JPS62115158A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To carry out rapid bleach fixing by imagewise exposing and developing a silver halide color photographic sensitive material contg. a specified magenta coupler and by processing the material with a bleach fixing soln. contg. a ferric complex salt of an org. acid. CONSTITUTION:A silver halide color photographic sensitive material having <=50mg/dm<2> in total of silver coated and contg. a magenta coupler represented by the formula in the green-sensitive silver halide emulsion layer is imagewise exposed, developed and processed with a bleach fixing soln. contg. at least one kind of ferric complex salt of an org. acid. At least one of the silver halide emulsion layers of the sensitive material contains silver halide particles contg. >=0.5mol% silver iodide, the total thickness of the photographic constituent layers is <=25mum and the binder in the photographic emulsion layers has <=25sec rate T1/2 of swelling in the form of a film. By this method, the processing of the color photographic sensitive material having high sensitivity can rapidly be carried out and silver is completely removed by the processing.

Description

[Detailed description of the invention] [Industrial application power! IF]

The present invention relates to a method for processing V1 silver halide color qJ photosensitive material. More specifically, the present invention relates to a method for processing silver halide color photographic sensitizers having rapid silver bleach-fixing ability.

[Prior art]

In general, in order to obtain a color image by processing an imagewise-exposed true light-sensitive material, after the color development step, a processing solution is applied to bleach the metallic silver produced. Bleaching solution and bleach-fixing solution are known as processing solutions with bleaching ability.When a bleaching solution is used, it is usually used next to bleaching culm. Ha1
A step of fixing silver 1genide with a fixing agent is added, but sometimes a bleach-fixing process is performed in which bleaching and fixing are performed in one step. Inorganic oxidizing agents such as blush salts and monoacid salts are widely used as oxidizing agents for bleaching silver halide color photographic materials (J1 images). However, some serious drawbacks have been pointed out to processing solutions with bleaching ability containing these inorganic oxidizing agents. However, it decomposes when exposed to light and may generate cyanide ions, hexavalent glue [1], and ions that are harmful to the human body, and has undesirable properties such as "Pollution Prevention". In addition, because these oxidizing agents have extremely strong oxidizing power, silver halide solubilizers such as thiosulfates (
It is difficult to coexist the fixing agent) in the same processing solution.
It is almost impossible to use these oxidizing agents in bleach-fix solutions, making it difficult to achieve the goal of speeding up and simplifying processing (7). Furthermore, processing solutions containing these inorganic oxidizing agents 'M without discarding waste liquid after treatment
It has the disadvantage that it is difficult to use raw silk. On the other hand, there are fewer problems with pollution, faster oil processing, and
In order to meet the demands of simplification and reuse of waste liquid, treatment liquids using metal complexes of fJ organic acids, such as aminopolycarboxylic acid metal complexes, as oxidizing agents have come to be used. However, processing solutions using metal complex salts of organic acids have weak oxidizing power, so the image silver formed during the development process (
It has the disadvantage that the bleaching speed (oxidation speed) of silver (metallic silver) is slow. For example, Edge 1 nondiaminetetraacetic acid iron 00, which is considered to have a strong bleaching edge among aminopolycarboxylic acid metal complex salts,
) Complex salt (JAlthough it has been put into practical use as a bleaching solution and a bleach-fixing solution in some cases, it is also used in high-sensitivity silver halide color photographic photosensitive materials containing silver bromide and silver iodobromide emulsions, especially halogenated Color negative films and color reversal films that contain silver iodide as silver do not have enough bleaching blades.
Even after long-term processing, traces of image silver remain, resulting in poor desilvering. This tendency is particularly noticeable in bleach-fix solutions in which an oxidizing agent, thiosulfate, and sulfite coexist because the redox potential is lowered. In particular, it was found that the desilvering property of the high-sensitivity silver iodide gold-If-Cl silver-genide color photographic photosensitive + A-ray containing black colloidal silver for halation and rain prevention was remarkable at 47p. Furthermore, the above-mentioned silver iodide-containing high-sensitivity emulsion is made into fine grains, and is highly effective against silver. There is a core-shell emulsion that uses the preceding silver halide emulsion as a crystal nucleus, and then successive precipitates are layered on top of it, and the composition or environment of each precipitate is determined.
Is it graphically controlled and made? ) are dispersed core-shell emulsions.Among these, the core-shell type high-speed emulsions containing silver iodide in the core and/or shell have extremely favorable photographic performance characteristics, but are not as good as conventional bleach-fixing methods. In the bath, silver
): In the case of 1, it was found that the bleach-fixing quality of developed silver and silver halide was extremely poor. That is, developed silver of a photographic silver halide emulsion containing 0.5 mol % or more of silver iodide, especially an 21 acyel emulsion, containing 0.5 mol % or more of silver iodide in the core and shell. - developed silver of silver halide grains containing silver iodide (J, sensitivity, graininess,
Even if the covering power and the like are excellent, in color photographic photosensitive monthly printing, in which the developed silver must be bleached, the bleaching properties are significantly poorer because the form of the developed silver is different from that of conventional methods. In particular, as an emulsion, JP-A No. 58-1+3930-, and 5L-
No. 113934, No. 58-127921 and No. 58-
There is a method using tabular silver halide grains as described in, for example, No. 108532;
It is said that even if the number of photons captured by the silver halide grains increases, the amount of silver used will not increase and the image quality will not deteriorate due to the silver halide grains. However, even these tabular silver halide grains have the disadvantage that developed silver formed by development with a p-phenyleneamine color developing agent has poor silver bleaching properties. As a result of research, the present inventors have found that a silver halide color photographic light-sensitive material having a silver iodide-containing silver halide emulsion layer as described above and an antihalation layer made of black colloidal silver can be produced using an organic acid ferric acid. In order to perform rapid processing with a bleach-fix solution containing a complex salt, the total thickness of all photographic layers excluding the support of photosensitive H14 and the membrane swelling rate T% of the binder in the photographic emulsion layer need only be kept below a certain value. I found out. That is, the present inventor has developed a high-sensitivity fine grain having a) silver halide emulsion layer of at least 3 WJ containing black colloidal silver as a resin prevention layer and an emulsion containing at least 0.5 mol % of silver iodide. % silver halide color photographic light-sensitive materials, and as a result of extensive research, we found that the total coating silver amount and emulsion layer thickness of silver halide color photographic light-sensitive materials are below a certain value. It has been found that if the film swelling rate T of the binder is 25 seconds or less, even a bleach-fix solution containing an organic acid ferric complex salt can be sufficiently desilvered. Furthermore, when treated with a bleach-fix solution containing a combination of specific compounds according to the present invention,
It has been found that the darkness after completion of bleach-fixing of silver iodide-containing silver iodide/silver lodenide color photographic light-sensitive materials to be processed is further shortened. In particular, it has been found that when the photographic layer consisting of a silver halide emulsion in a photographic material is thinned to a certain value or less according to the present invention, bleach-fixing properties are clearly improved and desilvering defects are improved. Furthermore, surprisingly, the present inventor found that the larger the molecular weight of the organic acid in the organic acid ferric complex salt, the greater the bleaching promoting effect due to the decrease in the binder film swelling rate T of the photographic constituent layer (gelatin film). , discovered the fact that the bleaching time was significantly reduced. On the other hand, it was also discovered that the smaller the molecular weight of the organic acid in the ferric organic acid salt, the greater the bleaching accelerating effect due to the reduction in the thickness of the photographic constituent layer (gelatin film), and the bleach-fixing time was similarly shortened. did. That is, in general, the larger the molecular weight of the organic acid of the ferric acid salt, the greater the oxidizing power of silver, but the harder the effect of hardening the photographic structure, the more difficult the diffusion and penetration of the bleach-fixing components. This will cause bleach-fixing inhibition, which will be large compared to the thickness of the photographic constituent layers, but this inhibition will not occur if the gelatin film has a property of extremely rapid swelling. On the other hand, organic acid ferric complex salts with small molecular weights have a slightly weaker silver oxidizing power, but they also have less bleach-fixing inhibition, so that the photographic constituent layers may become thinner than the certain value according to the present invention, or gelatin may be thinned as described above. It has been found that a substantially sufficient bleaching blade can be obtained if the membrane swelling degree is large. Furthermore, as the film thickness of the photographic constituent layer of the silver iodide-containing silver halide color photographic material increases, the boundary between the black colloidal silver-containing halide layer and the silver iodide-containing silver lodenide emulsion layer increases. Due to the occurrence of desilvering defects in the
l! It has been found that the inhibition of bleach-fixing caused by this can be reduced by thinning the photographic constituent layers to a certain value or less according to the present invention and by increasing the swelling rate of the gelatin film to a certain value or more. 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 organic acid complex salt of any molecular weight is used. However, in the course of subsequent research, it was discovered that in this rapid bleach-fixing process, traces of silver inevitably remain in the photographic constituent layers.In other words, the bleach-fixing end time is generally defined as the point at which the emulsion film becomes transparent. Although this is often the case, residual silver at this time is hardly detected by spectral absorption at 1000 nm, and of course, even when visually observed, the emulsion film is completely transparent and no silver can be observed. However, traces of silver are always detected with fluorescent X-rays. This is also confirmed from electron micrographs. The reason why it is generally preferable to continue the treatment for at least twice the time the emulsion film becomes transparent is considered to be to completely desilver this trace of silver. If even traces of silver remain in the photographic constituent layers, the basic gradation of the emulsion will often be subtly intensified in order to absorb all the blue, green, and red light during printing. do. In addition, during long-term storage of images, they undergo gradual changes (for example, silver sulfide), causing yellow staining, which is a serious problem for color photosensitive materials that require stable color image storage for over a century. Therefore, there is a need for a bleach-fixing process that does not impair rapid processability and does not leave even traces of silver.

[Purpose of the invention]

OBJECTIVES OF THE INVENTION (J) Firstly, to provide an excellent bleach-fix processing method for high-sensitivity fine-grain type high-sensitivity silver iodide-containing silver halide color photographic sensitization that can achieve both resource conservation and ultra-high sensitivity. A second object of the present invention is to provide a processing method that enables rapid processing of high-sensitivity color photographic publications and uses a dilute bleaching solution from which silver is completely removed.

[Structure of the Invention] As a result of intensive research, the present inventor has found that blue sensitivity, green sensitivity and
A photographic constituent layer containing a red-sensitive silver saponide emulsion layer is
However, the total coating silver amount is 50 mg/dm2 or less and the halogen
At least one of the silver emulsion layers contains 0.5 mol% or more of iodine.
Contains silver halide grains containing silver oxide and is green-sensitive
Maze whose silver halide emulsion layer is represented by the following general formula [C1]
Contains an intercoupler, and the total thickness of the photographic constituent layers is
25 μm or less, and a binder film of the photographic emulsion layer
When the swelling speed TB is 25 seconds or less, Ruha [I Silver Genide Color]
- After imagewise exposure and development of photographic material, organic acid
treated with a bleach-fix solution containing at least one ferrous salt;
It is believed that the object of the present invention can be achieved by understanding
I found it. In the formula, Z is a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle
and the ring formed by Z may have a substituent.
stomach. X is formed by a reaction with a hydrogen atom or an oxidized product of a color developing agent.
represents a substituent that can be removed. Moreover, +1 represents a hydrogen atom or a substituent. Preferably, the organic acid ferric complex salt is
Examples include those selected from (a) to (q) described in Section 13.
Let's go. Here, the photographic constituent layer refers to the blue-sensitive, green-sensitive,
At least three silver halide emulsion layers coated with red sensitivity
All the parts on the same side as the surface of the support that are involved in image formation.
This refers to the hydrophilic colloid layer of black colloidal silver halide.
It is particularly effective when there is an anti-yellow layer;
[In addition to the silver 1-genide emulsion layer, for example, a subbing layer, an intermediate layer (
intermediate layer, filter layer, ultraviolet absorption layer, etc.), protective layer
etc. More preferably, the bleach-fix solution and/or pre-fix solution contains
A bleach accelerator selected from the following general formulas [l] to [■1]
Examples include embodiments containing the above. General formula (1:) General formula (1) General formula (It
l ) 1 (Saki ＼ General formula (IV) General formula [■] R喀2 1
i1ko R1! In the general formula (g), Q is a heterocycle containing one or more N atoms (5
~At least one 6-membered unsaturated ring is fused to it
Δ represents the atomic group necessary to form the
The unsaturated ring of [;Ul is at least 1-) fused to 1
．． +3 represents carbon number 1 to (1 carbon number)
11. , M is the divalent metal layer 1
' is one, 1<1. , X and X)) = S, -o
Also iJ, x + r ″ to 12, li′iJ hydrogen
bii r-1 carbon atoms 1~(r i'・1 alkyl
Le' I (, citaloargyl group, aryl'1 waist hair!
j:: "1 residue J+'; (5-6H unsaturated ring is at least
61 Tsugoi 1 (, - fused Otsu atom, ammonium
ノ, J, l;, )・Mino J, I; , nitrogen-containing hete [1゛
1 ton. or alkyl'-1 (It' is hydrogen 1 r.,
Algel having 1 to 6 carbon atoms, (7, taloargyl
Jil;, aryl group, hete [! Ring residue jll; (5~G
At least one unsaturated ring of Ll is fused to it (two rings).
2. +ton'
3. lton', R5, and I and R each represent hydrogen l11 (child
, an argyl group having a carbon number of I to G, hydroquine) I(, car
Bokino J, 1:, Amino'+1;, Carbon y; 111-3
% to acyl, aryl group, Jte or alnorr=le
Let the groups t,, (:,, t i, rt' and R'
fJ, -R3S Z is represented by b''-ku, and R and R'
, R2 and R3, R' and R'respectively 17: Ini
Cyclization to form a heterocyclic residue (5 to [ijl with less unsaturated ring)
At least 1 m) Condensed with this, including the t of O)
may be completed. Iζ', 11' represent each person, +t jl is an argyl group or -(CLl 2)
n8S O3- (lj L R11?-(CI
I2) When n8s o s-, g(JO or (express Jl)
4-. ) G- is an anion, ml to nl, and nl
Ishi 116 is an integer from 1 to 6, and m5 is an integer from 0 to 6.
State the number. Fya8 is a hydrogen atom, alkali d-oHowever, Q
' (synonymous with Q in J111j. D is under the η beat bond
-1111 Alkylene group with 1 to 8 prime numbers or vinylene
represents a group, and q is an integer from 1 to 10 as shown in Table 4. Multiple D's
Same but different -
ring ('', which may further be fused with an unsaturated ring of 5 to [1[1)
stomach. X'+J, -000M', -0Tr, -8O,M
', -CON II,, -S O, N I-I 2,
-N II 2, -9 Hl-CN, Co, Itl
o, -so, rtlo, -〇 R18, -N R"'R
17, -S RI Q, -8o,, R'', -N I-I
COR", -NIISO, R'6, -0COR16 or
represents -9o, Tl10, M' represents 11"R"R2 or a hydrogen atom, and m and niJ each represent 1 to 1o.
Represents an integer. R eye, R eye, Iji4 (115, R'7 and
r? , l14 is a hydrogen atom, lower argyl
or (Jl1" ■ -(C)-Xno1" R1+ , RIB represents a lower alkyl group. R19 is -
-N R20R2o represents R22 or -3R22, r
t20 and R'' represent a hydrogen atom or a lower alkyl group;
, R22 is an element necessary to connect with R'8 to form a ring.
Represents a child group. R" or R21 and R" are connected to form a ring
You may. M' represents a hydrogen atom or a cation. In addition
, the compounds represented by the general formulas (1) to (V) are eno
This includes silica and its salts. According to a preferred embodiment of the invention, silver halide color
-The film thickness of the photographic constituent layer of the photographic light-sensitive material is 2271 m or less
, particularly preferably 20 μm or less, and the binder film
Swelling speed T is 20 seconds or less, particularly preferably 15 seconds or less
, most preferably 10 seconds or less, 1ii1i bleaching
The fixing accelerator and the organic acid that forms the organic acid ferric complex salt are
Examples include the following compounds. Through these, the purpose of the present invention was effectively achieved.
I found out. Details τ(i's 1-!: (no change in content) S
S (4) I O-CH, -CI-1-CI
(2S Hl 0!-■ (5) H8-C112
CI-12-COOH details layer
) Engraving of the specification (no change in content) H Zhan H (2B) H8CH2CH2NHCH,CH,0
H(29) H8CH,CH2NC)I2CH2
0H2Hs or (a) Diedilent)'minol11oxic acid (b) To cyclo
Gysandiaminotetraacetic acid (C) Triedyleneatosimine hexaacetic acid (d) Glycol ether diamine tetrahedral acid (e) 1
．． 2--Diaminopropylene ``!pantetraacetic acid (f) 1.3-a
Minob I-1 Pan-2-ol Tetraacetic acid (g) Ethylene diamine di 0-human [1 Gysif J-nil
Acetic acid (h) Ethylenediaminetetraacetic acid (i) Nitrilotriacetic acid (j) Iminoni6'1 acid (k) Medyliminodiacetic acid (1) Hydrogynoethyliminodiacetic acid (m) Ethylenediaminetetrabu'l pionic acid (n) Ji
Hitroni) - Noko, Jirgurin (0) Nitrilotripe
dilpionic acid (p) ethylene di)'min-'', 6'1 acid (q) ethyl 1
Diamine Nobu 1 Novionic Acid More Most Effective Embodiment
After color development processing, but before bleach-fixing processing.
By using a processing method that performs fixing treatment as a pretreatment step,
It has been found that the objects of the present invention described above can be achieved most effectively.
I put it out. From now on, this fixing process will be referred to as pre-fixing process or pre-fixing process.
The processing liquid used for the pre-fixing process is called the pre-fixing process liquid.
Pre-fixing solution or pre-fixing cloudy product → Processing bath or pre-fixing bath
It is called. The present invention will be explained in more detail below. First, the map represented by the general formula (C1) used in the present invention is
The Zenta coupler will be explained. General formula (CI) In general formula [C1], Z forms a nitrogen-containing heterocycle
represents a group of nonmetallic atoms necessary for Z, and the ring formed by Z
may have replacement threads. X is a hydrogen atom or a color developer
Represents a substituent that can be separated by reaction with the oxidized form of the image agent
. Moreover, R represents a hydrogen atom or a substituent. As a substituent in Table d of R (Jl, for example, a halogen atom)
, alkyl group, cyclo)′lkyl], (, alkenyl group
, cycloalkenyl, (arginyl group, aryl group,
Heterocycle 3,1:, acyl group, sulfonyl group, sulfinyl group
Nyl group, bosubonyl J1 (, carbamoyl group, sulfa
Moyl group, cyano Jl (, Spi "1 compound remaining" k, Arihashi
Hydrocarbon compound residue, alkoxy J1 (, aryl
So group, heterocycle 1 ogyne J, l6, norogishi group, acyl
amino, 12, carbamoyl oxine group, amino group, ano
Ruamino group, sulpon)'mido'I (, imido group, urethane group)
Ido group, sulfamoylamino group, alkoxycarbonyl
lylamino group, aryloquine group, luponylamino group,
ni1ginowonorbonil) old, aryl ogishi carbonil
112, alkylthio 3. (, aryldio group, to
Examples include te
In particular, the chlorine piece 1'- is preferably expressed at 5°R.
11. and 1. Then, carbon number 1-32
Alkenyl groups with 2 to 32 carbon atoms, 1 alkyl group, cycloa
The lekenyl group has 3 to 12 carbon atoms, especially 5 to 7 carbon atoms.
is preferable, and an alkyl group, an alkenyl group, an alkynyl group
may be linear or branched. In addition, these alkyl groups, alkenyl groups, arginyl groups
, cycloalkyl group, and cycloalkenyl group are substituents [e.g.
For example, aryl, cyano, halogen atom, heterocycle, cyclo
loalkyl, cycloalkenyl, spiro compound residues,
In addition to bridged hydrocarbon compound residues, anlu, carboquino, and carbo
Bamoyl, alkoxycarbonyl, aryloquinocal
Those substituted via a carbonyl group such as ponyl, and
substitutes through a heteroatom (specifically, human [
1 giso, alkoxy, acyloxy, heterocyclic ogino,
Oxygen such as sorogine, acyloxy, carbamoyloxy, etc.
Substitution via atoms, nitro, amino (dialky)
), sulfamoylamino, alkoxy
cyclocarbonylamino, aryloxycarbonylamino
, acylamino, sulfonamide, imide, ureido, etc.
substituted through the nitrogen atom, alkylthio, ali
ruthio, heterocyclic thio, sulbonyl, sulfinyl,
Those substituted via the sulfur atom such as sulfamoyl,
(substituted through a phosphorus atom such as postbonyl)
1"1, is good. Specifically, for example, methyl J, l;, ethyl group, isopropyl group.
Lopyl group, t-butyl group, (, bentadenol group, hepta
Denru'ru, 1 hegysolnonyl group, 1,1'-dipene
Dirunonil J, waist 2-rishi! 1-rubutyl group, trif
fluoromethyl group, l-gisotridenol group, 1-methyl
Toginseob L! Pirno I (, methanesulfonylethyl
3152, /I-di L amylfenogine methyl"j
(,)'Nilin' 111-Fjnylisop [1-biru group,
3-m-butanesulponaminophenoquinepropyl group,
3-4′-[α-( 4”(p-hydroxybenze
nsulfonyl)fuJnoxy]dodecanoylamino)fe
Nilzo[J pill'1(,3-(4'-Cα(2)
), i,))--di-t-amylphenoxy)butanea
mido]phenyl)-propyl group, 4-[α-(0-k)
Rolfenoquine) Tetradecanamidophenoxy] Pro
Pyr group, allyl group, cyclopentyl group, cyclohegisol
Examples include groups. The aryl group represented by R is preferably a phenyl group.
, substituents (e.g., alkyl groups, alkogine groups, acyl groups)
amino group, etc.). Specifically (J1 phenyl group, 4-t-butylphenyl group
, 2.4-di-t-amyl phenyl group, 4-tetradeca
amidophenyl group, hexadesiloxophenyl group, 4
/-[α-(4”-t-butylphenoquine]tetradeca
[Amido] phenyl group, etc. The heterocyclic group represented by R is preferably 5- to 7-membered.
may be substituted, or may be fused. Specifically, 2-furyl group, 2-chenyl group, 2-pyrimi group
Examples include a diinyl group and a 2-benzothiazolyl group. Examples of the acyl group represented by R include an acetyl group and a fluoride group.
phenylaceder group, dodecanoyl group, α-2,4-di
Argyl carbo such as L-amylphenoxybutanoyl group
Nyl group, benzoyl group, 3-pentadenluoquinobenzo
Aryl carbonyl group, p-chlorobenzoyl group, etc.
methyl sulfonyl represented by R.
Nyl group, dodecylsulfonyl Jl (such as argylsul)
Bonyrunsulfonyl is mentioned. Sulphini Jl/J. I; Close (J
, ethylsulfinyl J, -icutylsulfiel)
, (, 3-phenogisibutylsulfinyl J1 (such as
argylsulfinyl pentadesulfenylsulfinyl 7, (Aryls such as
Rusulfinil J, l;, etc.)% will be stolen. Phosbonyl JI (butyl ocdji) represented by R
Ruphosphonyl j. (like)'lugilposphonyl]11
>, ocdyloxyphosphonyl J1 (,
gysyposponyl group, fluoroxyphosphonyl group (as in
aryloxyphosphonyl J,l;
Examples include arylphosphonyl group such as honyl group. Carbamoyl L', 4j, represented by R: , argyl j
Co(, aryl group (preferably tubonyl group) etc. is substituted
For example, N-methylcarbamoyl group, N,
N dibutylcarbamoyl group, N-(2-pentadecy
carbamoyl group, N-J6 thiru-N
-dodecylcarbamoyl group, N-(3-(2.4-n-
(amylphenoquino)propyl)carbamoyl group, etc.
Can be mentioned. The sulfamoyl group represented by R is an alkyl group, an aryl group
It may be substituted with a group (preferably a phenyl group), etc.
For example, N-propylsulfamoyl group, N. N-n-ech
Rusulfamoyl group, N-(2-pentadecyloxye
thyl) sulfamoyl group, N-ethyl-N-dodecyl group
Rubamoyl group, N-phenylsulfamoyl group, etc.
It will be done. ■ Examples of spiro compound residues represented by E include spiro compound residues.
Examples include [3.3]hebutan-1-yl. The bridged carbonized compound residue represented by 11 is, for example, pinot.
chlorij2.2.1] hebutan-■-yl, trinochloride
) 3.3.1.1”'] decan-1-yl, 7,7-n
Methyl-pisic cr l' 2, 2, l
] List butane-1-yl5. Al represented by R: 1xy group (J1 and the above alkyl group
``Replacement to ``1 (and 1, you may replace the 〇 listed in
For example, Metogishi J11, ``1-boxo group, 2-ethyl group''
toxoethoxo group, pentadenorochine group, 2-dodecy
xyethoxo group, pheothylogiethoxo group, etc.
You can ride it. , aryloxy J, I represented by R;
Oxy is preferred, and aryl Azusa is further converted to the aryl group.
even if substituted with any of the substituents or atoms listed in
Often, for example, phenoxy group, pt-butylphenol:1
’ group, m-pentadecyl group, J group, etc.
．． . Hair III 1′; represented by R, “1” as a chino group
is preferably a 5 to 7 heterocyclic ring.
Tero ring (J further contains substituents, b, 4: <
, for example, 3. 4, 5, 6-sutrachtnobishe-2-ogishi
'1(,1-)J Nyltetrazole 5 Ogiso group listed
can be lost. The siloxy group represented by R is further substituted with an alkyl group, etc.
For example, it may be
Ethylsiloxy group, dimethylbutylsiloxy 1, etc.
You can get ￥. As the acyl group represented by R, for example, argyl
Carbonyloxy group, arylcarbonyloxy group, etc.
¥, and may further have a substituent, specifically
Acedeloxy group, α-chloroacetyloxy group, pen
Examples include zoyluoquine group and the like. ■The carbamoyloxy group represented by E is an alkyl group,
Aryl groups etc. may be substituted, for example N-ethyl
Carbamoyloxy group, N,N-diethyl group, carbamoyl group
Examples include hydroxyl group, N-phenylcarbamoyloxy group, etc.
It will be done. The amino group represented by R is an alkyl group or an aryl group (preferably
or phenyl group), etc.
For example, ethylamino group, anilino group, m-chloroanilino
group, 3-pentadecyloxycarbonylanilino group, 2
-Chlor-5-hegisadecanamide anilino” 111 etc.
) Y is lost. Annruamino J11 represented by R; Tojito ('', Al;
)-rucarbonylamino J, l2, )' lylcarbonylamino
Rubonylamino group (preferably ('')) J Rule Rubonylamino
10 etc. are listed and replaced with history J,! , (1-1, Tera
3. Specifically, acetamide J, I:, α'', chill
Propanamide group, N-phenylacetamido group, 2.4-1-h mil-diacetamide group
do group, α-3 1-dityl 4-hydrogisof
Tanamito J,l; etc. are mentioned. As a sulboamide group represented by R ('', alkyl
The sulfonylumino group etc. are substituted in A history J,l;
, 1-i. Specifically, ``mer sulfo;
, Hensensulfo
amide group, p-toluenesulfonamidoxo-5-[-amylhensensulponamide JIH
etc. can be mentioned. Imide group represented by R ('', both open-chain and cyclic
Even if it is 31-<, substitution "1" may be 6 shi,
For example, succinimide group, 3-heptadecyl succinimide group,
Mido group, phthalimide group, glutarimide J11; etc.
Can be mentioned. The ureido group represented by R is an argyl group, an aryl group (
(preferably phenyl group) etc.
, for example, N-ethylureido group, N-medyl-N-dene
Luureido group, N-phenylureido group, N-1')-
3. Examples include 1-lylureido group. The sulfamoylamino group represented by R is argyl"i
l, substituted with an aryl group (preferably a phenyl group), etc.
For example, N,N-dibutylsulfamoyl
Amino group, N-methylsulfamoylamino group, N-ph
Examples include phenylsulfamoylamino J,l; and the like. As the alkoxycarbonylamino disorder represented by R,
It may further have a substituent, for example,
Bonylamino group, methoxyethoxysulfonylamino group
, octadecyl oquine carbonylamino group, etc.
Ru. R represents aryl-aS+-ampJ group
The group may be substituted with J-, (1"), for example,
)! Nokimp J Report Neil Amino” 11,, 4-Meg
・Rufu J Nogino Calponylamino J11, is listed 1, is
reactor,. Al represented by R:+=l゛nocarbonyljj:
iJ may further have a substituent, for example,
sulfonyl group, zojiruo; 1-7 carponyl group, dodenol
Okinriki Ruboniru'l (, Otatadecyl Okinuriki Ruboni
1 (pen)
Ziroquine force rubonyl J11', i, · are mentioned 3
, R represented by aryloxocarponylno 1f, (J
Further replacement];I;, for example, Fugo
Noggin carbonyl Jll; , IT ta[norfu r
Noginocarbonyl group, m-bentadenoleo S1-F
-1 Tsugitsubu J) Reform groups, etc. can be mentioned. R represents an argylthio group (J, further substituted 311;
Even if it has l-<, for example,
Desolthio group, octadenludio” 11,, fugonedil
Examples include thio group, 3-] J Tsuginob 1 nopylthio group.
. The arylthio group represented by R is preferably a phenylthio group.
Furthermore, it may have a substituent, for example, a phenylthio group,
p-methogysophenyldio group, 2-t-octylphenyl
ruthio group, 3-octadecylphenylthio group, 2-cal
Boggin phenylthio group, p-acetaminophenylthio
Examples include groups. As a heterocyclic dio group represented by Tj (Jl 5-7 membered
is preferably a heterocyclic dio group, which may further have a fused ring.
It may also have a substituent. For example, 2-pyridyl
Thio group, 2-penzothiazolyldi group, 2.4-Schiff J
Noquin-1,3,5-triazole-6-thio
Examples include groups. Table 4 of X - Separation I due to reaction with oxidized product of color developing agent
, As a substitution method, for example, a halogen atom (chlorine atom)
, bromine atom, fluorine atom, etc.), oxygen atom,
71; substituted via a sulfur atom or a nitrogen atom;
can be lost. As a substitute through a carbon atom (j1 carpogycyl
In addition to the group, for example, the general formula N --' N, - (R1' is the same as the above R, and Z' is the same as the above Z
Yes, R, / and 11. ′ is a hydrogen atom, an aryl group, an atom
a group represented by alkyl group or henaro ring j- (represents),
Examples include hydrogine methyl group and triphenylmethyl group.
Ru. Substituting via an oxygen atom 1 (for example, alkaline
Koxy group, aryloxy group, heterocyclic oxy group, acyl group
ruoxy group, sulfonyloxy group, alkylcarbonyl
Oxy group, aryloxycarbonyloxy 31ζ, a
Lukiluo; 1-zaryluogishi group, alkoxyoxalyl
Examples include O S1-on J, j; The alkoxy group (J may further be substituted with J+L, e.g.
For example, ethgyne group, 2-]Jnokinethogycy group, 2-
Anoetquine group, ``Neddyluoquine group, p=chlorobene
Examples include "Jirogin" 111. As the aryloxy group, C'' and phenoxy J^ are preferred.
and the aryl group may further have a substituent.
. Specifically, phenoxy group, 3-methylphenogyso group,
3-dodecylphenoxy group, 4-methanesulfonamide
Phenoxy group, 4-[α-(3'-pentadecylpheno
xy)butanamide] fenogysi group, hequindecyl group
Bamoylmethoxy4 group, 4-cyanophenoxy group, 4
-methanesulfonylphenoxy group, l-naphdyloxy
group, p-methquinphenoxy group, and the like. The heterocyclic oxy group is a 5- to 7-membered heterocyclic oxy group.
A cy group is preferable, and it may be a condensed ring or have a substituent.
You may do so. Specifically, 1-phenyltetrazoli
2-benzodeazolyloxy group, etc.
It will be done. Examples of the acyloxy group include acetoxy group, butane
Alkylcarbonyloxy groups such as trunoxy groups, thinner
alkenyl group such as moyloxy group,
Arylcarbonyl ogiso group such as penzoyl oxine group
can be mentioned. The sulfonyloxy group is, for example, butanesulfonyloxy group.
luogishi'l'i, methanesulponyl ogyne group is mentioned.
It will be done. As the alkylcarbonyloxy group, for example, ethoxy
Silylluponyluogine group, penzyloxycarbonyluogine group
Examples include N groups. The aryloxycarbonyl J11;
Examples include cycarbonylogino group. As the alkyloxalyloxy group, for example, medyl
An oxalyloxy group is mentioned. The alcogine ogizalyl ogine group includes ethoxy
Examples include the quizalyloquine group. J+1.substituted via a sulfur atom. For example, a
alkylthio group, )2lylthio group, peterocyclic thio group, alkylthio group,
Examples include alkyloxythiocarbonylthio group. As the alkylthio M, examples include dwarf, 2-dia
Tsuedirujio J, (2) "netylthio group,
Examples include O groups. As the arylthio group, phenylthio group, 4-methane
Sulfonamidophyldio group, 4-dodecylphenethi
Ruthio group, 4-nonafluoropencunamidophenethyl
Thio group, 4-carboxyphenylthio group, 2-ethoxy
-5-t-butylphenylthio group and the like. Examples of the heterocyclic thio group include 1-phenyl-1,
2,3,4-tetrazolyl-5-thio group, 2-benzode
Examples include azolylthio group. As the alkyloxythiocarbonylthio group, dode
Examples include syloxythiocarbonylthio group. Examples include those represented by the general formula -N.
group, heterocyclic group, sulfamoyl group, carbamoyl group
, acyl group, sulfonyl group, aryloxycarbonyl
group, represents an alkoxycarbonyl group, and R4'/ and R5'
may be combined to form a petero ring. However, R4' and R
Neither 5' is a hydrogen atom. The argyl group may be straight chain or branched, preferably carbon
It is a prime number of 1 to 22. Also, alkyl groups are substituted with
([ may also be used as a substituent, for example, aryl
group, alkoxy group, aryloxy 3i1 argyl
The O' Director (, Ari Luna No. 13., alkylamino group
, arylamino group, acylamino group, sulfonamide
No 1 (, imino J, 1 acyl group, argylsulfonyl Rubamoyl" II,, sulfamoyl J, I; , Al
Coggincarbonylkyluoginylponylamino J, It, aryloxy
Carbonylamino J1 (, Hill:'
Ruboxyl group, Noatsuno 11, and Hat'l gene atoms are listed.
can be lost. Specific examples of the argyl group include, for example, ethyl group.
, oxytyl"1(,2.r, dillheginol group, 2-chloro
Examples include ruethyl group. As an aryl group represented by R4' or It,,'
has a carbon number of 6 to 32, especially fluor JI (, naphthyl).
If the group is Iff, the aryl J11, (J1-substituted) 1
(The above-mentioned It4' or iJ:
J2, listed as a substituent to the argyl bridge represented by '
and alkyl groups. with the aryl group
Specific examples include phenyl group, 1-na
Examples include phthyl group and 4-methylsulfonylphenyl group.
Ru. ■(The heterocyclic group represented by 4/ or R,' is 5 to
6H is preferable, it may be a fused ring, and the substituent
It may have. Specific examples include 2-furyl group, 2-
Gynolyl group, 2-pyrimidyl group, 2-benzodeazolyl group
group, 2-pyridyl group, etc. R. ) or the sulfamoyl group represented by R5'
, N-argylsulfamoyl group, N,N-sialgyl
Sulfamoyl group, N-arylsulfamoyl group, N
, N-diarylsulfamoyl group, etc.
The alkyl group and aryl group of these are the above-mentioned argyl group and
It may have the substituents listed for the ryl group. vinegar
In the specific example of the rufamoyl group and 17, for example, N,N-die
Tylsulfamoyl group, N-methylsulfamoyl group,
N-dodecylsulfamoyl group, N-p-4lylsul
"Famoile", ζ) is fired. R4′ or IJ: It. ′ is represented by carbamoyl group and
is N-alkylcarbamoyl J, (, N, N
Sialkylcarhamoyl J, 1. ,N arylcarba
Moyl group, N,N-diarylcarbamoyl Jij:
etc., Argyl J11 of Koi et al., and Ally
The aryl group is 1] 11 Argyl J11) and the aryl group
It may have any of the substituents listed above. Carbamoyl
Specific examples of the group include N,N-J4delcarbamo.
yl group, N-methylcarbamoyl group, N-todenrucar
Bamoyl group, N-1)-cyanophenyl group
and Np-tolylcarbamoyl group. R4' or ii T'l , ,' is an acyl group;
('', for example, argyl carbonyl j + (, aryl carbonyl
carbonyl group, heterocyclic carbonyl group, and
Kyl group, the aryl group, the hete [J ring j; j; is a substituent
(may be f), specific acyl group
For example, Hegizafluoro τ゛lbutamyl group, 2
. 3 , 4 , 5 , 6 Pentafluoro l'J benzoi
Jilζ, acedel group, henzoylno 1 (, naphthoni)
ruJ+'i, 2-]lyl carbonyl group, and the like. The sulfonyl group represented by R4' or R,' is
lugylsulfonyl group, arylsulfonyl group, hete [J
Examples include ring sulfonyl groups, which may have substituents, and
For example, ethane sulfonyl group, benzene
sulfonyl group, octane sulfonyl group, naphthalene group
Examples include sulfonyl group, p-chlorobenzenesulfonyl group, etc.
It will be done. Aryloxycarbonyl represented by R4' or R, i'
The substituents for the aryl group include those listed above for the aryl group.
Specifically, it may have a phenoquinocarbonyl group.
etc. The alkoxycarbonyl group represented by R,' or R5' is
, may have the substituents listed for the alkyl group above.
, specific examples include methoxycarbonyl group and dodenyl group.
benzyloxycarbonyl group, benzyloxycarbonyl group, etc.
can be mentioned. ri,,' and R. ' is combined to form a heterocycle.
A 5- to 6-membered one is preferable, and it can be saturated or unsaturated.
It may or may not have aromaticity,
Also, 6 fused rings are sufficient. Examples of the heterocycle include N-phrase.
Kluimito group, N-succinimide group, 4-N-urazo
Lyle group, 1-N-hydantoynyl group, 3-N, 2.4
-diogysoogizazolidinyl group, 2-N-I-dio
xo, -3-(2H)-oxo-1,2-benzothiazo
Lyle group, 1-pyrrolyl group, l pi [! Linneal J+l
:, I-pyrazolyl group, l-pyrazolidinyl J+i'r
, I-piperidinyl group, I-pyrazole ring, (,1
imidazolyl group, 1-imidazolyl group, I indoly
group, 1-isoindolinyl J+';, 2-isoindolinyl
, 2-'-isoindolinyl group, 1-
Benzotriazolyl group, l-benzimidapryl J old
, 1-(1,2,4-1-riazolyl) jj:, I-
(+, 2.3~ triazolyl) group, I-(+,
2, l, 4-atrazolyl) J, (, N-morpholin
group, I, 2.3.4-tetrahydrogynolyl"kl
2 oxo 1 pi[7lysinyl group, 2- l T-
[-pyridone] 11 phthaladione group, 2-oxo-1-
piperinol J, (etc.); these heterocyclic groups are
Alkyl J, (,, aryl group, argyloxy group, a
Ryloxy group, acyl group, sulfonyl group, alkyl group
Mino group, arylamino group, acylamino group, sulfone
Amino group, carbamoyl group, sulfamoyl group, alkyl group
ruthio group, arylthio group, ureido group, alkoxy group
Rubonyl group, aryloxycarbonyl group, imide group,
Nitro group, soano group, carboxyl group, halogen atom, etc.
may be replaced by As a nitrogen-containing heterocycle formed by Yota Z or Z',
, pyrazole ring, imidazole ring, triazole ring or
may include a tetrazole ring, etc., and the ring may be
Examples of substituents include those mentioned for R above.
Ru. In addition, general formula [:+l) and general formula (CII) to be described later ~ [
Substituents on the heterocycle (for example, R, R,
~R, l) is 56-moiety (where R'', X and 7.'' iJ, general formula 1:
CI) R, X, 7. 3) which is synonymous with
Of course, if it is white, it will form a so-called screw type coupler.
Included in the present invention. Also, 7. , Z', Z'' and the following
The ring formed by Zl may further include other rings (for example, 5 to 7
cycloalkene) may be condensed. For example, one
In the general formula (CV), 4j and ζJ: l'j b and RIl are
, in the general formula (CVI), +J: R, , and 111.
Or i! T, Ic is bonded to the ring (e.g. 5-7 days
More specifically, what is represented by the general formula (Cl) is
It is represented by the following general formulas [CII) to [C■]. General formula (Cn) General formula (Cl) -N--N General formula [CN3 N-N--Nll General formula (CV) General formula (CVI) N'-'-N ---Nl+ General formula (CVll) N −' ”N ”””””-N In the above general formulas (cIt) to (CVll), R
1-Re and X have the same meanings as R and X in 1111. Also, among the general formula (CI), preferred are ]τ
It is represented by the general formula (CVl). In the formula, R, , X and Z + donkey set [III R in Cl3
, X and Z. . Magenta represented by the general formula (CII) ~ [C■]
Particularly preferred pullers have the general formula (Crl).
is a magenta coupler represented. In addition, the substitution of heterocycle 1- in the general formula CCI) to [C■]
Regarding substituents, in the general formula [Cl3, R is
In addition, in general formulas [C■] to [C■], R7 is
It is preferable that condition 1 is satisfied, and more preferably the following condition is satisfied.
The following cases are particularly preferable when conditions 1 and 2 are satisfied.
This is a case where conditions 1.2 and 3 are satisfied. Condition 1 The root atom directly connected to the heterocycle is a carbon atom. Condition 2 Only one hydrogen atom is bonded to the carbon atom
, or not bonded at all. Condition 3 All bonds between the carbon atom and adjacent atoms are single bonds.
This is the case. Most preferred as the substituents R and R1 of the heterocycle -J-
Ino is represented by the general formula (CIX) below.
be. General formula (CIX) No. R+oC- R1+ In the formula, Re, Rho and RIt are hydrogen atoms and halo, respectively.
Gen atom, alkyl group, cycloalkyl group, allo-alkenyl group, cycloalkenyl group, arginyl group, ali
group, hete [1 ring group, acyl group, sulfonyl group, sulfonyl group,
Finyl group, phosphonyl group, carbamoyl group, sulfa group
"Moyl", (, cyano group, spiro compound residue, bridged carbonization
Hydrogen compound residue J1 (, alkoxy group, acylamino group,
Heterocyclic oxy group, siloxy group, acyloxy group, carboxylic group
Bamoyl group, amino group, acylamino group, sulfo group
amide group, imide group, ureido group, sulfamoyl group
Mino group, alkoxycarbonylamino group, arylox
Cycarbonylamino group, alkoxycarbonyl group, ali
oxycarbonyl J, (, alkylthio group, ary
Represents a ruthio group, a heterocyclic thio group, and R9,R. and at least two of R8 are not hydrogen atoms. Also, two of the above R9, Itto and R++, for example, R
8 and RIO combine to form a saturated or unsaturated ring (e.g.
even if they form (loalkanes, cycloalkenes, heterocycles)
In addition, 111. is added to the ring. is combined to form a bridged hydrocarbon compound.
The group represented by R9 to R1+ may have a substituent.
, specific examples of groups represented by R9-R11 and nucleating agents are included.
Examples of substituents that may be substituted include the above-mentioned general formula [Cl3].
Specific examples of groups and substituents represented by R are listed. Also, for example, a ring formed by combining Rg and Rlo and R9
~ Bridged hydrocarbon compound residue formed by RIt
Examples of compounds and substituents that they may have include the above-mentioned general
Cycloalkyl, cycloa represented by R in formula (CI)
Specific examples of rukenyl and heterocyclic group-containing bridged hydrocarbon compound residues
and its substituents. Among the general formula [CIX], (')Re
If two of -Rl+ are alkyl groups, (ii) R9
~ One of RIt, for example R11, is a hydrogen atom,
The other two, R8 and R3°, combine to form a cylinder with the root carbon atom.
When forming chloroalkyl, Furthermore, among (1), preferable ones are among R11 to RII.
two are alkyl groups, and the other one is a hydrogen atom or
is for an alkyl group. where the alkyl, the n(1 alkyl further has a substituent)
The argyl, the cycloalkyl and its substitution
As a specific example of the substituent, R in the general formula (C1) is
Specific examples of alkyl, cycloalkyl and their substituents
can be mentioned. In addition, general formula (ring formed by Z in C13 and
The ring formed by 13 and Z in the general formula [C■] is
Substitutions that may have "l(," as well as general formulas [CII) ~(
R7-R8 in 1-J in CVI) is represented by the following general formula (
CX) is preferred. General formula [CX] 11'=so, -R2 In the formula, R1 is alkylene, 1 and 2 are argyl, cycloa
Alkylene or (' represents aryl. Alkylene represented by R1 (J preferably straight chain carbon)
The prime number is 2 or more, more preferably 3 or 3, and is directly
There are no gaps between the three branches of the chain. Also, alkylene is a substituent
It may have. Examples of the substituent include the above-mentioned general formula (C1)
When R is an alkyl group, substitutions that the alkyl group may have
Examples include those shown below. Preferred substituents include phenyl.
Ru. Preferred specific examples of alkylene represented by R1 are shown below.
show. The alkyl group represented by R2 may be a linear, monobranched group. Specifically, methyl, ethyl, propyl, 1so-propyl
Butyl, 2-ethylhexyl, octyl, dodecyl
, tetradecyl, hexadecyl, octadacil, to 2-
Examples include xyldecyl. The cycloalkyl group represented by R2 includes a 5- to 6-membered cycloalkyl group.
is preferred, such as cyclohexyl. Argyl and cycloalkyl represented by R2 have a substituent.
For example, the above-mentioned substituent to [N1
The following are examples. Specifically, the aryl represented by R2 is phenyl.
, naphthyl. The aryl group has a substituent
It's okay. Examples of the substituent include linear or branched atom groups.
In addition to Lugyl, those exemplified as substituents for R' mentioned above
can be mentioned. In addition, if there are two or more substituents, those substituents are
They may be the same or different. Particularly preferred among the compounds represented by general formula (C1)
is represented by the following general formula [C″A]. General formula (CXI) In the formula, R and X are synonymous with R and X in general formula [C1].
Yes RI, R2 is RR2 in general formula (CX)
is synonymous with Specific examples of compounds used in the present invention are shown below.
Ming is not limited to this, and also includes
The general formula of the present invention as disclosed in No. 228252 (
A polymer having a structure represented by C1) in the pendant part
Couplers are also included. (M-1) (M-2) (M-3) (M-4) (M-9) (M-5) (M-6) (M-7) 01゜(M-8> CH. t ν -1'1 CI+. (M -10) (M -11) (M -12) LM-1,3 (M -14) (M -15) (M -16) 2H5 (M -17) ( M -18) (M -19> (M-20) (M-21) (M -22) (M-23) (M -24) (M -25) (M -26) (M-27) ( M-28) C declaration 01121 (M-29) (M-30) (M-31) (M-32) (M-33) (M-34) (M-35) (M-36) (M- 37) (M -38) (M -39) (M -40> (M-41) (M -42) H3 (M -43) , at---7,, (M-44) (M-45 ) (M-46) (M-47) C711+s (M-48) (M-49) (M-50) (M-51) (M-52) (M-53) C, I+. (M-54 > (M-55) C211゜(M-56) (M-57) (M-58) (M-59) CI. (M-60) (M-61) (M-62) Di11゜(M -63) c, II, s (M-67) (M-64) (M -65) (M -66) (M-70) C,11,3 (M -68) (M -69) Shi2 !1゜(M-73) C11゜(M-74) (M-75) (M-76) (M-77) (M-78) (M-79) -87= (M-80) C211゜(M-81) (M-82) ■" (M-83) C2I+5 (M-84) (M-85> (M-86) (M-87) 2H5 (M-88) (M-89) ( M-90) (M-91) (M-92) (M-93) (M-94) 2115 (M-95) (M-96) (M-97) (M-98) (M-99 ) (M -100) 2H5 (M -1101 (M-109) (M -1105 (M -113) (M-112) (M -115) (M -116) QC211° (M -117) (M - 118) (M -119) (M -120) ShiN3 (M-121) (M -122) (M -123) CI. (M -124) (M -125) C11゜ (M -126) C11゜(M -128) (M -129) (M -130) CI. (M-131) (M-132) C11゜(M-133) (M-135) (M-136) (M-137) (M-138) 2tlS -10:'l- (M-139) 113CCHa (M -140) (M-141) (M -142) (M -144) (M -145) (M -146) (M -147) (M -148) 0((:112)2U(: 12125 (M-153) N -N -N (M-156) (M-107- (-N -N (M-1610 N -N -NH (M-162) rN (M-167) C,H. (M-168) (M-169) (M-174) (M-175) (M-178) ■ (M-179) (M-183) N -N -N II (M-191) (M- 192) (M-195) (M-196> (M-197) (M-1991) The synthesis of the coupler is also described in the Journal of the Chemistry.
Cal Society (Journal of theC
chemical 5ociety), Pergin (Per
kin) I (1977). 2047-2052, U.S. Patent 3.725.0674'
;-1 JP-A-59-99437, JP-A-58-420
45Y3, JP-A-59-162548, JP-A-5! l
t-171956, JP-A No. 60-33552 and JP-A No.
It can be synthesized by referring to No. 60-43659 etc.
Wear. The couplers of the present invention are typically halogenated (lX per mole of silver
l0-3 mol to 1 mol, preferably lXl0-2 mol
It can be used in the range of 8 x 10-' moles.
. The coupler of the present invention may also be used with other types of magenta couplers.
It can also be used in combination with Silver halide coating for color photographic light-sensitive materials
The hydrophilic binder used to
However, high-molecular polymers may also be used, and membrane
The swelling rate T must be less than 25 seconds. Ba
The swelling rate T of the inder is determined by a method known in this technical field.
can be measured according to any desired method, e.g.
Photographic Science by A. Green et al.
・And-J'- Engineering (Photo, Sci,
Eng.), Volume 19, No. 2, 124-129.
By using a swellometer (swelling membrane) of the type shown in
T can be measured using a color developing solution at 30℃ for 3 minutes and 15 seconds.
The saturated film thickness is defined as 90% of the maximum swollen film thickness reached when
, is defined as the time it takes to reach this film thickness. The membrane swelling rate T is the gelatin as a binder and a hardening agent.
It can be adjusted by adding Hardening agents include aldehyde-based, aziridine-based IIL (for example, PR Report 19,92 U.S. Patent 2,950
, No. 197, No. 2,964,404, No. 2,983,
No. 611, No. 3,271,175, Special Publication No. 1977-40
8'lRshi J., JP-A No. 50-'II'' A15, etc.
), isoxazolium-based (e.g., U.S. patent
3,321,323S;-), epoxy system
(For example, U.S. Patent No. 3,047.394, West German Patent No. 1
, No. 085,663, British Patent No. 1.033, 51 g
-:・, 6 described in Special Publication No. 48-35495, etc.)
, vinyl sulfone type (e.g. PB Report 19,9
20, West German patent 1. Ion, 9421 (, 2.337
．． No. 412, 2,545,722 shi), 2.6″3
5,518 Bow-1 2゜742.308, 2,74
9,260, Missing Circle Patent No. 1,251,091, U.S. Pat.
3,539.644 yen, 3,490,911 yen etc.
), acryloyl-based (e.g., U.S. Patent 3゜
640.720), carbodiimides (
For example, U.S. Pat. No. 2,938.892), U.S. Pat.
3,818㎢・, No. 4.061,499, Special Publication No. 1973
- agylsl-, those described in H, etc.), triazines
system (for example, West German Patent No. 2.LIo, No. 973, No. 2,5
No. 53,915, U.S. Patent No. 3,325,287, JP
(described in No. 52-12722, etc.), polymer type (e.g.
For example, British Patent No. 822,061, US Patent No. 3,623
, No. 873, 3゜396.029 Bow-1 3,226
, No. 234, Special Publication No. 47-18578, No. 18579
No. 47-48896, etc.), and other materials.
Reimide type, acetylene type, methanesulfonic acid ester
Hardeners such as N-methylol and N-methylol can be used alone or in combination.
Can be used. As a useful combination technique, for example,
No. 2,447,587, No. 2.505.746, No.
No. 2,514.245, U.S. Pat. No. 4,047,957
, No. 3,832,181, No. 3,840.370,
JP-A No. 48-43319, JP-A No. 50-63062,
No. 52-127329, Special Publication No. 48-'A2364
Examples include combinations described in . The binder of the photographic constituent layers used in the color photographic material of the present invention
The membrane swelling rate T is 25 seconds or less, and the
It is preferable that the lower limit is too small, but if the lower limit is too small, it will not be hardened and the
It is preferable to wait for more than 1 second as it may easily cause clutch failure.
stomach. More preferably 2 seconds to 720 seconds, particularly preferably
is 15 seconds or less, most preferably 10 seconds or less. 25
If it is longer than 2 seconds, the desilvering performance, that is, the bleach-fixing performance will deteriorate.
, especially when using a low molecular weight organic acid ferric complex salt or a high molecular weight organic acid ferric complex salt.
Even when using a ferric complex salt of an organic acid with a high molecular weight, when the concentration used is high.
Deterioration is young. The bleaching accelerator of the present invention is represented by the general formula [1] to [■].
However, typical examples include the following:
Can include, but are limited to, Kinora.
isn't it. [Exemplary compounds] (I-3) (1-4) (1-7>
(1-8) (I-9)
(1-10) (1-13
) (I-14)C1
12COOII C112CH
3(I-23) (1
-24) (I -27) (
I-28) (1-31)
(Summer -32) (1-33)
(, -34° (1-35)
(, -36° (■-37)
<1 3 g> (II-1)
(TI-2) (II 13)
(1114) (II-3)
(If-4) (It-5)
(If-'6) (II-7) (
II-8) (■-9) (II-10) (II t 1 ) < n
12 > (II-21) (I [-15) (■, 6) (I
I-17) (II-18>
(IF-19) (It-20) (II-22) (II-23) (II-24) (ff-25) (II-26) (II-27) (II-28) 11□N C5NIINIICS Nll2 (II
-29) (II-30) (II-31) (TI-32) (IT -33) (It -34> H2N C5NH(CH2)2NHCS NO3(
II-35) 112N-CSNH(CIl□)aNHCS-NO3
(TI-36) H2N C5NH(CH2)5NHCS NO3(
II-37) (Il-38) (Il-39> (II-40) (U-41) (n-42) (II-43) (II-44) (II-45) (rl-46) ( I[-47) S (If-48) (If-49) (I[-50) (n-51) (It-52) (II-53) (It-54) (II-56) (IT- 57) (Il-58) (I[-59) (I[-60) (II-61) (I[-62) (II-63) (Il-64) (I[-65) (II-66 ) (Il-67) (II-68) II Na Na (II-69) (II-70) (II-71) δ (II-72) (I[-73) (II-74) CH3NHCH2CH2NHCSCH2CH2CHzC
OOt1(TI-76) (It-77) (■ -78) δ (Il-79) (II-80) (II-81) (H-82) (]l-83) (II-84) (Il -85> (II-86) (II-87> (II-88) (II-89) (It -90) (II-91) (II-92) (II-93) (II-94) (II -95) (TI-96) ■ (II-97) (II-98) (n-99) (U -100) (II-101) (I[-102) (II-103) (II-104) (II-105) (II-106) (II-108) +1 i-109) <II -111) (II -1
12) (Il-123)
(ll-124) (II-113)
(n -114) (II -115)
(II-116)(It-1
17) (I[-118)(I
I -119) (If -1
20) (II-121) (
If -122)S (■ ~131)
(IT-132) (ll-1,25)
(TI, 126) (II-127)
(H-1z8>(II-12
9) (If -1,30)
S S (TI-133) (I
I -134)1':L (II -135) (I
I-136) (IT-137)
(II-138) (II-139)
(l-140) (If-141)
(IT-142) (II-
143) (II-144) 1l (n-145) H (u-147) (II-148) (If-149) (If-150) (II-151) (II-152) (II-153) (II-154) (n-155) (II-156) (II-158) H2N CH2CH25R (III-2) (III-3) HOOC-CH2CH2・SR (III-6) (III-7) (DI- 8) (Ill-9
) Clf. (III-11) C0i Cl13/□-λ ON-Cl1. CI+2-511 (It-13) Cl3 (III-14) C112CH2-5R (Ill-15) (III
-16) (III-17)
(I[l -18)Ha し■3 (1-19) (Ill-20
) (nl-21) (III
-22) CI! 2CI+2-S! 1 (1-23) (In-2
4) (1-25> (II
-26) (I[[-28) (III-29) (1-3
0) (1-31) (II-
32) (III-34) (III-35) (III-37) (TV-1)! HV-2) CI! 3 CI+3 (FV-3) (IV -4) (■-5) H3 F13 (V-1) (V-2)! 1 (V-3) (V-4) (V-5
) (V-6) (V-7)
(V-8>(V-9>
(V-10) (V-11)
(V -12) (V -13) (
V -14)H (V -15) (v,6)(
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-:'18) (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-5
2>(V 53 ) (v
s, s > CI+3 (V-55) (V-56) (V
-57) (V -58) (V
-59> (v, 0°(V-
61) (v, 2) (V -63
) (V-64) (V-65
) (V -66) (V -6
7) (V -68) (V -6
9) (V-70) (V-7t
) < v 72 ) (V
-73) (V-74) (V-
75) (V-76>(V-7
7) (V-78) (■-79
) (V-80)
(V-81) (V-82) (
V-83) (V-84)
(V-85) (v-se>(
■-87) (
V-88) (V-89) (V
-90) (V -91) (V
-92) (V-93> (
V-94) (V-95) (
V-96) (V-97)
(V-98>C112N112
C112C1128I+2 (V -99)
(V-100) (V-101)
(V-102)II
C2115 (V −103) (V −
104) (V-105)
(V -106)NH2N)12 (V -107> (V -108) (V -109) (y -no) (V -111) (V -112) (y -113) (V-114) (V -115) (y-iie) (V -117) (V -118) (V -119) (V-120) j (V-121) (V -122) (V 123) (y 124
) (V -125) (V -12
6) (V-127)
(V-128) (V-129)
(V-130) (V-131)
(V-132) (V-133)
(V-134)Nl2
SH(V-135)
(V -136)03Na (V -137) (V -138
>(V 139 ) (v-14
o > (V −141) (V −
142) (V -143) (V
-144) (V -145) (V
-146) (V -147) (V
-148) (V -149) (y
-150) (V -151) (V
-152) (V -153)
(V-154) (V-155)
(V -156) Gu II (V 157) (V
15B) (V-159)
(V -160) (V -161)
(V-162) (V-163)
(V-164) (V-165)
(V-166) (V-167)
(V -168)SHNH2 (V -169) (V -
170) (V -171) (
V -172) N11+ 1l (V -173) Tatsu (V -174) (V -1
75) (■-176) SH (■-1fufu) (V-
178) (V -179) N = N II O (V -180) (V -1
81) (V -182) (V
-183) SHSll (V-184) Sll (Vl-1) (Vl-2) (VI
-3) (Vl-4) (Vl -
5) (Vl-6) (Vl-7) (
Vl-8) (■-9) (Vl-1
0) (Vl-11) (■-12>
(W-13) (W-14) (Vf-15)
(Vl-16) (Vl-17)
(Vl-18) (Vl-19) (VI-
20) (VI-21) (■-2
2) (Vl-29) (Vl-30)
(Vr-31) (VI-32) (V
l-:13) (Vl-34)n■ (Vl-35) (Vl-36)
(■-3) ISCH2CI2NHCH2CH2
CH2SO3H)2(■-16) 1lSC
+1. C11, NCl1. Cl12CONl+2CIl
. (■-17) ll5c112C112NI
IC112CI+2011(■-18) l
lSC112llSC112C112+2011C21
+5 (■-19) tlsclI 2C112M
C112CI+ 28 (CIl :l) 2 glances C11° (■-20) ll5cII□C112MC
II□CII□0C112CII□OCLCOCl+
The compounds described in 3- are, for example, described in British Patent No. 1,138.842.
No., JP-A-52-20832, JP-A No. 53-28426
, No. 53-95630, No. 53-104232, No. 53-104232, No. 53-95630, No. 53-104232, No.
No. 53-141632, No. 55-17123, No. 60
-95540, U.S. Patent No. 3,232゜936, No. 3
, No. 772,020, No. 3,779,757, No. 3,
893゜858, etc., using the known technology.
can be synthesized into The bleach accelerator of the present invention bleaches the silver image obtained by development.
It only needs to be present in the bleach-fixing bath.
Preferably, the bath prior to the bleach-fix bath (pretreatment solution, especially prefixing bath)
silver halide color photographic materials.
By bringing it into the bleach-fixing bath,
Also preferred is the method of Most preferably a pretreatment liquid, especially a pretreatment liquid.
It is present in both the fixing solution and the bleach-fixing solution. In this case, it is present in the pre-treatment solution, and the bleach-fix solution contains
It may be brought in through photographic materials, or it may be brought in at the time of manufacture.
Contained in advance in silver halide color photographic light-sensitive materials
Pretreatment baths or bleach-fixing baths.
A tightening method etc. may also be used. These bleach accelerators of the present invention may be used alone in r111
7. Two or more species may be used to accelerate the bleaching process.
The promoter is added to the bleach-fix solution or similar bath prior to the previous bath (
1iij processing solution, especially 1111 constant i'''1 processing solution).
The amount added is generally about 0.01 per 1θ of each processing solution.
Good results can be obtained in the range of ~100g. 1. While nibbling
Generally, when the amount added is too small, bleaching (IC promotion effect is small)
Also, the amount of Il added is too large compared to the required amount -]-! J is sinking
Silver halide color ``true photosensitive material'' processed by forming sludge
0 per processing liquid IQ as it may contaminate the
．． 05 to 50 g is preferable, and more preferably treatment liquid I
It is 0.05 to 15 g per Q. The bleach-fixing effect and/or bleach-fixing effect of the bleach accelerator of the present invention
In the bath preceding the bath (+ii7 treatment bath, especially the pre-fixing treatment bath)
If added, it may be added and dissolved as is, but water
,) 2 It is best to dissolve it in alkali, organic acid, etc. and add it in advance.
methanol, ethanol, alcohol as needed.
Even if it is dissolved and added using f1 solvent such as setone,
It has no effect on the bleach-fixing effect. Metal ions can be supplied to the bleach-fix solution of the present invention by any method.
It is desirable that this be supplied in order to improve the bleach-fixing properties. For example, halides, hydroxides, sulfates, phosphates, vinegar
It can be supplied in any form such as acid salt, but preferably the following
The compound shown in can be supplied as a complex salt of a chelating agent.
(Hereafter, the metallization that supplies these metal ions
The compound is referred to as the metal compound of the present invention. ). But this
However, the supply method is not limited. Furthermore, chelate
Examples of agents include organic polyphosphoric acid, aminopolycarboxylic acid, etc.
It can be whatever you want. [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-I+ double blind balt sulfate (A-19) dibalt acetate (A-20) Zeliuno sulfate, (A-21) Magnesylano chloride, (A-22) Magnesylano sulfate, (A-23) Magnesylano acetate, (A-24) Calcilano chloride, (A-25) Calcilano nitrate, (A-26) Valiumo chloride. , (A-27) barium acetate, (A-28) barium nitrate (Δ-29) strontium chloride (A-30) strontium acetate (A-31) sulfur nitrate), rhodium (Δ-32) manganese chloride (A-30) 33) Manganese sulfate (Δ-34) Manganese acetate (A-35) Lead acetate (Δ-36) Lead nitrate (Δ-37) Ditane chloride (Δ-38) Stannous chloride (Δ-39) Zirconium sulfate' ( A-40) Zirconium nitrate (All) vana
Ammonium dinate (A-42) Ammonium metavanadate (Al1)
Sodium tungstate (Δ-44) Ammonium tungstate (Δ-45)
Aluminum chloride (Δ-46) Aluminum sulfate (A-47) Aluminum nitrate (A-48) Yttriuno sulfate, (A-49) Yttriuno nitrate, (A-,50) Yttriuno chloride (A-51) Zamariu chloride J1 ( A-52) Zamariuno bromide, (A-53) Zamariuno sulfate, (A-54) Zamariuno acetate, (A-55) Ruthenium sulfate, (A-56) Ruthenium chloride, These metal compounds of the present invention are You can also use
It is also possible to use two or more types of -I- in combination. This amount is gold
From 0.0001 mol per 112 of the working liquid as a genus ion
2 mol is preferred, particularly preferably 0.001 mol to 1 mol
The bleaching accelerator of the present invention has a molar range of 3°.
Among them, It', R2, R3, R4, R5, R
8, RII, ASB, D, Z, Z', R, R',
jlf2 and R and T-L', R2 and R3, R4 and
Heterocyclic residue formed by R5 and QSQ', amino group
, aryl group, alkenyl group, and alkylene group, respectively.
May be replaced. The substituent is an alkyl group
, aryl group, alkenyl group, cyclic alkyl group, aral
Kyl group, cyclic alkenyl group, halogen atom, nitro group,
Cyano group, alkoxy group, aryloxy group, carboxy group
cy group, alkoxycarbonyl group, aryloxycarbo
Nyl group, sulfo group, sulfamoyl group, carbamoyl group
, acylamino group, heterocyclic residue, arylsulfonyl
group, alkylsulfonyl group, alkylamino group, dial
Kylamino group, anilino group, N-alkylanilino group,
N-arylanilino group, N-acylanilino group, hydro
Examples include Roquin group. Also, the RI-R5
, R8, R9, Z', R, R'
The group may also have a substituent, and the substituent is
Of the 6 listed above, all except the alkyl group are
Can be mentioned. The bleach-fix solution of the present invention contains an organic acid ferric complex as a bleaching agent.
Contains a salt (hereinafter referred to as the organic acid ferric complex salt of the present invention).
It will be done. As an organic acid that forms the organic acid ferric complex salt of the present invention-4'
The following are representative examples. (1) Diethylenetriamine II', ff' + acid (M
Y: (93,27) (2) dielenetriamine l
I methylenephosphonic acid (M guest = 573.12) (3) Cyclohegysandiaminotetraacetic acid (MW = 36L
35) (4) Cyclohegysanaminetetramethylenephos
Fonic acid (MW = 508.23). (5) Triethylenetetosimine hexaacetic acid (MW-364,
35) (6) Triedylenetetramine hexamethylenepospo
(MW = 710.72) (7) Glycol ether diamine tetraacetic acid (MW = 3
80(8) Glycol ethernoamine V9 methylenepo
Sulfonic acid (MW 52L23) (9) 1,2-noaminobu-1-nopanetetraacetic acid (MW = 3
06.27) (10) 1.2--diaminop Vl pan 4
Methylene phosphonic acid (MW...l150.+5) (1,1) I, 3--diaminobu I-1 pan-2
-oltetraacetic acid (MW=322.27) (+2)1,3-diaminopropan-2-oltetraacetic acid
Renphosponic acid (M!= 466.15) (13) Ethi
Diamine diorthohydroxyphenylacetic acid (M!=
360.37) (14) Ethylenediamine diorthohydroxyphenyl
Methylenephosphonic acid (MW = 432.31) (15)
Edylenoamine tetramethylene phosphonic acid (MW = 43
6.13) (16) Ethylenediaminetetraacetic acid (MW = 292.2
5) (17L-trilotriacetic acid (MW = 191.14)
(18) Nitrilotrimethylenephosphonic acid (M!=2
99° (19) iminoniacetic acid (M!= 133.10)
(20) Iminone methylene phosphonic acid (MW = 205
．． 04) (21) Methyliminoniacetic acid (MY=147.
13) (22) Methyliminodimethylenephosphonic acid (M
W = 219° (23) hydroxyethyliminodiacetic acid
(MW = 177, 1.6) (24) Hydroxyethyl
Iminodimethylenephosphonic acid (M!= 249.10) (25) Ethylenediaminetetrapropionic acid (MW=
348.35) (26) Hydrogyso, r-Dilgurindin (M!=
163.17) (27) Nitrilotripropionic acid (
MW = 233.22) (28) ethylenediamine,
/I'+acid (MW-=, 176, 17) (29)
Tilene diamine dipropionic acid (M!= 277゜Main origin)
Ferric acid complex salts (including, but not limited to, J)
One type can be arbitrarily selected and used from among these,
”: Use a combination of 2 inserts-1- according to the 8 stars.
I can do it. Among the organic acids forming the ferric salt of the organic acid of the present invention, particularly preferred are
A typical example of this is the one in the book Jz. (1) Edilene triamine pentaacetic acid (MW = 393.
27) (3) Cyclohegizanediaminotetraacetic acid (MW=
364.35) (5) Triethylenetetraminehexaacetic acid (
M! = 49L45) (7) glycol ether di)'
Minetetraacetic acid (MW = 31'1O(9)1,2-diami
Nopropane tetraacetic acid (MW = 306.27) (]I) 1
．． 3--Diaminopropan-2-oltetraacetic acid (11m
= 322.27) (13) Ethylenediamine diorthohydroxyphenyl
Acetic acid (MW = 360.37) (16) Ethylenediaminetetraacetic acid (MW = 292.2
5) (19) Iminoniacetic acid (MW= ] 33.10)
(21) Methyliminoniacetic acid (MW = 147.13)
(23) Hydroxyethyliminodiacetic acid (M!= 17
7.16) (25) Ethylenediaminetetrapropion
Acid (MW = 348.35) (26) Hydroxyethylglycine (MW = 163
．． 1.7) (27) Nitrilotripropionic acid (MW=
233.22) (28) Endylene diamine diacetic acid (M
W = 176.17) (29) Ethylenediamine dipro
Pionic acid (MW = 277゜organic acid ferric complex salt of the present invention)
is free acid (hydrogen salt), sodium salt, potassium salt
, alkali metal salts such as lithium salts, or ammonium
salts, or water-soluble amine salts such as triethanolamine.
It is preferably used as potassium salt, sodium salt, etc.
Um salts and ammonium salts are used. These secondary iron
At least one type of complex salt may be used, but two or more types (7
1 for 4' can also be used. The amount used can be chosen arbitrarily.
The amount of silver and halogenation of photosensitive ItAFl to be processed
It is necessary to select it depending on the silver composition, etc. That is, it is used at 0.01 mol or more per 1 ρ of the working liquid.
is preferable, more preferably 0.05 to 1.0 mol.
used. In addition, for replenishment fluid, we use concentrated and low replenishment solutions.
Concentrate it to a relatively high solubility and use it as a replenisher.
This is desirable. The bleach-fix solution of the present invention has pt12. Used in Q~10.0
It is preferable to have a pI-f of 3.0 to 9.
．． 5. Most preferably used at pH 4.0 to 9.0.
Ru. The treatment temperature is preferably 80°C or lower.
, more preferably 55°C or lower, most preferably 45°C or lower
Use at the bottom to prevent evaporation, etc. Bleach-fixing processing time is 8 minutes
It is preferably within 6 minutes, more preferably within 6 minutes. The bleach-fix solution of the present invention can be used as a bleaching agent as described in +iiJ.
The organic acid ferric complex salt of the present invention also contains various additives.
You can As an additive that contributes to bleach-fixing properties,
Especially alkali halides or ammonium halides, e.g.
For example, potassium bromide, sodium bromide, sodium chloride,
Ammonium bromide, ammonium iodide, sodium iodide
It is desirable to contain potassium iodide, etc. Also
Solubilizers such as reethanolamine, acedelacetone,
Vosbocarboxylic acid, polyphosphoric acid, organic phosphonic acid,
xocarboxylic acids, polycarboxylic acids, alkyl amines,
Can be added to ordinary bleaching solutions such as polyethylene oxide.
Those known to have the following properties can be added as appropriate. The bleach-fix solution of the present invention contains halogens such as potassium bromide.
A bleach-fixing solution containing a small amount of chemical compound, or
Conversely, potassium bromide, ammonium bromide and/or ammonium iodide
Large amounts of halides such as ammonium and potassium iodide
A bleach-fixing solution comprising the added composition, and also a bleaching solution of the present invention.
Combinations of agents with large amounts of halides such as potassium bromide
It is also possible to use a special bleach-fixing solution with a composition consisting of
can. As a silver halide fixing agent to be included in the bleach-fixing solution of the present invention,
silver halide, such as those used in normal fixing processes.
Compounds that react with water to form water-soluble complexes, such as thio
Potassium sulfate, sodium diosulfate, ammonium diosulfate
Diosulfate such as um, potassium thiocyanate, thiosulfate
salts such as thorium anoate and ammonium thiocyanate.
Osocyanates, dioureas, dioethers, high concentrations of bromides
Typical examples include chloride, iodide, etc. These establishments
The agent is 5g/Q or more, preferably sog/Q or more.
, more preferably 70g/& less-1-Dissolvable range
Can be used in full. The bleach-fix solution of the present invention contains boric acid, borax, and sodium hydroxide.
Ugly potassium hydroxide, Ugly sodium carbonate, Potassium carbonate
, potassium bicarbonate, acetic acid, triacetate
various PT+ buffers such as ammonium, ammonium hydroxide, etc.
Including (j' (]
I don't mind if you leave L. Furthermore, various optical brighteners and antifoaming agents
It is also possible to contain a fungicide or a fungicide. Also
Hydroxylamine, hydrazine, sulfites, isomeric bicarbonate
Sulfates, bisulfite additives of aldehydes and ketone compounds
Preservatives such as, other additives, methanol, dimethyl
Apply organic solvents such as formamide and dimethyl sulfoxide.
It can be added as desired. Furthermore, the patent application 1973 (1-51
The vinylpyrrolidone nucleus as seen in the specification of No. 803
It is desirable to add a polymer or copolymer having the following properties. Another substance that can be added to the bleach-fixing solution of the present invention to promote bleach-fixing properties.
Preferred compounds include tetramethylurea and triphosphate.
Sudimedylamide, ε-caprolactam, N-methylpi
lolidone, N-methylmorpoline, tetraedylene glycol
Col monophenyl ether, acetonitrile, glyco
and monomethyl ether. In the processing method of the present invention, the bleaching method of the present invention is applied immediately after color development.
Fixing is the preferred processing method, but color development
After washing with water or rinsing or stopping, etc.), the main
The invention may be subjected to bleach-fixing treatment. most preferably tJ
Pre-fixing treatment was performed after color development as described in 1'+ii.
After that, the bleach-fixing treatment of the present invention is performed, and in this case,
, the bleach accelerator of the present invention may be included in the 01i fixing process;
good. The bleach-fixing process of the present invention requires washing with water and stabilizing treatment.
You can also wash it with water and then stabilize it.
stomach. In addition to the above steps, dura mater, neutralization, black and white development, reversal
, small filtration, water washing, etc., various auxiliary procedures as necessary.
(・1 may be added. Typical examples of preferred treatment methods
For example, the following steps are included. (1) Color development, white fixing, water washing (2) Color development
Image/Bleach fixed i'f/Small 111 water wash-/Water wash (3) Color development
Image・,i:1. li white setting valley - water washing - stable (4) color development
Development, t1゛4 white fixation i'f, stability (5) color development - bleaching
In white fixer - 1st stability - 2nd stability (6) Color development -
Washing with water (also (J stable) - bleach-fixing - / washing with water (or stable) (7) Color development / pre-fixing - / bleach-fixing - / washing with water (8)
Color development - Pre-fixing - Bleach-fixing - Stable (9) Color development - Pre-fixing
Coloring - Photoconductivity - 1st stable → 2nd stable (10) Color development - Stop → Bleach fixing - Washing → Stable
The effects of the present invention are more noticeable in the treatment steps of
Therefore, the processing of (3), (4), (5), (8) and (9)
A physical process is more preferably used in the present invention. And most preferably (4), (5), (8
) and (9). Various inorganic metal salts are added to the bleach-fix solution of the present invention.
It is preferable. These inorganic metal salts are
・It is also preferable to add the metal complex after forming the metal complex with the agent.
This is a good method. The bleach-fix solution of the present invention may contain a chelating agent other than the present invention and/or
may be added with its ferric complex salt. However, the book
The ferric complex salts other than the invention are different from the organic acid ferric complex salts of the present invention.
It is preferable to use it in an amount of 0.45 mol% or less. The pre-fixer may contain the bleach accelerator of the present invention.
Preferable things are as described above, and in this case, bleach-fixing
Most preferably, the liquid contains a bleach accelerator.
It's a method. Matadashi and toshiraka are included only on one side (j u
j, meranoko 11 is also 1-y. Promotes bleaching only in pre-fixer
When a bleaching agent is added (JThe bleaching agent is added to the pre-fixing agent.
From silver halide color to true light-sensitive materials,
L:, lj, , jj are included in the bleach-fix solution to achieve the effect.
I will do it. 43 In the bleach-fix solution, iron complex salts occur in the bleach-fix solution.
Oxidation treatment is applied to the reduced form of the oxidized form.
However, as the oxidation treatment, for example, air oxidation treatment is preferable.
A physical process is used. Here, the air oxidation process and
Bubbles in the processing solution in the bleach tank or bleach-fix tank of the imager
Forced oxidation process where oxidation treatment is performed by forcibly mixing and contacting
It refers to the temperature of the liquid, and may be oxidized by natural contact with air on the liquid surface.
included, but this means is usually called aeration,
Air sent out from a device such as a compressor,
of air distributor to increase oxidation efficiency
A diffuser with microscopic pores allows the air to
The diameter of the tank is made smaller to increase the contact area with the liquid.
The process liquid comes into contact with the air bubbles sent into the liquid from the bottom.
It is preferable that the oxidation be performed at high oxidation efficiency. This aeration is mainly done inside the processing tank.
, you can do it in batches in a separate tank, or you can do it on the tank side.
This is done by a secondary tank for aeration mounted on the surface.
You can. Especially when regenerating bleach solution or bleach-fix solution.
If this is the case, it is preferable to do it outside the tank liquid. Main departure
In light, it is usually called overaeration.
There is no need to think about this, so air ventilation is maintained throughout the processing time.
Aeration may be performed, and strong aeration may be performed intermittently.
It can be done in any way you like. however
The smaller the air bubble diameter, the better the efficiency.
Preferably, it can be prevented from mixing with other liquids by using plastic etc.
It can be said to be a method. In addition, in the present invention, when the whitening machine is stopped,
Perform array spraying and stop aeration during treatment.
The method is also a preferred method. Also, air lanes are treated with
The liquid may be conducted separately by directing it outside the tank. Air as mentioned above
Laneyon is from Tokukai Showa 4! + 55' A 3 G
! +1'il 5] -99831 No. 54-
952: One-way shower and spray shower listed in Nsuko t1
Can be used in combination with one-way spray method and two-way spray method.
, also described in West German patent (01,, S) 2,113,651.
Please feel free to use the method provided. Silver halide color photographic light-sensitive material that can be used once a month according to the present invention
The total coating silver 1n is one layer of colloidal silver filter and colloidal silver 1n.
ζThis is a value including the silver halenoFlin prevention layer, and is 80m
g/dm' or less, at which time the effect of the present invention is exhibited.
It will be done. Preferably 60B/dm', particularly preferably 50
It is effective when heard below mg/dm'. photographic performance
From the point of
is preferable and exhibits the effects of the present invention. The silver saponide cuff of the present invention - Photographic composition of photosensitive monthly interest
Layer 1 thickness (Zekudin thickness) and (photo composition excluding J support)
layer, layer, layer, halation rainproof layer, intermediate layer, small layer
The entirety of Kutomu 3's emulsion layer, filter layer, protective layer, etc.
The total membrane III of the hydrophilic 2111-ide layer is
There are only 11 photographic constituent layers. Microphone is used to measure PI.
[This is carried out using a J-meter, but in the present invention, the photographic constituent layers are
The total thickness is 25 μm or less, preferably 22 μm or less.
below, especially below 2011m, most preferably below 1871m
It's below. From the point of view of photographic performance, '8Bm or higher' is preferable.
Therefore, the effects of the present invention will be exhibited. The silver halide emulsion layer of the present invention contains at least
Also contains 0.5 mol% silver iodide grains, but silver halide color
-Sensitivity and photographic properties of photographic materials and bleach-fixing of the present invention
In order to maximize performance, silver iodide (J photographic properties and
05 mol% to 25 mol% is preferable from the viewpoint of bleach and fixing properties.
stomach. In the present invention, when it exceeds 25 mol%, photographic properties
is more preferable, but bleach-fixing properties are significantly reduced.
. In the present invention, more preferably 2 mol% to 20 mol
% of silver iodide. The black coat for preventing halation used in the present invention [1 item]
The silver halide dispersion layer is a support for silver halide color photographic materials.
Visible for incident light from the surface or emulsion surface
(especially red light).
Ru. Also, silver halide color photographic sensitivity + A month emulsion surface?
The reflectance is sufficiently low for the incident light of I:, 17.
,ing. Is the black color Ll F silver I Maki layer reflectance and bleach fixability?
From this point of view, it is desirable that the colloidal silver be fine particles in
However, if the colloidal silver particles are sufficiently fine, the absorption will be yellow ~
17 The optical density against red light did not increase due to brown color.
Therefore, the particles have to become coarse to some extent, and as a result,
1. Physical development occurs with the silver particles of the iron as the nucleus.
Bleach-fixing properties at the boundary with the silver halide emulsion layer may be poor.
It can be thought of as In particular, the silver halide emulsion layer contains at least 0.5 mol% iodine.
Contains silver oxide particles (in the case of f4', especially those closest to the support)
C [l] The silver saponide emulsion layer contains at least 0.05 mol% iodide.
Phenomenon in which bleach-fixing properties are reduced when containing grains
Kayri:s, with three or more silver iodide table emulsion layers.
4” filter multilayer silver halide color photographic light-sensitive material
The effects of the present invention are especially noticeable when
Shi! aIn the past, H1 was established. In particular, how the present invention exhibits its effects is
When processing a photosensitive material containing core nonyl emulsion.
Regarding some core-shell emulsions used (J1 Special
Although it is described in detail in Kaisho 57-154232, etc.
, a preferred silver halide color photographic light-sensitive material has a core halide
Silver halide composition is 0°1 to 20 mol% of silver iodide, preferably
silver halide containing 0.5 to 10 mol%;
Silver is silver bromide, silver chloride, silver iodobromide, silver chlorobromide, or
It consists of a mixture of these. Particularly preferably, the shell consists of silver iodobromide or silver bromide.
It is a silver halide emulsion. In addition, in the present invention, the core
with substantially monodisperse silver halide grains and no shell
It is preferable to set the thickness to 0.01 to 0.8 μm.
It has a great effect. The silver halide color photographic light-sensitive material of the present invention is characterized by:
Silver halide grains containing at least 0.5 mol% silver iodide
The bottom layer consists of a halide layer consisting of black colloidal silver.
has a coating prevention layer, and the total coating silver amount is 80 mg/dm2 or less,
Preferably 60 mg/dm2, particularly preferably 50 mg
/dm2 or less, and the photographic composition excludes the support.
The thickness of the layer (geladine thickness) is preferably 25 μm or less
IJ: 22 It m, more preferably 2071 m. Especially below 187zm Af) 5, especially core and/or
Using hali:l silver genide grains containing double silver iodide,
Silver bromide, silver chloride, salt;
The silver halide seeds from the mixture are grown to the specified thickness.
By concealing the core using a plastic seal,
Towards higher sensitivity of silver chloride tar particles containing silver oxide (I)
The point of making use of the qualities of the person and hiding the disadvantageous qualities of the area.
It is in. Silver halide grains with shells of the above specific thickness are
For silver halide emulsion i, ! l' into a dispersible emulsion
These shells have silver halide grains as a core.
1.
, the ratio of silver iodide to silver bromide when the shell is silver iodobromide
It is preferable that the amount of carbon is 20 mol% or less. To make the core a monodisperse silver halide grain, pAg is
While keeping the j5 constant, the desired size is obtained using the double jet method.
Sano t-) It's all about getting a child. Also 11 dispersion of altitude
The production of silver saponide emulsion is disclosed in Japanese Patent Application Laid-open No. 54-4852.
Applying the force ′θ, which is 11 self-absorbed, to No. 1.
I can do it. A preferred embodiment of the method is as follows:
Potassium iodobromide-geladine aqueous solution and ammonium nitric acid
An aqueous silver solution and an aqueous geladine solution containing silver halide seed particles.
during which the addition rate is varied as a function of time.
It is manufactured by a method. At this time, the addition rate
Appropriately select time function, pH, pΔL7m degrees, etc.
It is possible to obtain highly monodisperse silver halide emulsions by
can. The particle size distribution of monodisperse emulsions is almost normal distribution.
Therefore, the standard L deviation can be easily obtained. From this, if we define the distribution width (%) using the relational expression, then the absolute thickness of the coating
The distribution is less than 20% wide enough to meaningfully regulate
It is preferable to have a monodispersity of 10
% or less. Next, the thickness of the shell that covers the core is a desirable quality of the core.
The thickness does not hide the
It must be thick enough to hide your true nature. Immediately J'
), ++7 is a narrow limit limited by such upper and lower limits.
Be limited in scope. Such a shell is a soluble
A compound solution and a soluble silver solution were mixed using the double jet method.
・It can be formed by depositing it on the Il'i dispersive core.
can. For example, average grain size l)1 containing 2 mol% silver iodide in the core
m substantially dispersed Jl'+'l silver halide grains
coating with 0.2 mol% silver iodobromide as a shell.
According to experiments with various thicknesses, for example, 0.85
When making a saw with a thickness of 71 m, this method
Dispersive halo v1 genification nJ l'f, child is covering power
was low. Add a solvent to dissolve the silver halide.
Processed with a processing liquid that has physical developability 15, scanning type 7Ii
When observed with a submicroscope, filaments of developed silver were visible.
Naiko Shichi was angry. Dirt reduces iJ optical density and
further (') suggests that it reduces the covering power.
Therefore, considering the filament form of the developed silver, the core
Adjust the thickness of the silver bromide seal on the surface while changing the abrasion diameter.
As a result of thinning the shell, the thickness of the shell is equal to the average grain size of
Regardless of the diameter, the absolute thickness is 0.8 μm or less (preferably
A large number of well-developed silver fibres, with a diameter of 0.5 μm or less
filaments are formed to provide sufficient optical density, and the core
It was found that the quality of high sensitivity was not impaired. On the other hand, if the shell is too thin, it will contain silver iodide in the core.
There are parts where the base material is exposed, and the effect of covering the surface with the shell is
effects, i.e. chemical sensitization effect, rapid development and rapid fixing properties, etc.
ability is lost. The limit of its thickness is 0.01μm.
is preferred. Furthermore, the highly monodisperse core with a distribution width of 10% or less ensures
Accordingly, the preferred shell thickness is O,L1~0.06/
1 m, and the most preferable thickness is 0.03 μm or less.
Ru. The developed silver filament described below is sufficiently generated and exposed to light.
Improves the optical density and takes advantage of the high sensitivity of the core.
sensitization effect, rapid developability, and fixability.
The reason is that the thickness is -1- due to the highly monodisperse core.
regulated nonyl and core and shell halogens
This is due to the synergistic effect between the silver
If the shell can satisfy the thickness regulation of hV
Silver saponide is silver iodobromide, (silver chloride, silver chloride)
Alternatively, silver chlorobromide or a mixture thereof may be used.
Wear. Among them, the familiarity of the core table, +jl ability stability or preservation
I like it from the point of view of gender, etc. <! J Silver bromide, silver iodobromide or
It is a mixture of these. The photosensitive silver halide emulsion used in the present invention has a core and
611! Precipitation generation o, ljS powder
At the time of r growth or (21 after the end of J growth), various metal salts
Or apply 1-1 pink using metal complex 1i11X.
Do it, 1; yes. For example, gold, platinum, Badgeul 13, Iri
Gold such as Giuno 3, rhodium, hismuth, cadmium, copper, etc.
Genus salts or complex salts and their combinations can be applied.
. In addition, the excess halide produced during the preparation of the emulsion used in the present invention
chloride compounds or by-products or unnecessary nitrates.
Salts and compounds such as acid salts and ammonium are removed.
Good too. This method is commonly used in general emulsions.
Nutel water washing method, dialysis method, coagulation precipitation method, etc. are used as appropriate.
Can be used. In addition, the filter emulsion used in the present invention ("applied at 1° to the general emulsion)"
Various chemical sensitization methods can be applied. Namely, activated gelatin, water-soluble gold salt, water-soluble platinum salt, water-soluble
V1: Palladium salt, water-soluble rhodium salt, water-soluble iridine
Noble metal sensitizers such as aluminum salts, sulfur sensitizers; selenium sensitizers,
Chemical sensitizers such as polyamines, reduction sensitizers such as stannous chloride, etc.
Chemical sensitization can be carried out singly or in combination by
You can do it. Furthermore, this silver halide is optically sensitive to the desired wavelength range.
can be sensitized. Especially for optical sensitization methods of emulsions.
There are no restrictions, such as zeromedine dyes, monomedine dyes,
Anine pigments such as trimethine pigments or melon anine
Using an optical sensitizer such as a dye alone or in combination (for example, using a strong
Color sensitization) Can be optically sensitized. These techniques are described in U.S. Patent No. 2,688,545.
, No. 2,912,329, No. 3,397,060,
3,61.5,635, 3,628,964,
British Patent No. 1,195,302, 1,242°588
No. 1,293,862, West German Patent (OLS) 2.
Column 030,326, No. 2,121,780, Special Publication No. 4
No. 14936, No. 44-14030, etc.
Ru. The selection depends on the wavelength range to be sensitized, sensitivity, etc. of the photosensitive material.
It is possible to arbitrarily define it depending on the purpose and use. The haI:I silver saponide emulsion used in the present invention further includes
Reru ha [! In forming silver saponide, the core
Silver halide grains with a grain size of substantially 1° IJi
A shell is formed on the core grain using a silver halide emulsion of
Monodisperse with almost uniform shell thickness depending on the coating width
However, it is possible to obtain a silver halide emulsion with
A substantially monodisperse silver halide emulsion has a fineness
Even if the cloth is used as is, two or more types with different average particle sizes can be used.
The above monodisperse emulsion was prepared at any stage 11.5 after grain formation.
It is blended to obtain the desired gradation and then used.
You may. The silver halide emulsion used in the present invention has a wide distribution.
The shell is coated with a substantially monodisperse core of not more than 20%
in the emulsion in a proportion equal to or greater than that of the emulsion obtained by
The silver halide of the present invention was
Those containing silver halide grains are desirable. But that (
J or halo other than the present invention to the extent that it does not impede the effects of the present invention.
3. The halogen other than the present invention which may contain silver germide grains
The silver oxide may be of the core-el type, or may be of the core-shell type or more.
It may be a different material, and it may be monodisperse or polydisperse.
It's okay. The silver halide emulsion used in the present invention
The silver halide grains contained in the emulsion are at least
It is preferable that the silver halide grains of the present invention have a 65-fold claw shape.
Indeed, almost all of them are silver halide grains of the present invention.
It is desirable that The present invention provides that the silver halide emulsion contains at least 0.5 mol of silver halide emulsion.
Milk containing tabular silver halide grains containing % silver iodide
This includes cases where it is an agent. That is, the present invention used in the silver halide emulsion layer of the present invention
In the emulsion, the silver halide grains are
Being a shell grain, ■ legalized silver tabular silver halide
grains (the legalized silver tabular silver halide grains are
Whether it is of the Asher type or of any other type.
You can. ), ■ being a mixture of ■ and ■, etc.
Any embodiment is included in the present invention. Below, legalized silver tabular silver halide grains will be explained.
Ru. The tabular silver halide grains have a grain size 5 times the grain thickness1
-I like Norano. The plate-like silver halide grains
(J Unexamined Japanese Patent Application Publication No. 58-11393, No. 58-11393)
4 shi (, same, 58-, +27921 shi J., 1ii1
58 No. 108532, No. 59-99433, No. 59
++9: Non-general manufacturing method described in (so+; etc.)
In the present invention, the colored stain
Also, from the viewpoint of the effect on image quality, etc., the particle size is 5 times the particle thickness.
, preferably 5 to 100 times, particularly preferably 7 to 30 times
It is better to use twice as much. Furthermore, the particle size is preferably 0,371 m or less, and 0.5 to 6
μ■μ is particularly preferably used. These flat plates
The silver halide grains are composed of at least one layer of silver halide emulsion.
A layer containing at least t+ 501R, "lt%" in
The aim of the present invention is to
The effect of the target is better than the previous one, and almost all of them are
When the tabular silver halide grains shown below are used,
Especially preferred 1. Let's make a good effect. Tabular HA [l silver saponide matter 1°Ir is a core-shell particle
(J3), and the core-shell
If it is a particle, the requirements mentioned above for core shell are met.
It is preferable that both conditions are satisfied. Generally, tabular silver halide grains have two parallel faces.
Therefore, in the present invention, "thickness J"
Distance between two parallel planes constituting a tabular silver halide grain
It is expressed in distance. In addition, "grain size" refers to the tabular size of tabular silver halide grains.
Refers to the diameter of the projection surface when observed perpendicular to the surface.
, if it is not circular, use the longest diameter as the diameter
Assuming that, this diameter is used. The halogen composition of the tabular silver halide grains is bromide.
Preferably silver and silver iodobromide, especially silver iodide content
It is more preferable that the silver iodobromide is 0.5 to 10 mol%.
preferable. Next, a method for producing tabular silver halide grains will be described. There are several methods known in the art for producing tabular silver halide grains.
This can be achieved by appropriately combining the methods described above. For example, an atmosphere with a relatively high pAg value of pB rl, 3 or less.
In the air, the silver saponide f11 particles were 40% with 17 clear days.
Forms seed crystals that exist above the
Seed crystals were formed by adding silver and halogen solution to the same II♂.
Obtained by lengthening. No new crystal nuclei are generated during this grain growth process.
j; It is desirable to add sea urchin silver and
stomach. The size of tabular silver halide grains is determined by temperature control and solvent
Selection of type, silver salt used during grain growth, and halogen
adjustment by controlling the rate of addition of compounds, etc.
can. When producing tabular silver halide grains, halogen is added as necessary.
Grain size and grain size can be controlled by using silver generide solvent.
Shape (diameter/thickness ratio, etc.), particle size distribution, particle formation
You can control long speed. Use of silver halide solvent 1 is I x 10 of the reaction solution
-3 to 1.0% by weight is preferred, as described in Patent I
' ~ I X 101% by weight is preferred. For example, with the increase in the amount of halogenated solvents used, halogenation
By making the silver particle size distribution monodisperse, the growth rate can be increased by 220 degrees. On the other hand, the use of silver halide solvents
There is also a tendency for silver halide grain thickness to increase with dose.
be. The silver halide solvent used is ammonia, dichloromethane, etc.
Examples include ethers and thioureas. dioe
Regarding the ether, U.S. Pat.
See No. 3,790,387, No. 3,574,628, etc.
It can be considered. Accelerate grain growth during production of tabular silver halide grains
Silver salt solution (e.g. AgNO3 aqueous solution) to be added for
and the addition rate of the halide solution (e.g. KBr aqueous solution).
A method of increasing the amount and concentration of addition is preferably used.
It will be done. Regarding these methods, see, for example, British Patent No. 1,335゜9.
No. 25, U.S. Patent No. 3,672,900, U.S. Patent No. 3,650
．． No. 757, No. 4,242,445, Japanese Unexamined Patent Publication No. 1983-1
See descriptions in No. 42329, No. 55-158124, etc.
can do. Tabular silver halide grains are chemically sensitized if necessary.
be able to. Regarding this chemical sensitization method, please refer to
You can refer to the description of the sensitization method explained in
From this point of view, the tabular silver halide grains of the present invention are gold-sensitized or gold-sensitized.
or sulfur sensitization, or these (preferably for Jl: 1.
. Tabular ha[! In the layer containing silver saponide particles ('', the average
Plate-shaped [J saponified root grains cover all silver halide grains in the layer]
40% or more, especially 60% or more by weight of
The thickness of the layer containing the 3° tabular silver halide powder is preferably 0.
．． 5 μm to 5.071 m is preferable, and 1. O) 1m
-3, OJlm is more preferable. In addition, tabular C [coating amount of 1 silver saponide grain (on one side)
) is preferably 0.5 g/m2 to 6 g/m', and Ig/m
More preferably, it is 2 to 5 g/m'. Other configurations of layers containing tabular silver halide grains
, For example, Ba, Ingu, Hardening agent, Anti-cazori 114 agent, Ha
Silver halide stabilizers, surfactants ('l agents, spectral sensitizing dyes)
There are no particular restrictions on dyes, purple I-line absorbers, etc.
For example, IN+! st! arcl+D 1sclo
surc volume 176, pages 22-28 (December 19784
).Next, from the layer containing tabular silver halide grains in 1.
The silver halide emulsion layer (hereinafter referred to as
, ``--silver halide emulsion layer'')
decrease. ” 1st place Silver halide grains used in silver halide emulsion layer
The child is a high-sensitivity halo used in ordinary direct X-ray film.
Silver germide grains are preferably used. The shape of silver halide grains is spherical or polyhedral.
or a mixture of two or more of these (7)
stomach. Especially if the particles are spherical and/or the diameter/thickness ratio is 5 or less.
60% or more (weight ratio) of the total polyhedral particles
is preferred. The average particle size should be 0.5 μm to 37 zm.
is preferable, and ammonia, dioether as necessary.
It can be grown using a solvent such as , diurea or the like. Silver halide grains are produced using gold sensitization method or sensitization method using other metals.
, or reduction sensitization method, or sulfur sensitization method (j These two
Sensitivity is increased by a sensitization method using a combination of the following
It is preferable that ” Regarding other compositions of the 1st emulsion layer, tabular halogen
Contains converted root nodules (with no particular restrictions, similar to the filtration layer).
, Said, it! s(!arch l) 1sclo
You can refer to the description in vol. 176 of Surc. Also, the emulsion used in the present invention is disclosed in JP-A-53-10372.
No. 5, No. 59-133540 S2, No. 59-1625
No. 40 etc.
It is also desirable to include Qf. According to the silver saponide emulsion iJ of the present invention:
Various commonly used additions Δ11 may be included. For example, azaindenes, lyazoles, tetrazoles
compounds, imitazoliuno compounds, tetrazolium salts, polyhydric salts,
Stabilizers and antifoggants such as doloxo compounds; aldehydes
aziridine-based, isoogizazole-based, vinyl sulfonate-based
Acrylic acid, carbodiimide, maleimi
methane sulfonic acid ester, triazine, etc.
Hardening agent: benzyl alcohol, polyoxyethylene based
Development accelerators such as compounds, Chroman series, Claman series, Bisfu
Phenol-based and phosphite-based image stabilizers; Waraku
Glycerides of higher fatty acids, higher alcohols of higher fatty acids
There are lubricants such as coal ester. Also, surfactants
As a coating aid, a permeability improver for processing liquids, etc.
Control of various physical properties of foam agents or photosensitive materials
Anionic, cationic, and non-ionic materials can be used as materials for
Various on-type or amphoteric types can be used. Especially drifting
These surfactants are eluted into processing liquids that have whitening properties.
is preferable. Diacetyl as an antistatic agent
Cellulose, perfluoroalkyl sodium
Reate copolymer, styrene-maleic anhydride copolymer
The alkali of the reaction product of and p-aminobenzenesulfonic acid
Salt etc. are effective. Polymethacrylic acid as a matting agent
Methyl, borisdylene, alkali-soluble polymers, etc.
Can be mentioned. It is also possible to use roughly colloidal silicon oxide. Ma
As a latex added to improve the physical properties of the film,
Acrylic esters, vinyl esters, etc. and other ethylene
Examples include copolymers with monomers having groups. Ze
Glycerin and glycol compounds are used as Radin plasticizers.
etc., and as a thickener,
Sodium inric acid copolymer, alkyl vinyl ether male
Indic acid copolymer activity may be mentioned.1゜C of the present invention:
Preparing emulsions and other colloidal layer coating solutions of 1 ml of water.
Hydrophilic polymers used for gelatin, gelatin,
Grafting of derivative gelatin, gelatin and other polymers
Polymers, proteins such as aldimine, casein, human
xyethylcellulose, carboxymethylcellulose t-north
cellulose derivatives, starch derivatives, polyvinyl)
-! -L, polyvinylimidazole, polyacrylamide
Synthesis of copolymers such as t11 aqueous polymers, etc.
The offspring of , those of α are included. Hattl Silver Saponide Color Photographic Sensitivity +A Another Support of the Present Invention
as ('', e.g. Gallis tentative, Zel [J-suacetate
, cellulose nitrate or polyethylene terephthalate
-1 Polyester film, polyamide film etc.
, polycarbonate film 1 Borisdylene film, etc.
In addition, conventional reflective supports (e.g. baryta paper 2
, polyethylene coated paper, polypropylene synthetic paper, reflective layer
A transparent support with a reflector or a reflector) may also be used.
These supports can be used as appropriate depending on the purpose of use of the photosensitive material.
Be selected. Silver halide emulsion layer used in the present invention and its
Other photographic composition layers can be applied by dipping, air coating, etc.
Doctor application, curtain application, hopper application re-application
A fabric method can be used. Also, US Pat. No. 2,761. , No. 791, 2,94
Simultaneous application of two or more layers by the method described in No. 1,898
Laws can also be used. The silver halide emulsion of the present invention is applicable to color photosensitive materials.
To achieve this, the red sensitivity, green sensitivity, and blue sensitivity are sensitized and adjusted.
Cyan, magenta and
Coupled with yellow couplers, etc.
By applying the methods and materials used for color photosensitive materials,
good. Silver halide color photographs to which the bleach-fix solution of the present invention can be applied
True photosensitive (O14 (J, color former or contained in the photosensitive material)
Internal development method 1 ((U.S. Pat. No. 2,376.679, same)
2,801,171), as well as color formers in the developer.
(U.S. Pat. No. 2,252,7)
18th, 2,592,243 shi (, 2,590,9
70-), see L). Also a coloring agent
may be any commonly known in the industry.
. For example, as a cyan coloring agent, naphthol or fluoride is used.
Based on the phenolic structure, Indian anidine is produced by coupling.
Those that form phosphorus pigments, and as magenta coloring agents, are active
The skeleton structure is a 5-pyrazolone ring with a polymethylenyl group.
Active methylene is used as a yellow coloring agent.
benzoylacedoanilide with chain, pivalyl acetate
Items with acylacedoanilide structure such as toayulite
etc., with a substituent at the coupling position, such as rT L.
You can use any of the following. As a coloring agent like this
is a so-called 2-equivalent type coupler and 4, +-1j-(H1
Any coupler can be applied. The black and white developer which can be used in the processing of the present invention is generally known.
For processing silver halide color photosensitive material 1, which is
What is called the black and white first developer used, or black
It is used for processing white photographic materials, and is generally
Contains various additives added to black and white developer.
I can do it. A typical additive is 1-phenyl-3-pyrazolide.
developing agents such as methane, metol and hydroquinone,
Preservatives like sulfates, sodium hydroxide, sodium carbonate
Accelerators consisting of alkalis such as aluminum, potassium carbonate, bromide
Potassium, 2-methylbenzimidazole, methylben
Inorganic or organic inhibitors such as tuthiazole, po
Water softeners like lyphosphates, trace amounts of iodides and merca
Examples include surface overdevelopment inhibitors consisting of photochemical compounds.
can. Color developer used before processing with the bleach-fix solution of the invention
The aromatic primary amine color developing agent used in the developing solution is
Widely used in various color photographic processes
It includes a variety of things. These developers are amino
Contains phenolic and p-phenylenediamine derivatives.
be caught. These compounds are more stable than the free state.
Generally used in salt form, e.g. hydrochloride or sulfate.
Ru. In addition, these compounds (well, generally color developer IQ
It is preferably used at a concentration of about 0.1 g to about 30 g.
More preferably +J: about 1g for IQ
Use at a concentration of ~15 g. Examples of aminophenol-based developers include 〇-amino
Phenol, p-aminofurol, 5-amino-2
-human [l gisotoluene, 2-amino-3-hydroxy
Tol'°, n, 2-hydroxy-3-amino-1,4 di
Contains methylhenzen etc. A particularly useful aromatic primary amine color developer is N. N-dialkyl-p-)J-nirenno)2mine-based compounds
Yes, argyl J+'i lk, and phenyl L';
may or may not be replaced. Among them, the most important compound is N,N-die.
Chil-p-phenyleneno)'mine hydrochloride, N-methyl
=p-phenyleneamine hydrochloride, N,N-dimethyl-
p-phenylenediamine hydrochloride, 2-amino-5-(N
-Ejiru N-dodecylamino)-toluene, N-ethyl
LeuN-β-methanesulfonamidoedyl-3-methyl
-4=aminoaniline sulfate, N-ethyl-N-β-hyperoxychloride
)・Roxyethylaminoaniline sulfate, 4-amino-
3-Methyl-N,N-diethylaniline sulfate, 4-a
Mino-N-(meth)xyethyl1)-N-ethyl-3
-Medyl aniline-p-1 luene sulfonate etc.
can be done. Particularly useful color developing agents in the present invention include amino group-1
- at least one water-soluble group (hydrophilic group)
It is a laphenylene diamine color developing agent.
The following compounds are typical color developing agents.
However, the present invention is not limited thereto. (1) (+ll+ C2111NllS
DzCII+ゝ, / ■ (2) CHlli C+1LOll\, / ■'', N11゜(3) C+ll+ CH111011■ N11゜(4) CHll, C+1LOClh゛\\ / Nll. (S) C, Il, C, 11, So, 11
(6) CH, C, Il, OH\, / (7) 1lOc+IL C, ILOI+□ 811□ ”” C, 11, ciniso, u□ NH. (91C, 11, C, 11, 5Dl11ゞ・/ (+0) II C1hCOO11■ ,l N11゜(II) C411h (cll, cll, o)
, cll. Nll. (121C1l+, (C1bC1l, O), el
l. N/Nt(+3)Cn115(C11,C1hO1,C1l+. (+4) C+lIi (ClhCII+0h
CJi゛,' th Color developing agents particularly useful in the present invention include
-(Ctl,)ncH7oll, -(CI
l2) mNH302(Ctlp)nctls, (
Compounds having CIl, )mo(CI,)nCH3 groups
Specific compounds include (]) of the above specific examples,
(2), (3), (4), (6) and (7) are listed.
Ru. However, m and n are integers of 0 to 6, preferably O
~5. The paraphenylenediamine color developing agent is
It is preferable to mix it into the bleach-fix solution. Alkaline used before treatment with the bleach-fix solution of the invention
The phosphorescent color developer is the aromatic primary amine color developer.
In addition to the color developer, various
Ingredients such as sodium hydroxide, sodium carbonate,
Alkaline agents such as potassium, alkali metal sulfites, alkaline
Potash metal sulfites, alkali metal thiocyanates,
alkali metal [l saponified product, benzyl alcohol, diene
thylenetriamine Il acetic acid, l hydroxyethylidene
- Water softeners and thickeners such as 1,1-diphosphonic acid, etc.
It can be included as desired. pHi of this color developer
J, usually more than 7-1 U, most commonly about 10 to about
It is 13. The bleach-fixing solution according to the present invention is suitable for color paper, color
Positive film 8, color positive film, color for slides
- Reversing film, color reversing film for movies, TV cameras
Invention of color reversal film Is, reversal color paper, etc.
Silver halide color photography using emulsions applied to different photosensitive phases
However, especially when the total amount of silver coated is 50mg/dm
High-sensitivity color photographic photosensitive material containing silver iodide of 2 or less (A
most suitable for processing. [Example] Hereinafter, the present invention will be explained in detail with reference to Examples.
The embodiments of the present invention are not limited thereby. Example 1 High-sensitivity silver halide color photography in the industry
Following the layer structure adopted in the
The anti-halation layer and the red-sensitive film are applied from the support side.
Silver halide emulsion layer, green-sensitive silver halide emulsion layer and blue
A light-sensitive silver halide emulsion layer, and the blue-sensitive silver halide emulsion layer.
A highly sensitive silver halide emulsion layer with high sensitivity dispersion is placed on the outermost side of the silver emulsion layer.
Arranged. That is, the sample was prepared according to the following, but the amount of coated silver was kept constant.
'; Change the amount of gelatin to adjust the film thickness and change the dry film thickness.
A sample was prepared. The amount of silver applied is approximately 47mg
/dm2. However, the following are standard coating conditions, and due to changes in film thickness.
Each formulation was adjusted by varying the amount of gelatin. Layer 1: Using hydroquinone with silver nitrate as a reducing agent
Reduces to provide high absorption of light in the wavelength range of 400 to 700 nm.
Dispersion of 0.9 g of black colloidal silver shown in 3 g of gelatin
An anti-halation layer was applied. Layer 2: Middle layer made of gelatin. (Dry film thickness 0.8
low-sensitivity red-sensitive silver iodobromide emulsion (Ag
l. 6 mol%), 2.0 g of gelatin 11 and I, Q O
g of l hydroxy-4-(β-methoxyethylaminoca
(rubonylmethoxy)-N-rδ-(2,,I-)-t
-aminophenoxy)butyl 1-2-naphthamide (hereinafter referred to as
Below, cyan coupler (referred to as C-1)) 0.030g
1-Human D-Hydroxy 4 t4-(+-Hydroxy 2-
Ace!・Amide 3. (i-disulfo-2 naphthylazo
) Phenoquine L-N-1δ-(2,4-di-t-amino
Nophenoxy)butyl-1z naphthamide dinatri
Uno (hereinafter referred to as colored cyan coupler (CCI)
・0.5g of tricresylpofu in which 1') was dissolved:
r, -1' (hereinafter referred to as 1/'', 'l'CI') (
Low-sensitivity 11 red-sensitive silver-genide emulsion layer. Layer 4: 1.3 g of crystal-sensitive red-sensitive silver iodobromide emulsion (A
gl; 7 mol%), 1.4 g of gelatin
．． 39g of cyan coupler (C2), O, (124g of
Q, 18 in which colored cyan coupler (CCI) was dissolved
High-sensitivity red-sensitive halogen containing g'i' CI)
silver emulsion layer. Layer 5...009g of 2.5-di-t-octylhydro
Quinone (hereinafter referred to as anti-pollution agent (1-IQ-1))
Dissolved (7004g of embodilphthalate (hereinafter referred to as D
13 P) and 1.2 g of gelatin.
middle class. Layer 6...1.6g of low-sensitivity green-sensitive silver iodobromide emulsion (Δ
g1; 18 mol%), 1.7 g of gelatin and 0.4
4g of 1-(2,4,6-dolichlorophenyl)-3-
i:3-(2,4-di-t-amylphenoxyacetoacetate)
(mido)hensenamide]-5-pyrazolone (hereinafter referred to as
Zenta coupler (referred to as Comparison-1)), 0.064 g
1-(2,4,,6-1-lichlorophenyl)-4=(
1-naphthylazo)-3-(2-chloro-5-octade
cenylsuccinimidoanilino)-5-pyrazolone (hereinafter referred to as
Below, colored magenta coupler (CM-+))
Low sensitivity green light containing 0.3g dissolved TCP
silver halide emulsion layer. Layer 7...1.5 g of high-sensitivity green-sensitive silver iodobromide emulsion (A
gl. 11 mol%), 1.9 g gelatin and 0.137 g
magenta coupler (comparison-1), 0.051. g's ma
Zenta coupler (M-2), 0.04! Ig colored
Dissolve magenta coupler (CM-, 1) 1. 80, 12
Sieve sensitivity green photosensitive Ha v1 containing g i' CI)
Silver saponide emulsion layer. Layer 8... 083g of yellow 2IU) silver, 02g of
Dissolving the antifouling agent (HQ-1) 1. 80, l Igo
) I)! 31' and 2.1 g of gelatin.
1 degree ruye [no filter one layer. Layer 9...1.02g of low-sensitivity blue-sensitive silver iodobromide emulsion (
Agl; 4 mol%), 1.9 g of gelatin, 11ζ and
1.84 g of α-[4,-(1--benzyl-2-])
J Nilu 3.5-Giogyso 1.24-1-Riazolidi
]-]α-pivaloyl-2-chloro517-(
2,4-di-t-amylphenoxy)butanamide]a
Cetanilide (hereinafter referred to as yellow coupler (Y-1))
0.93 g of D 11 P dissolved in
Sensitivity Blue-sensitive silver halide emulsion layer. Layer IO...1.6g of high-sensitivity dispersion blue-sensitive silver iodobromide
Emulsion (Agl; 4 mol%), 2.0g Nozeradji: / 1
11<bi+,: 0.46g of yellow coupler (Y-1
) dissolved in 0.23g of I) BP containing high sensitivity
Blue-sensitive silver halide emulsion layer. Layer 11: 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 each sample was 3.
5/Z 4 types: m, 2571m, 20μm, 1871m
Samples No. 1 to 4 in the class. As yet another trial 1, in the green-sensitive silver halide emulsion layer
Compare the magenta couplers in -1 and the same number of moles in -2
Changed materials (No. 5 to 8), example mazen according to the present invention
Sample replaced with Tacoupler IVI-5 (No, 9~)
-2), sample replaced with M-44 (No, 13-16
) was also created. In addition, the film swelling rate T% of the binder is 2
It was 0 seconds. Processing steps include color development for 3 minutes and 15 seconds, bleach fixing for 3 minutes, and first stabilization.
The stabilization period was 2 minutes, and the second stabilization period was 30 seconds. Each treatment was performed at 37.8℃, and each treatment solution was treated as follows.
A treatment solution prepared by the method was used. [Color developer] Potassium carbonate 30g sulfite
Natriuno・2.0g Hitrogishi
Ruamine sulfate'f, A2, 0 gl-
Hydrogine J'-Dylidene 1.1-diphosphonic acid ((
10% aqueous solution) 1. Og Kariuno Bromide,
1.2g magnesium chloride,
0.6g hydroxide
rSino,
3.4g N-ethyl-N-β-hi
Add 4.6g of water to the mixture
and adjust the pH to 10.1 with thorium hydroxide.
3. [Bleach-fix solution] Ethylenediaminetetraacetic acid noammonium salt 7.5g diethyl
0.35 mol ammonium sulfite, (50% solution)
, Ogdiosulfuric acid ammouno (70% solution lr&)
Add 200.0g water and get IQ and 17, ammonium hydroxide
The pH was adjusted to 7.5 with sodium chloride. [First stable solution] ■-Hydroxyethylidene 1.1-diphosphonic acid 3,0g 5-chloro
Rho-2-medyru-4-isothiazolin-3-one], Og Edylene
Glycol 1.0g Add water
and adjusted to pI-17.1 with potassium hydroxide. [Second stable solution] Polmarin (37% solution) 7,0
Add mI2 water to make it +12. Exemplary compound (+) is added to the bleach-fix solution as a bleach accelerator.
0.7g was added per C. The processed sample had a residual silver content of 1100 in the green-sensitive emulsion layer.
Measured using two methods: spectral absorption at 0n and fluorescent X-ray.
and compared them. Spectral absorption measurements are performed using l(10(lnm)
It was measured with an optical densitometer using an interference filter. The results are shown in Table 1. Comparative magenta coupler (2) Table 1 As shown in Table 1, among the constituent requirements of the present invention, film thickness and barrier
Even if the inder film swelling speed TX and coated silver amount are satisfied, the conventional
As long as you use a magenta coupler, there will be only traces of residual silver.
Accepted (sample 2.3.46.78), L or the present invention
By using a magenta coupler related to
degree of silver can be completely removed (sample 10.+1.12.1
4. +5.16) A surprising effect was obtained. Again, this trace
The degree of silver cannot be removed simply by reducing the film thickness to Qj.
, both are shown. Note that the magenta coupler is an exemplary coupler M according to the present invention.
-7, M-18, M-It, M-4M-59, M-1
00, M-104, M-116, M-142
The experiment was repeated with a thickness of 25 μm or less, but the spectral absorption was
No residual silver was detected by either the collection method or the fluorescent X-ray method.
. Example 2 Samples 1.5.9 and 13 of the same composition as in Example 1
Using emulsion, 100 8/d+a', 70t++H/d
111i in 3 types of theory 2.30 lees 8/c1m2! Arranged,
And by changing the amount of hardening agent, the film swelling speed T was increased to 10 seconds.
A total of 24 types of samples were prepared by adjusting W4 to two types of 35 seconds.
Samples 17-40). The film thickness was adjusted to 20 μm. Exactly the same as Example 1
The amount of residual silver was measured after processing and bleaching and fixing time was set to 3 minutes.
Ta. The results are shown in Table 2. Table 2 also shows that the amount of coated silver and the film swelling rate T are outside the conditions of the present invention.
Below, even if we use the magenta coupler of the present invention,
Effect of completely removing trace amounts of silver in the film at the final stage of desilvering
It turns out that you can't get it. Only when all the constituent requirements of the present invention are satisfied can the bleach-fixing speed be increased.
Extremely fast and completely removes trace amounts of residual silver in the film
As a result, the bleach-fixing time of Tenkawa can be significantly shortened.
That thing is buried. Example 3 Among the samples prepared in Example 1, one with a film thickness of 20 μm (test
Fee 3,7. 1+ and 15) in the bleach-fix solution.
The effect of changing the ferric acid complex salt as shown in Table 3 is compared.
compared. ^11 results are shown in Table 3. Table 3 As is clear from Table 3, various organic acid ferric complex salts were used.
However, the effect of using the magenta coupler according to the present invention is
It is fully demonstrated. 1.2-diaminopropanetetraacetic acid
In the case of ferric complex salt and ethylenediaminetetraacetic acid ferric complex salt
The effect is slightly reduced and a small amount of silver remains. This exists
There is no difference between the molecular weight and oxidizing power (desilvering ability) of the ferric acid complex salt.
This suggests that there is a correlation between 1. I haven't come to a conclusion yet
It is difficult. However, in any case, there is no practical problem.
The amount of residual silver is not a problem, and it does not impair the effects of the present invention.
isn't it. Applicant Roku Konishi Photo Industry Co., Ltd. 5, 11 hand-edited pieces subject to correction? I IT , -+ to Xi IV (-gar 1:
() 1985 Mochiju 1'1 Application No. 25 [i 382
2. Name of the invention Silver halide color copying L"L exposure + A processing method 3.
Special case related to amendment 3'F Ill 1rI 11 people
Address: 1-1126-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Contact information: 191 Bundle 1; f+1-1! I! F City Sakuracho 1 Konishiroku
Photo (°Kuchinigyo Co., Ltd. (Telephone: 0425-83-152)
) of the description [Special j)'1 Claim 1 column and [Invention
Detailed explanation 1 column (authentic handwriting 1-14 and 31-33) 6. Details of amendment r) a↑11 As per attached sheet (no change in content)

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 green-sensitive silver halide emulsion layer has the following general formula [C I
contains a magenta coupler represented by ], and the total thickness of all photographic constituent layers excluding the support is 25 μm or less,
and the membrane swelling rate T1/2 of the binder in the photographic emulsion layer is 2.
A silver halide color photograph, characterized in that a silver halide color photographic light-sensitive material is imagewise exposed for 5 seconds or less, developed, and then processed with a bleach-fix solution containing at least one organic acid ferric complex salt. How to process photosensitive materials. General formula [C I] ▲ Numerical formulas, chemical formulas, tables, etc. You may. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Moreover, R represents a hydrogen atom or a substituent. (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 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 1.25 mol % or less. A method of processing photographic materials. (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 includes ▲mathematical formulas, chemical formulas, tables, etc.▼▲mathematical formulas, chemical formulas, There are tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲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. ▼, -SZ' or n_1-valent heterocyclic residue (including those with at least one 5- to 6-membered unsaturated ring fused to it) represents,
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 fused to it) or an amino group, and Y represents ▲a mathematical formula, a chemical formula, a table, etc.▼or ▲a mathematical formula, a chemical formula, a table, etc. ▼, Z is 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 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
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 have ▲mathematical formula, chemical formula, table, etc.▼, ▲mathematical formula, chemical formula,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ , where R^8 is an alkyl group or -(CH_2)n_8
Represents SO_3^- (however, R^8 is -(CH_2)n_
When 8SO_3^-, l represents 0 or 1. )G^-
are anions, m_1 to m_4 and n_1 to n_
8 represents an integer from 1 to 6, and 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 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. X' is -COO
M', -OH, -SO_3M', -CONH_2, -S
O_2NH_2, -NH_2, -SH, -CN, -CO
_2R^1^6, -SO_2R^1^6, --OR^1
^6, -NR^1^6R^1^7, -SR^1^8, -
SO_3R^1^8, -NHCOR^1^8, -NHS
O_2R^1^6, -OCOR^1^8 or -SO_2
Represents R^1^8, and Y' is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼ Or represents a hydrogen atom, and m and n each represent an integer from 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) ) ▲ 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