. will not affect the bleach-fixing effect. has no effect.

The bleaching accelerator of the present invention is represented by the general formulas (1) to [■], among which %R1, R2, R3, R1, R6, R
8, R,, A18%D, Z, Z', R%R', and a heterocyclic residue formed by R and R', R2 and R3, R4 and R7, and Q, Q' , ami7 group, aryl group, alkenyl group, and alkylene group may each be substituted, and examples of the substituents include alkyl group, aryl group, alkenyl group, cyclic alkyl group, aralkyl group,
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, 7 alkylamides, 7 noalkylamides, anilino group, N-furkylanilino group, 7 N-7lylanyl groups, N -acylami/group, hydroxyl group, etc. can be mentioned. In addition, the above R, -R,, R3
, Z', R%R' may also have a substituent, and examples of the substituent include all of those listed above except for the alkyl group.

As peroxides according to the present invention, hydrogen peroxide, percarbonates, perborates, and persulfates are preferably used.

Further, examples of these salts include potassium salts, sodium salts, ammonium salts, and the like. The preferred amount of these used is 0.01 to 6.0 mol/Q, more preferably 0.05 to 3.0 mol/Q.

The pH of the treatment solution containing peroxide used in the present invention is 0.1 to
It is necessary to adjust to a range of 8.0, particularly preferably 0.
．． It is in the range of 5 to 5.5.

When the peroxide according to the present invention is decomposed, it easily becomes water and oxygen or sulfate, and can be easily and completely rendered harmless.

Furthermore, the materials used in the treatment solution according to the present invention are inexpensive and have excellent bleaching ability even when used at low concentrations.This advantage is directly reflected in terms of resources, with a low pollution burden. This makes it possible to easily supply an inexpensive bleaching solution or bleach-fixing solution.

The treatment liquid having bleaching ability of the present invention may contain organic acid ferric complex salt, ferric chloride, red blood salt, etc. for the purpose of further enhancing the bleaching ability. Representative examples of organic acids that form organic acid ferric complex salts include the following.

(1) Ethylenediaminetetraacetic acid (2) Ethylenediaminetetraacetic acid (3) Noethylenediaminepentaacetic acid (4) Diethylenetriaminepentamethylenephosphonic acid (5
) Cyclohexanenoamine tetraacetic acid (8) Cyclohexanediamine tetramethylene phosphonic acid (7) Triethylenetetramine hexaacetic acid (8) ) Lyethylenetetramine hexaacetic acid (9) Glycol ethernoamine tetraacetic acid (10) Glycol ether diamine tetramethylene Phosphonic acid (11) 1.2-diaminopropaneisoacetic acid (12) 1.
2-diaminopropane tetramethylenephosphonic acid (13) 1.3-noaminopropan-2-ol tetramethylenephosphonic acid (14) 1.3-diaminopropan-2-ol tetramethylenephosphonic acid (15) ethylenediamine no-0-hydroxy 7Enylacetic acid (16) Ethylenecyamineno-0-uniloxyphinylmethylenephosphonic acid (17) Iminoniacetic acid (18) Iminonimethylenephosphonic acid (19) Methyliminodiacetic acid (20) Methyliminonimethylenephosphonic acid (21) ) Nitrilotriacetic acid (22) Nitrilotrimethylenephosphonic acid (23) Hydroxyethylethylenedi7minetetraacetic acid (24) Hydroxyethylethylenenoaminetetramethylenephosphonic acid (25) Nitrilotripropionic acid (26) Hydroxyethylgrin (27) ) Hydroxyethyliminodiacetic acid (28) Hydroxyethyliminonimethylenephosphonic acid (29) Ethylenecyamine diacetic acid (30) Ethylenenoamine niprobionic acid Particularly preferred among these organic acids forming ferric complex salts The following items can be mentioned.

(3) Diethylenetriaminepentaacetic acid (5) Cyclohexanediaminetetraacetic acid (a) Triethylenetetraminehexaacetic acid (1) Ethylenediaminepentaacetic acid (11) 1,2-noamitsupropanetetraacetic acid (9) Glycol etherdiaminetetraacetic acid These organic acids Ferric acid complex salts are free acids (hydrogen salts), sodium salts, potassium salts,
Alkali metal salts such as lithium salts, ammonium salts, or water-soluble amine salts such as triethanolamine salts are used, but potassium salts, sodium salts, and ammonium salts are preferably used. At least one type of these ferric complex salts may be used (71, two or more types may be used in combination, etc.).The amount used can be selected arbitrarily. Although it is necessary to select it depending on the amount and silver halide composition, it generally has a high oxidizing power, so it can be used at a lower concentration than other aminopolycarboxylic acid salts.

That is, it is preferably used in an amount of 0.01 mol or more, more preferably 0.05 to 0.6 mol, per IQ of the working liquid. Note that it is desirable to use the replenisher in a highly concentrated form with the highest solubility in order to achieve high concentration and low replenishment.

It is desirable that metal ions be supplied to the treatment liquid having bleaching ability of the present invention by any method in order to improve the bleaching ability. For example, it can be supplied in any form such as a halide, hydroxide, sulfate, phosphate, acetate, etc., but it is preferable to supply it as a complex salt of the chelating agent using the following compounds (hereinafter, these A metal compound that supplies metal ions is referred to as a metal compound of the present invention). However, it is not limited to these supply methods. Incidentally, the chelating agent may be any one such as organic polyphosphoric acid and amide/polycarboxylic acid.

[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) Phosphorus Nickel acid (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-21) Chloride Magnesium (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-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 (A-35) Lead acetate (A-36) Lead nitrate (A-37) Titanium chloride (A-38) Stannous chloride (A-39) Silconium sulfate (A-40) Norconium nitrate (A-41) Ammonium vanadate (A- 42>
Ammonium metavanadate (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) Intritum nitrate (A-501 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 These metal compounds of the present invention may be used alone, or 2
It is also possible to use more than one species in combination. The amount of metal ions to be used is preferably 0.0001 mol to 2 mol, particularly preferably 0.001 mol to 1 mol, per 1 cubic meter of the liquid used.

The processing liquid having bleaching ability of the present invention can contain various additives together with the peroxide of the present invention as a bleaching agent as described above. It is desirable to contain an alkali halide or ammonium halide, such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, etc., as an additive for bleach-fixing properties. , also borate,
pHM of oxalate, acetate, carbonate, phosphate, etc., flfi
Solubilizers such as triethanolamine, acetylacetone, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids, polycarboxylic acids, alkylamines, polyethylene oxides, etc. can be added to ordinary bleaching solutions. Those that are known can be added as appropriate.

The processing liquid having bleaching ability of the present invention includes a bleach-fixing liquid having a composition in which a small amount of a halide such as potassium bromide is added, or conversely, a composition having a composition in which a large amount of a halide such as potassium bromide or ammonium bromide is added. Further, a special bleach-fix solution having a composition consisting of a combination of the bleaching agent of the present invention and a large amount of a decadenide such as potassium bromide can also be used.

Silver halide fixing agents to be included in the bleach-fixing solution include compounds that react with silver lodenide to form water-soluble complex salts, such as potassium thiosulfate and sodium thiosulfate, such as those used in ordinary fixing processes. Typical examples include thiosulfates such as ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, thioethers, and high concentrations of bromides and iodides. These fixatives are 5
It can be used in an amount that can dissolve 8/Q or more, preferably 50 g/Q or more, more preferably 70 g/2 or more.

In addition, the bleach-fix solution contains various pHl1 buffers such as boric acid, borax, 17um hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. Even if these are contained alone or in combination of two or more, there is no effect. Furthermore, various optical brighteners, antifoaming agents, or antifoaming agents can be contained. In addition, preservatives such as hydroxylamine, hydrazine, sulfites, isomeric bisulfites, bisulfite adducts of aldehydes and ketone compounds, and other additive layers, methanol, trimethylformamide,
An organic solvent such as dimethyl sulfoxide can be appropriately contained.

Other powerful compounds that can be added to the processing solution having bleaching ability of the present invention and significantly reduce the bleaching properties include tetramethylurea, trisdimethylamide phosphate, ε-caprolactam, N-
Examples include methylpyrrolidone, N-methylmorpholine, tetraethylene glycol mono-7 enyl ether, 7-cetonitrile, glyfur monomethyl ether and the like.

In the processing method of the present invention, it is preferable to carry out the bleaching of the present invention immediately after color development; however, after color development,
After washing with water, rinsing, stopping, or other treatments, the bleaching treatment of the present invention may be performed.

The method of the present invention includes independent steps of development, bleaching, and bleach-fixing, but here, development means black-and-white development and color development, and there may be cases where only color development or both black-and-white development and color development are included. used.

The above steps do not necessarily have to be consecutive, and various processing steps can be included before and after each of the above steps. Such a process is called an auxiliary process, and the auxiliary process includes a stop bath,
There are stop and fix baths, hardening baths, neutralization towers, water washing, rinsing, image stabilization baths, etc.

From the viewpoint of simplifying the processing steps, the bleach-1 or bleach-fix solution of the present invention is preferably applied to a processing process in which both color development and development are followed by bleaching or bleach-fixing. In some cases, it is more preferable that the fixing solution does not contain a developing agent or halogen ions, and the type of color photosensitive material to be processed and other considerations: - If necessary, washing with water after color development,
Bleach-fixing can be carried out after appropriately undergoing one or more treatments such as rinsing treatment, stop treatment, bleach-fixing treatment, pre-bleach-fixing bath (so-called Fundigitan for efficiently performing bleach-fixing), or hardening treatment. More desirable.

Further, after the special one-time bleach-fixing process, it is optional to separately process with a bleach-fix solution or a fixer solution that is not according to the present invention. That is, it is optional to place a bleaching solution or a brightening/fixing solution according to the present invention at the processing bath location to remove image silver.

Next, specific examples of treatment processes will be shown, but the present invention is not limited to the following process examples.

■During film - Neutralization - Development 1 stop - Water washing 1 Color development 1 stop - Constant deposition - Water washing 1 Final treatment 1 Drying ■Development - Water washing - Antipine 1 Color development 1 Adjustment 1 + Constant deposition 1 Water washing 1 Final treatment 1 Drying ■Color development - constant wear - washing with water - final treatment - drying ■ color development - t+ - small amount of water washing constant wear - washing with water - washing with water -
Final processing - Drying ■Color development - Country I ■ Preliminary water washing - Water washing - Final treatment - Drying ■ Color development - Tadashi II - Final treatment - Drying ■ Color development - Tadashi fixed - Final treatment - Drying Final treatment The method is to perform water washing or a waterless washing treatment as described in JP-A-57-8543, JP-A-58-57903, etc., and the water-free washing treatment is particularly advantageous in terms of resource saving and image preservation.

Thickness of the photographic constituent layer of the color photosensitive material of the present invention (gelatin m
pi-> refers to photographic constituent layers excluding the support, i.e., subbing layer;
This is the total film thickness of all hydrophilic colloid layers such as the halenmine prevention layer, intermediate layer, three emulsion layers, filter layer, H-retaining layer, etc., and is the thickness of the dried photographic constituent layer.Thickness measurement In the present invention, the total thickness of the photographic constituent layers is 25 μm or less, preferably 22 μm or less, most preferably 20 μm or less,
Most preferably it is 18μ or less.

The silver halide of the silver halide emulsion layer used in the present invention contains at least 0.5 mol% of silver iodide grains, but it maximizes the sensitivity and photographic properties of the color light-sensitive material and the bleach-fixing performance of the present invention. For this purpose, silver iodide is preferably used in an amount of 3 to 25 mol % due to its photographic properties and bleach-fixing properties. In the present invention, if the content exceeds 25 mol%, the photographic properties are more favorable, but the bleach-fixing properties are markedly lowered. In the present invention, it is more preferable that silver iodide be contained in an amount of 3 mol % to 20 mol %.

Black color for preventing Halesian a used in the present invention
It is necessary that the colloidal silver dispersion layer has a sufficiently high optical density in the visible region (particularly red light) with respect to light incident from the support surface or emulsion surface of the color light-sensitive material. Further, it is necessary that the color light-sensitive material has a sufficiently low reflectance to light incident on the emulsion surface.

From the viewpoint of reflectance and bleach-fixing properties, colloidal silver with sufficiently fine particles is desirable, but the absorption becomes yellow to yellowish brown, and the optical density against red light does not increase.
Therefore, the grains have to be coarse to some extent, which makes it difficult for physical development to occur using these silver grains as nuclei, and it is thought that the bleach-fixing properties at the boundary with the silver halide emulsion layer deteriorate. In particular, if the silver halide emulsion layer contains at least 3 mol % of silver iodide grains, then the bleach-fixing process can be carried out if the silver halide emulsion layer closest to the support contains at least 3 mol % of silver iodide grains. It can be seen that the method of the present invention is effective because the phenomenon of deterioration in optical properties becomes more noticeable in multilayer color light-sensitive materials having three or more silver iodide-containing emulsion layers.

The photosensitive silver halide emulsion used in the present invention may be doped with each of the 81 metal salts or metal complex salts during the formation of silver halide precipitate, during grain growth, or after the completion of grain growth. For example, metal salts or complex salts of gold, platinum, palladium, iridium, ronium, bismuth, cadmium, copper, and combinations thereof can be used.

Excess halogen compounds generated during the preparation of the emulsion or by-products or unnecessary salts and compounds such as nitrates and ammonium 9m may be removed.

As a method for removal, a nude washing method, a dialysis method, a coagulation precipitation method, etc., which are 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 salts, water-soluble platinum salts, water-soluble balanum salts, water-soluble rhodium salts, water-soluble iridium salts; sulfur sensitizers; selenium sensitizers; polyamines, chloride 111 Chemical sensitization can be carried out using chemical sensitizers such as reduction sensitizers such as, alone or in combination. Furthermore, this silver halide can be optically sensitized to a desired wavelength range.6 There is no particular restriction on the method for optically sensitizing the emulsion of the present invention. Alternatively, optical sensitization can be carried out using an optical sensitizer such as a merocyanine dye alone or in combination (for example, supersensitization). These techniques are described in U.S. Pat.
No. 912.329, No. 3,397,060, No. 3゜6
No. 15.635, No. 3,628,964, British Patent 1
, No. 195.302, No. 1,242,588, No. 1,
No. 293,882, West German Patent (OLS) 2,030,3
No. 26, No. 2,121,780, Special Publication No. 43-493
No. 6, No. 44-14030, etc. The selection can be arbitrarily determined depending on the wavelength range to be sensitized, sensitivity, etc., and the purpose and use of the photosensitive material.

The average grain size of the silver halide grains used in the present invention is preferably 0.5 μII to 3 μ II, and if necessary, the grain size may be grown using a solvent such as 7 mmoni 7, thioether, thiourea, etc. It's a monkey that lets you do it.

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 contain epitaxially bonded silver halide grains as described in No.

The silver halide emulsion can contain various commonly used additives depending on the purpose. For example, stabilizers and antifoggants such as 7-endenes, triazoles, tetrazoles, imidazoliums, tetrazolium salts, polyhydroxy compounds; sildehyde-based, aziridine-based, inoxazole-based, vinylsulfone-based, acryloyl-based, carbodiimide Hardening agents such as those based on chroman, maleimide, methanesulfonic acid ester, and triazine; Development accelerators such as pencil flucol and polyoxyethylene compounds; Image stabilizing agents such as chroman, claman, bisphenol, and phosphite esters Agents include lubricants such as wax, glycerides of higher fatty acids, and higher alcohol esters of higher fatty acids. In addition, anionic, cationic, and nonionic surfactants are used as coating aids, permeability improvers for processing solutions, antifoaming agents, and as materials for controlling various physical properties of photosensitive materials. Alternatively, various species of both sexes can be used. Particularly the place J that has bleaching ability! I! It is preferable that these surfactants are eluted into the liquid. As antistatic agents, diacetylcell a-XS styrene perfluoroalkylsonium maleate copolymer, alkali salts of reaction products of styrene-mannic anhydride copolymer and p-7 minobenzenesulfonic acid, etc. are effective. . Examples of matting agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers. *Furthermore, it is also possible to use colloidal silicon oxide.

Examples of the latex added to improve the physical properties of the film include copolymers of acrylic esters, vinyl esters, and other monomers having ethylene groups.

Examples of gelatin plasticizers include glycerin and glycol compounds, and examples of thickeners include styrene-sodium maleate copolymers and alkyl vinyl ether-maleic acid copolymers.

In the color 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, albumin, Examples include proteins such as casein, cellulose derivatives such as hydroxyethyl cellulose and carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinyl-imigzol, and polyacrylamide. Ru.

1 Examples of the support for the color photosensitive 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, a polystyrene film, etc.
Furthermore, conventional reflective supports (e.g. baryta paper, polyethylene-coated paper, polypropylene synthetic paper, with a reflective layer attached,
or a transparent support in combination with a reflector), and these supports are appropriately selected depending on the intended use of the photosensitive material.

For coating the silver halide emulsion layer and other photographic constituent layers used in the present invention, a number of coating methods can be used, such as dipping coating, air doctor coating, curtain coating, and hopper coating.

Also, U.S. Patent No. 2,761,791, Z, 94L89
It is also possible to use a simultaneous coating method of 2N or more according to the method described in No. 8.

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.

The color photosensitive materials to which the bleach-fix solution of the present invention can be applied include internal development methods (see U.S. Pat. No. 2,376.679 and U.S. Pat. No. 2,801,171) in which a color former is contained in the photosensitive material. , an external development method in which a coloring agent is contained in the developer (U.S. Pat. Nos. 2,252,718 and 2,592,2)
No. 43 and No. 2,590,970).

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 Examples include those with an acylacedoanilide structure such as benzoylacedoanilide and bivalyl7ceto7nilide having an active methylene chain and having a substituent at the coupling position;
You can use any one you don't have. Thus, as the color former, both so-called 2-equivalent couplers and 4-equivalent couplers can be used.

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 in processing color photographic materials, or a developer used in 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, methol, and 1-hydroquine, preservatives such as sulfites, and alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. from accelerators, inorganic or organic inhibitors such as potassium bromide, 2-methylbenlimigsol, methylbenzthiazole, water softeners such as boron 1717 salts, and trace amounts of iodides and mercapto compounds. Examples include surface overdevelopment inhibitors.

The aromatic 11th & amine color developing agents used in the color developing solution used prior to processing with the bleach-fix solution of the present invention include a variety of those that are widely used in various color photographic processes. These developers include amine 717-yl and p-phenylenenoamine 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.
is preferably used at a concentration of about 0.1 g to about 30 Fl for IQ, and more preferably from about 1 g to about 1
．． Use at a concentration of 5 g.

Examples of aminophenol-based developers include 〇-Ami/
7er7-el, p-ami/7er/-el, 5-ami7-2-
Hydroxytoluene, 2-7minor-3-hydroxytoluene, 2-hydroxy-3-ami/-1,4-tumethylbenzene, and the like are included.

A particularly useful aromatic primary amine color developer is N.

It is an N-dialkyl-p-phenylenenoamine compound, and the furkyl group and phenyl group may be substituted or unsubstituted.

Among these, particularly useful compounds include N,N-diethyl-p-phenylenediaminefflFl1m, N-/chiru1]-phenylenenoamine salt rl&salt, N,N-ymethyl-p-phenylenenoamine hydrochloride, 2 -ami/-5
-<N-ethyl-N-dodecylamine/)-toluene, N
-ethyl-N-β-methanesulfonamidoethyl-3-
Methyl-4-amino/aniline sulfate [, N-ethyl-N-
β-Hydroxyethylamine/aniline sulfate, 4-7minor 3-methyl-N,N-noethylaniline sulfate, 4
-7mi/-N-(methoxyethyl)-N-ethyl-3-
methyl7niline-U-)luenesulfone)Sll'
can be done.

Preferably, the color developing agent based on phenylenenoamine is mixed into the bleach-fixing solution of the present invention.

The alkaline color developing solution used before the treatment with the processing solution having bleaching ability of the present invention contains, in addition to the above-mentioned aromatic primary amine color developing agent, various types of color developing solutions that are usually added to color developing solutions. Ingredients, such as alkaline agents such as sodium hydroxide, sodium carbonate, potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali 4 halides, benzyl alcohol, diethylenetriaminepentaacetic acid, l- h) Water softeners and thickeners such as P-oxyethylidene-1,1-nophosphonic acid can be optionally contained. The pH of this color developer is usually 7 or higher, most commonly about 1
0 to about 13.

The processing solution having bleaching ability according to the present invention includes 2-Hepar, Colornega film, Colorbock film, color reversal film for slides, color reversal film for movies,
It can be applied to color photosensitive materials using the emulsion of the present invention, such as color reversal films for TVs and color reversal vapors, but it is particularly suitable for processing high-sensitivity color photosensitive materials with a total coated silver amount of 20+ og/dm2 or more. Are suitable.

〔Example〕

Hereinafter, the present invention will be explained in detail with reference to Examples, but the embodiments of the present invention will be limited thereby. Following this pattern, a black colloidal silver antihalation layer, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer are formed from the support with various auxiliary layers interposed. A monodisperse highly sensitive silver halide emulsion layer was disposed on the outermost side of the blue-sensitive silver halide emulsion layer. That is, samples were prepared as described below, but the coated silver amount was kept constant and the film thickness was adjusted to vary the dry film thickness.

However, the following are the standard application conditions, and each prescription is 51! I arranged it.

Layer 1: A dispersion of black colloidal silver O0a, which exhibits high absorbency to light in the wavelength range of 400 to 700 nVA, is prepared by reducing silver nitrate with hydroquinone as a reducing agent in 3 g of gelatin to form an antihalation layer. Painted.

(Dry film ff2.0 μm) Layer 2: Intermediate layer made of gelatin. (Dry film thickness 0.8
μSWI3...1.5 g of low-sensitivity red-sensitive iodobromide plate emulsion (^8I; 8 mol%), 1.6. gelatin and O
, SOg 1-hydroxy-4-(β-methoxyethylami7carponylmethoxy)-N-[δ-(2t4-sheett-7milphenoxy)butyl 1-2-su7tamide (hereinafter referred to as cyan coupler (C- 1)), 0°02
8 g of 1-hydroxy-4-(4-(1-hydroxy-
8-7cetamido 3.6-disulfo-2-su7tylazo)7e/xy]-N-[δ-(2,4-di-7mil7e/xy)butyl1-2-su7tamide. 0.4 g of tricrenorphos 7 in which disodium (hereinafter referred to as colored cyan coupler (CC-1)) was dissolved.
(hereinafter referred to as TCP), a low-sensitivity red-sensitive silver halide emulsion layer.

Layer 4...Bow, 1. High-sensitivity red-sensitivity method of silver centralization emulsion (＾
g■; 7 mol%), 1.2 g of gelatin and 0.23
cyan coupler (c-i), 0.020g colored cyan (, 15-(...-1), 15gf
A highly sensitive red-sensitive silver halide emulsion layer containing l T CP.

Layer 5...0.07Fi of 2,5-no(-octylhydroquinone (hereinafter referred to as antifouling agent (HQ-1))
0.04g of butyl 7 tallate (hereinafter referred to as D) dissolved in
BP) and 1.2 g of gelatin.

Layer 6: Bow, 6g of low-sensitivity green-sensitive silver iodobromide emulsion (heg
■; 15 mol%)゛, 1.7 g of gelatin and 0.3
0 g of 1-(2,4,6-)lichlorophenyl)-3-
[3-(2,4-di-t-amyl72/xyacetamido)benzenamide 1-5-pyrazolone (hereinafter referred to as magenta coupler (M-a)), 0.20 g of 4゜4
-methylenebis-11-(2,4,6-)lichlorophenyl)-3-[3-(2,4-:)-t-amylphenoxyacetamide)benzenamide 1-5-pyrazolone (hereinafter referred to as magenta coupler (M -b)), Q, 0
66 g of 1-(2,4,6-dolichlorophenyl)-4
-(1-S7tylazo)-3-(2-chloro-5-octatecenylsuccinimideanilino)-5-pyrazolone (hereinafter referred to as colored magenta coupler (CM-1)) is dissolved in a 3Mi coupler. 0, 3F1 TCP
A low-sensitivity green-sensitive silver halide emulsion layer containing.

Layer 7: Bow, 5 g of high-sensitivity green-sensitive silver iodobromide emulsion (Ag
e; 11 mol%), 1.9 g of gelatin and 0.09
0,12 in which 3 g of magenta coupler (M-a), 0.094 g of magenta coupler (M +)), and 0.049 g of colored magenta coupler (CM-1) were dissolved.
A highly sensitive green-sensitive silver halide emulsion layer containing H TCP.

N8...0, 11. in which 0.2 g of yellow colloidal silver and 0.2 g of antifouling agent (IQ-1) were dissolved. of DBP and 2.1 g of gelatin.

(Dry film 1!J 1.2g ring) Layer 9...0.95g of low-sensitivity blue-sensitive silver iodobromide emulsion (
6 mol%), 1.9 g of gelatin and 1.8
4. a-[4-(1-benzyl-2-phenyl-3,
5-Shioxo 1.2.4-)lyacylinonyl)J-σ
Contains 0.93 g of DBP in which pivaloyl 2-ri-a-rho 5-[γ-(2,4-sheet t-7milphenoxy)butanamide]7cetanilide (hereinafter referred to as yellow coupler (y-i)) is dissolved. A low-speed blue-sensitive silver halide emulsion layer.

WJlo...1.2g of highly sensitive monodisperse blue-sensitive silver iodobromide emulsion (^gI; 7-tz, %), Z, Og, 7) 4f
Lachi, line, yu 0,46. A highly sensitive blue-sensitive silver halide emulsion layer containing a DBP of 0.23° in which a yellow coupler (Y-1) of ' is dissolved.

N11: Second 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 μm each.
130μm, 27μm, 25μ ring, 22μ gloss, 20μ+
There were eight types: a, 18 μm, and 15 μm III. These were designated as Sample Nos. 1 to 8. However, the film thickness and black colloidal silver content of the antihalation layer and the film thicknesses of the gelatin intermediate layer and the yellow filter layer were not changed at all.

A further sample was prepared by coating the same emulsion on a transparent polyethylene terephthalate film base without the bottom colloidal silver halide anti-layer. The samples are numbered in descending order of film thickness.

It was set as 9 to 16. The average coated silver amount for all samples is 50-58B
/d+a' i11! I arranged it.

Each sample was treated using a treatment solution prepared according to the following treatment steps and the following recipe.

Processing process Temperature Time color development 41℃ 3 minutes pre-bleach bath 38℃ 30 seconds bleach bath
Wash at 38℃ for 10 seconds and 5 minutes.
Fix at 33℃ for 1 minute 33
℃ Wash with water for 3 minutes 33℃
Stable for 2 minutes at 33℃
30 seconds [Color developer] Potassium carbonate 30g Sodium sulfite 2.0g Hydroxylamine sulfate 2.0g 1-hydroxyethylidene-1,1-diphosphonic acid 1.0g Potassium bromide 1.2g Magnesium chloride 0.6g Sodium hydroxide
364 g N-ethyl-N-β-hydroxyethyl-3-methyl-4-7 minoaniline sulfate 4.6 g of water was added to make IQ, and the mixture was hydroxylated. The pH was adjusted to 10.1 with IJ.

[Pre-bleaching bath]

Sodium sulfite to, og Sodium acetate 8.0g Glacial acetic acid
23-Water was added to make IQ, and the pH was adjusted to 3.8 with sodium hydroxide or acetic acid.

[i vote white liquor]

Sodium persulfate 60g Sodium chloride 20g Sodium dihydrogen phosphate (anhydrous) 9.0g Phosphoric acid (85%)
2,5,(11-hydroxyethylidene-1,1-nophosphonic acid (SO%>t, og
Gelatin 0.5g Add water to make IQ, pH 2 with sodium hydroxide or phosphoric acid
, adjusted to 3.

[Fixer]

Sodium thiosulfate 150g Sodium sulfite 12g Add water
(Let it be l.

[Stabilizing liquid]

Formalin (37% molten) IO! Add water to obtain IQ.

As shown in Table 1, 1.5 g of the exemplified compound of the present invention was added per batch to the pre-bleaching bath, and the bleaching time was varied in two steps of 1 minute and 3 minutes, and the residual silver amount Table 1 Table 1 As is clear from the results, when the multilayered silver lodenide color photographic light-sensitive material has a black colloidal silver antihalation layer, the bleaching property is extremely poor when the thickness of the photographic constituent layer (gelatin film thickness) is large; It can be seen that the film thickness of the photographic constituent layer (gelatin film thickness) increases rapidly as the film thickness of the photographic constituent layer (gelatin film thickness) decreases, and the change is greatest at around 25 μm. It can be seen that, although it is not effective when the thickness is large, it is clearly effective when the photographic constituent layer is thinned (gelatin thickness).

On the other hand, in a silver halide color photographic light-sensitive material that does not have a black colloidal silver antihalation layer, the thickness of the photographic constituent layer (
Although there is almost no effect on gelatin film thickness (gelatin film thickness) and the time taken to complete bleaching and fixing is extremely short, products without such an antihalation layer cannot be used for high-sensitivity silver halide color photography. It is difficult to put this into practical use as a high-sensitivity photographic material.

In addition, the accelerator of the present invention added to bleaching @ commonly used ■-28.
II-70, 11-85, ff-100, IT-10
1, TI-145°H-148, II 152.
II 15 [i, I 157. IT! 5
8. In-2, III-4, m5, m
6, I[l 33. III 34. V-7
Exactly the same treatment was carried out in place of 0°V-75, VI-1 and ■-11, but with the film thickness of the present invention, more preferable bleaching properties were exhibited in all cases.

Example 2 Sample Nos. 1 to 8 of Example 1 were prepared in the same building except that the coupler of the present invention (exemplified compound M-1) was added in place of the M6 and N7 magenta couplers Ma and M-b of each of Samples No. 1 to 8. Samples were prepared and numbered No. 17-24.

Examples of samples No. 1 to 8 and No. 17 to 24]
After processing in the same manner as above, the samples were stored for one month under forced deterioration conditions of 90°C and 90% relative humidity, and the maximum density of magenta pigment was measured using a Sakura photoelectric densitometer PDA-65 (Konishi Roku Photo Industry Co., Ltd. 1) and stored. The fading rate was determined relative to the previous density. However, a bleaching solution with the following composition was used as a comparative bleaching solution.

[Comparative bleaching solution]

Ethylenenoaminetetraacetic acid ammonium dihydrate 90g Ammonium bromide 150g Ethylenenoaminetetraacetic acid 20ga Acid (90%)
20J of water was added to bring the total volume to 1q, and the pH was adjusted to 6.0 with aqueous ammonia.

The results are shown in Table 2.

Table 2 As shown in Table 2, the density decrease of magenta dye due to storage (
Discoloration (fading) does not occur at all in the comparative bleaching solution, but in the bleaching solution of the present invention, it increases significantly as the photographic constituent layers become thinner. However, it can be seen that by using the magenta coupler of the present invention, the decrease in the concentration of magenta dye can be suppressed at the film thickness of the present invention.

Example 3 Magenta coupler M-1 (coupler of the present invention) of Example 2 was replaced with M-3, M-35, M-36, M-37 and M-3.
Example 2 was repeated in place of Example 8, but in each case, fading of the magenta dye after storage was significantly suppressed and good results were obtained.

Example 4 Contains the magenta coupler M-1 of the present invention prepared in Example 2, and has a film thickness of 30/7m and 20μ! Using multilayer color light-sensitive material samples No. 0 (No. 18 and No. 22), the maximum density of magenta dye obtained by processing according to the same processing steps as in Example 2 before and after storage was measured. However, when bleaching
0 was varied as shown in Table 3. The results are shown in Table 3.

Table 3 As is clear from Table 3, the fading rate of magenta dye due to storage is as high as the bleaching treatment IC when the film thickness is 30 μm! Although there is no change due to the difference between the two, when the film g becomes as thin as 20 μtI+, the rate of discoloration increases as the bleaching treatment time increases. However, if the bleaching treatment time was 3 minutes or less, good results were obtained in which the rate of discoloration was reduced.

Claims (1)

[Scope of Claims] (1) A photographic constituent layer including an antihalation layer containing black colloidal silver and a blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer is provided on a support, and the halogen Among the silver emulsion layers, the layer closest to the antihalation layer contains silver halide grains containing silver iodide, the total thickness of the photographic constituent layers is 25 μm or less, and is represented by the following general formula [C I ]: A silver halide color photographic material containing the compound shown above is developed after imagewise exposure, and processed with a processing solution having silver bleaching ability and containing peroxide as a bleaching agent. Method of processing photographic materials. General formula [C I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, Ar represents an optionally substituted phenyl group, and Y
represents a group that leaves when a dye is formed by coupling with an oxidized product of an aromatic primary amine color developing agent. X
represents a halogen atom, an alkoxy group, or an alkyl group, R represents a group that can be substituted on a benzene ring, and n represents an integer of 1 or 2. When n is 2, R may be the same or different. ](2
) Claim 1, characterized in that the treatment bath having bleaching ability and/or the bath preceding the bath contains at least one compound represented by the following general formulas [I] to [VI]. A method for processing silver halide color photographic materials. 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. ▼ [In the above general formula, Q is the N atom Heterocycle containing one or more (
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.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲Mathematical formulas, chemical formulas, tables, etc. ),
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 =NR''
R'' represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue (
(including those with at least one 5- to 6-membered unsaturated ring condensed thereto) or an amino group, Y represents >N- or >CH-, Z represents a hydrogen atom, an alkali metal atom,
Ammonium group, amino group, nitrogen-containing heterocyclic residue or ▲
There are mathematical formulas, chemical formulas, tables, etc. Represents ▼, Z' represents Z or an alkyl group, R_1 is a hydrogen atom, and has 1 carbon number
~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 a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms,
Represents an aryl group or an alkenyl group. However, R_4 and R_5 may represent -B-SZ, and R and R',
R_2 and R_3, R_4 and R_5 are each cyclized with each other to form heterocyclic residues (at least one 5- to 6-membered unsaturated ring
(including those condensed thereto) may also be formed. R_6 and R_7 each have ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ , where R_9 is an alkyl group or -(CH_2)n_8
Represents SO_3^■ (However, R_6 is -(CH_2)n_
When 6SO_3^■, l represents 0 or 1. )G＾■
are anions, m_1 to m_4 and n_1 to n_
6 represents an integer from 1 to 6, and m_5 represents an integer from 0 to 6. R_6 represents a hydrogen atom, an alkali metal atom, ▲numerical formula, chemical formula, 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 single primes, 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. Note that the compound represented by the above general formula includes enolized compounds and salts thereof. [3] The method for processing a silver halide color photographic light-sensitive material according to claim 2, wherein the compounds represented by the general formulas [I] to [VI] are the following compounds. (a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (b) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (c) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (d) ▲ Numerical formulas, chemical formulas, tables, etc. Yes▼(e)HS-
CH_2CH_2-COOH (f) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (g) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (h) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (i) ▲ Mathematical formulas, chemical formulas, There are tables, etc. ▼ (j) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (k) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (l) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (m) ▲ Mathematical formulas, There are chemical formulas, tables, etc.▼ (n)▲There are mathematical formulas, chemical formulas, tables, etc.▼ (o)▲There are mathematical formulas, chemical formulas, tables, etc.▼ (p)▲There are mathematical formulas, chemical formulas, tables, etc.▼ (q)▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (r)▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (s)▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (t)▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (u ) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ or (v) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (4) The silver halide color photographic light-sensitive material is characterized in that the thickness of the photographic constituent layer is 22 μm or less. A method for processing a silver halide color photographic material according to claim 1, 2 or 3. (5) The method for processing a silver halide color photographic material according to claim 4, wherein the thickness of the photographic constituent layer of the silver halide color photographic material is 20 μm or less. (6) The method for processing a silver halide color photographic material according to claim 5, wherein the thickness of the photographic constituent layer of the silver halide color photographic material is 18 μm or less. (7) Each of the silver halide emulsion layers contains 3 mol % to 25 mol %
7. A method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 to 6, characterized in that it contains silver halide grains containing mol % of silver iodide. (8) The silver halide color photographic light-sensitive material according to any one of claims 1 to 7, characterized in that the bleach-fixing process is carried out after the color development and after the fixing process. processing method.