JPS6271954A - Processing of silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To make possible to coexist the resource protecting with the upper sensitivity of the titled material by incorporating a specific cyan coupler into a red color photosensitive silver halide emulsion layer, and by specifying a thickness of the constituting layer and the swelling rate of a film of a binder, and by processing the titled material with a bleach- fixing solution contg. the two valent iron complex of an organic acid. CONSTITUTION:The red color photosensitive silver halide emulsion layer comprises the cyan couplers shown by formula I or II. And the sum of the thicknesses of the photosensitive constituting layers is especially preferable to be <=20mum. The film swelling rate T1/2 of the binder contd. in the photographic emulsion layer is the most preferable to be <=10sec. The titled material having the properties as mentioned above is exposed imagewise, and then developed followed by processing it with the bleach-fixing solution contg. the two valent iron complex of the organic acid. The photographic constituting layer means all hydrophilic colloidal layers which take part in the formation of an image, and lie in the same surface to that coated with at least 3 layers of a blue color, a green color and a red color photosensi tive silver halide emulsion layers on the surface of the substrate. When an anti-halation layer of the black colored colloidal silver is provided, the processing is especially effective. The concrete compds. of the cyan coupler shown by formula I or II are the compd. shown by formoula III.

Description

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

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

[Prior art]

Generally, in order to obtain a color image by processing an imagewise exposed silver halide color photographic light-sensitive material, after the color development process, the generated metallic silver is removed by a bleaching process. ! ! A process of processing with liquid is provided. As processing liquids having i-print whitening ability, N-print whitenami and bleach-fixing solutions are known. When a bleaching solution is used, the bleaching step is usually followed by a step of fixing the silver halide with a fixing agent, but sometimes a bleach-fixing process is performed in which bleaching and fixing are performed in one step. A5' Silver power 2 - Processing solutions with bleaching ability in the processing of photographic light-sensitive materials include inorganic oxidizing agents such as red blood salt and dichromate as oxidizing agents for bleaching WfJ image silver. is widely used. However, several serious drawbacks have been pointed out to processing solutions containing these inorganic oxidizing agents and having bleaching ability. For example, red blood salt and dichromate are relatively excellent in terms of bleaching blades for image silver, but there is a risk that they will decompose when exposed to light and produce cyanide ions and hexavalent chromium ions that are harmful to the human body. It has unfavorable properties in terms of pollution prevention. In addition, because these oxidizing agents have extremely strong oxidizing power, it is difficult to coexist with halogenated solubilizers (fixing agents) such as periosulfate in the same processing solution, and these agents are not included in the bleach-fix solution. It is almost impossible to use oxidizing agents of
This makes it difficult to achieve the goal of speeding up and simplifying processing. Furthermore, treatment liquids containing these inorganic oxidizing agents have the disadvantage that it is difficult to reuse them without discarding the waste liquid after treatment. On the other hand, metal complex salts of organic acids such as amine/polycarboxylic acid metal complex salts are used as oxidizing agents as they meet the requirements of speeding up and simplifying treatment, and enabling reuse of waste liquids, with less quantification in terms of pollution. In recent years, treatment solutions have come to be used. However, processing solutions using metal complex salts of organic acids have weak oxidizing power, so the image formed during the development process is silver (metal!
! The disadvantage of t) is that the bleaching rate (oxidation speed) is slow. For example, iron ethylenenoaminetetraacetate (II
I) Complex salts have been put to practical use in some areas as bleach-fixing solutions; Color negative film and color reversal film for photography that contain silver oxide lack a bleaching blade, and even after long processing, traces of image silver remain, resulting in poor desilvering. This tendency is particularly apparent in bleach-fix solutions in which an oxidizing agent and periosulfate and sulfite coexist because the redox potential decreases. In particular, it has been found that in high-sensitivity silver iodide-containing silver halide color photographic light-sensitive materials for photography which contain black colloidal silver for prevention of halation, the desilvering properties are markedly deteriorated. Furthermore, there is a core-shell emulsion that has recently been developed as a silver halide emulsion which is a highly sensitive silver iodide-containing emulsion, has fine grains, and effectively utilizes silver to meet the requirements for resource conservation. The preceding silver halide emulsion is used as a crystal nucleus, and the subsequent precipitation is applied on top of it by the sequential product/[N
L, monodisperse core-shell milk temperature created by graphically controlling the composition or elapsed environment of each precipitate, f. Among these, the core-shell type high-sensitivity emulsions containing silver iodide in the core and/or shell have extremely favorable photographic performance characteristics, but conventional bleach-fixing baths cannot be used for silver halide color photographic light-sensitive materials. When applied, it has been found that the bleach-fixing properties of developed silver and silver halide are extremely poor. That is, developed silver of a photographic silver helodenide emulsion containing 0.5 mol% or more of silver iodide, especially a core-shell emulsion, in which the core and shell contain 0.5 mol% or more of silver iodide. Developing silver particlesAlthough silver has excellent sensitivity, granularity, covering power, etc., in the case of color photographic materials that require bleaching of the developed silver, the form of the developed silver is different from conventional ones, so the bleaching properties are poor. Deteriorate. In particular, as an emulsion, JP-A Nos. 58-113930, 58-113934, and 5
8-127921 and 58-108532, etc., which use tabular silver halide grains, the number of photons captured by the silver halide grains increases. It is said that even if the amount of silver used increases, the amount of silver used will not increase, and the image quality will not deteriorate. However, even these tabular silver halide grains have the disadvantage that developed silver formed by development with a p-phenylenenoamine 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 Daishi salt, the total thickness of all photographic layers excluding the support of the light-sensitive material and the film swelling rate T of the binder in the photographic emulsion layer must be kept below a certain value. I found something good. However, implementing such rapid processing has created a new problem: fading of the cyan dye due to unrefined storage. The fact that dye fading occurs means that the information obtained has already begun to change at the time the dye begins to fade, which means that it is extremely difficult to preserve accurate information for a long period of time. This is also a major weakness of silver halide photosensitive materials compared to imaging systems using electronics, which have made remarkable progress in recent years. It has become important to improve both the speed and reliability of transmission systems6.

[Purpose of the invention]

The first object of the present invention is to provide an excellent bleach-fixing method for highly sensitive fine-grain type, high-sensitivity silver iodide-containing silver halide color photographic materials that can achieve both resource conservation and ultra-high sensitivity. be. A second object of the present invention is to provide a processing method using a bleach-fix solution that enables rapid processing of high-sensitivity color photographic materials and reduces the degree of fading of the obtained cyan dye.

[Structure of the invention]

As a result of intensive research, the inventor has found that blue sensitivity, green sensitivity and
It has a photographic constituent layer including a red-sensitive silver halide emulsion layer.
, the total coating silver amount is 50mH/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 halide and contains red-sensitive silver halide grains.
The silver halide emulsion layer has the following general formula (C1) * or (CII)
Contains a cyan coupler represented by :] and has a photographic composition
The total thickness of the layers is 25 μm or less, and the photographic emulsion layer
The film swelling rate Ty2 of the binder is 25 seconds or less.
Silver halide color photographic material is developed after imagewise exposure.
, containing a small amount of ferric salts of organic acids
By treating with a liquid, the eye general formula of the present invention (
CI) General formula (C[[) In the formula, Y is -con2, -CONIICOR2 or -CONHSO□R2(R2
is an alkyl group, an alkenyl group, a cycloalkyl group, an ali
R1 represents a hydrogen atom, an alkyl group, or a heterocyclic group;
ru group, alkenyl group, cycloalkyl group, ru group, aryl group
or represents a heterocyclic group, in which R2 and R1 are bonded to each other,
Five or six shell rings may be formed. ), and R1 is the bar
represents a last group, 2 is a hydrogen atom or an aromatic primary amine
Can be released by coupling with oxidized form of color developing agent
represents a group. Preferably, the organic acid ferric complex salt is
Examples include those selected from (a) to (q) described in Section 13.
It will be done. Here, photographic Mt layering refers to the blue sensitivity and green sensitivity of the present invention.
, coated with at least three silver halide emulsion layers on the red-sensitive surface.
It is located on the same side as the installed support surface and is involved in image formation.
Refers to all hydrophilic colloid layers, black colloidal silver halide
It is particularly effective when there is an anti-shock layer;
In addition to silver halide emulsion layers, for example, subbing layers, interlayers (single
intermediate layer, filter layer, ultraviolet absorption layer, etc.), protective layer
etc. More preferably, the bleach-fix solution and/or pre-fix solution contains
Bleaching accelerator selected from the following general formulas [I] to [VII]
Examples include embodiments containing the following. y margin General formula CI) General formula (, n) General formula CI [
l) General formula (IV) General formula (V) General formula (Vl
) General formula [■] 8 units R1 → In the above general formula, Q is a heterocycle containing one or more N atoms (5
At least one unsaturated ring of ~6 shellfish is fused to this
A represents the atomic group necessary to form rt
B
represents an alkylene group having 1 to 6 carbon atoms, and M is divalent gold.
represents a genus atom, and X and X″ represent =S, =O or =NR″
R' is a hydrogen atom, alkyl having 1 to 6 carbon atoms
group, cycloalkyl group, aryl group, heterocyclic residue (5
At least one unsaturated ring of ~6H is fused to this
1 to 6 alkyl groups, cycloalkyl groups, ants
group, heterocyclic residue (with at least 5 to 6 unsaturated rings)
(including those fused to this) or amine 7 groups
, R2, R, R', R5, R and R' are each,
Hydrogen atom, C1-C6 furkyl group, hydroxy group,
Carboxy group, amino group, acyl group having 1 to 3 carbon atoms, a
Represents a lyl group or an alkenyl group. However, R4 and R
5 may represent -B-8Z (also R, R', R2
and R3, R4 and R5 are each cyclized with each other to form a heterocycle.
residue (at least one unsaturated ring of 5 to 6 shells fused to it)
(including those that are) may be formed. RG, , R7 each represent a blank space R@R1 below, R1 is an alkyl group or -(CHz)n, 30.
0, provided that R8 is -(CH2)I16S O30
When, GO represents 0 or 1,)GO represents anion, ugliness, etc.
t・shi1 and nl to n are each integers of 1 to 6,
Ils represents an integer from θ to 6, R' is a hydrogen atom, an alkali
Lis. However, Q' has the same meaning as Q above. D is just a conclusion
Agate, 1 to 8 monovalent fullkylene groups or nylene groups
, q represents an integer from 1 to 10, and multiple Ds are the same
(The ring formed with the sulfur atom is
may be fused with 5 to 6 unsaturated rings, X'+! -C
OOM', -0Hl-8o1M', -CON H2, -
8O2N H2, -N H2, -8) 1, -CN, -C
O2R", -S 02R", -OR+ 6, -N R1
! RI? , -8R", -8o,R", -NHCOR
", -NH3O,R", -0COR or -502R'6, Y' is or water
Represents an elementary atom, and 1 and n each represent an integer from 1 to 10.
vinegar. RzJ2. R eyes RIS, R17 and RIB are hydrogen atoms
child, lower alkyl group, acyl group, or 1(+1 -(C+-X'), R+a represents a lower alkyl group. R" is +
N represents R20R21, -0R22 or -5R22,
R211 and R21 are hydrogen atoms or lower furkyl groups
R22 is necessary to connect with R+s to form a ring.
Represents an atomic group l (2° or R2+ and R'″ are connected
may form a ring. M' is a hydrogen atom or a cation
represent. In addition, compounds represented by the above general formulas [I] to (V)
The present invention includes black colloidal silver as an antihalation layer.
an emulsion containing at least 0.5 mole % silver iodide as
A high silver halide emulsion layer having at least three silver halide emulsion layers containing
Bleaching and fixing of sensitive fine-grain silver halide color photographic materials
Focused on the phenomenon of poor gender, and conducted extensive research.
As a result, the total amount of coated silver and
The thickness of the emulsion layer is below a certain value, and the g of the binder is
If the IwfR speed T1/2 is 25 seconds or less, the organic acid
Even bleach-fix solutions containing 2-iron salts can be sufficiently desilvered.
This is what we found. Furthermore, specific embodiments according to the present invention
When processing with a bleach-fix solution containing a combination of
Diffusion of silver halide color photographic materials containing silver iodide
It has been found that the time required to complete white fixation is further shortened. especially
A photographic constituent layer consisting of a silver halide emulsion in a photographic material was developed.
If it becomes thinner than a certain value due to light, the bleach-fixing properties will deteriorate.
It was also found that desilvering defects were improved.
It is. Furthermore, surprisingly, the present inventors have discovered the presence of organic acid ferric complex salts.
The larger the molecular weight of W1 acid, the better the photographic constituent layer (gelatin film).
Due to the decrease in the swelling rate T1/2 of the Bangu membrane,
The bleaching accelerating effect increases and the bleaching time is significantly shortened.
I discovered this fact. On the other hand, the smaller the molecular weight of the organic acid in the organic acid ferric salt, the more
Drifting due to decrease in thickness of true MIttit layer (gelatin film)
The whitening promoting effect is increased and the bleach-fixing time is also significantly shortened.
I also discovered that it can be done. That is, in general, the molecular weight of the organic acid in the organic acid ferric salt is large.
As the temperature increases, the oxidizing power of silver increases, but it is difficult to harden the photographic constituent layers.
The use of the bleach-fixing solution also increases, and the diffusion and penetration of the bleach-fixing solution decreases significantly, resulting in bleaching.
White fixation is inhibited, and this is compared to the thickness of the photographic constituent layers.
The gelatin membrane swelling rate is extremely fast.
This inhibition does not occur if the property is present. Contrary to this
APL with small molecular weight! The oxidizing power of silver in ferric complex salt is
Although it will be slightly weaker, the bleach-fixing inhibition will be small, so it will be better for photographic composition.
If the layer becomes thinner than a certain value according to the present invention or as described above,
If the membrane swelling rate of gelatin is high, there will be sufficient drifting.
It was discovered that a white blade could be obtained. Furthermore, photographs of silver halide color photographic materials containing silver iodide
As the thickness of the constituent layer increases, black colloidal silver-containing halide
Boundary area between silver iodide-containing silver halide emulsion layer and silver iodide-containing silver halide emulsion layer
Bleach-fixing highlighted due to significant desilvering failure in minutes
Inhibition is also achieved by thinning the photographic constituent layers below a certain value according to the present invention.
and increase the swelling speed of the gelatin membrane to a certain value or higher.
We have found that this can be reduced by Therefore, according to the present invention, ferric organic acids of any molecular weight can be used.
Revolutionary technology that does not impair bleach-fixing properties even when complex salts are used
They discovered a rapid bleach-fixing method. According to a preferred embodiment of the invention, silver halide color
-Photographic edge of photosensitive material/1! Layer thickness is 22μ or less
, particularly preferably 20 μI or less, and
Swelling speed T3A is 20 seconds or less, particularly preferably 15 seconds or less
10 seconds or less, most preferably 10 seconds or less, and
The organic acid that forms the promoter and the organic acid ferric complex salt is the following compound.
One example is that it is a thing. Through these, the purpose of the present invention was effectively achieved.
I found out. Below margin (3) )+2N CN11NHCNH211I (4) +1O-CH2-C)I-CI1251+
(5) Its-CI12C12-COOHH Akebono 0H (2B) 1ISCH2CH2NHC112CH2
0H (29) H5CII, CI, NCH2CH2
1.2
-7mi/propanetetraacetic acid ml, 3-diaminopropane
-2-oltetraacetic acid (g) ethylenenoamine di-hydroxy-7enyl vinegar
Acid (h) Ethylenecyaminetetrapropionic acid (i) Nitrilotriacetic acid (j) Iminodiacetic acid (k) Methyliminodiacetic acid (1) Human axyethyliminodiacetic acid (Import) Ethylenecyaminetetrapropionic acid (n) Dihyde
Droxyethylglycine (a) nitrilotripropionic acid (p) ethylenenoamine diacetic acid (q) ethylenediamine dipropionic acid and most effective
In a preferred embodiment, after color development processing, bleach fixation is performed.
A processing method that performs fixing treatment as a pretreatment process
Therefore, the purpose of the present invention described above can be achieved most effectively.
I discovered that. Afterwards, this fixing process will be performed as pre-fixing process or
This is called pre-fixing, and the processing liquid used in the pre-fixing process is
Physical solution or pre-fixing solution or pre-fixing treatment bath or pre-fixing bath
call. The present invention will be explained in more detail below. First, general formula (C1) or (Cn
) will be explained. Said one
In the general formula (CI) and [CH3, Y is -COR2
, ≧ -CONHCORz or -CONIISO□R2
This is the group that is used. Here, R2 is a furkyl group, preferably having 1 to 20 carbon atoms.
alkyl groups (e.g. methyl, ethyl, t-butyl, do
decyl, etc.), alkenyl group preferably having 2 to 20 carbon atoms
Alkenyl group (e.g. 7lyl group, heptadecenyl group, etc.)
, a cycloalkyl group, preferably one with 5 to 7 shells (e.g.
(e.g., cyclohexyl), aryl groups (e.g., phenyl),
group, tolyl group, naphthyl group, etc.), heterocyclic group, preferably
contains 1 to 4 nitrogen atoms, oxygen atoms or sulfur atoms.
Heterocyclic groups with 5 to 6 rings (example: 7-lyl group, chenyl group)
R1 is a hydrogen atom
Or 6R2 and R1 representing the group represented by R2 are mutually
bond to form a 5- to 6-shell heterocycle containing a nitrogen atom
You may. Note that any substituents may be introduced into R2 and R1.
For example, an alkyl group having 1 to 10 carbon atoms.
(e.g. ethyl, i-propyl, i-butyl, butyl
aryl groups (e.g. phenyl, octyl, etc.), aryl groups (e.g. phenyl,
Naphthyl lol? ), halogen atoms (fluorine, chlorine, bromine, etc.)
), cyano, nitro, sulfonamide groups (e.g. methane
Sulfonamide, butanesulfonamide, p-toluene
sulfonamide FW), sulfonyl moyl group (e.g. methyl
77 moyl, phenylsulfamoyl, etc.), sulfo
Niru! (e.g. methanesulfonyl, p-toluenesulfonyl)
(e.g.), fluorosulfonyl, carbamoyl group (e.g.
methylcarbamoyl, phenylcarbamoyl, etc.),
Oxycarbonyl group (e.g. ethoxycarbonyl, 7-ethoxycarbonyl)
7xycarbonyl, etc.), acyl groups (e.g. acetyl, base),
heterocyclic groups (e.g. bilinol group, pyrazoyl group, etc.), heterocyclic groups (e.g. bilinol group, pyrazoyl group, etc.)
(lyl group, etc.), alkoxy group, aryloxy group, acyl group,
Examples include oxy group. In the general formula (CI) and CCI[), R. is cyanka represented by general formulas (C1) and (CIO)
cyan color formed from the puller and the cyan coupler
Represents the neulast group necessary to impart diffusion resistance to the base material.
, preferably an alkyl group having 4 to 30 carbon atoms, an aryl group
or a heterocyclic group. For example, linear or branched alkaline
Kyl groups (e.g. L-butyl, n-octyl, -octyl)
n-dodecyl, etc.), alkenyl group, cycloalkyl group
group, a five-shell or six-shell heterocyclic group, and the like. In the general formula CCI) and [:C[[], Z is hydrogen
Coupling reactions with atoms or oxidation products of color developing agents
Represents a group that can be removed as needed. For example, halogen atoms (e.g.
(e.g. chlorine, bromine, fluorine, etc.), substituted or unsubstituted alcohols
xy group, aryloxy group, heterocyclic oxy group, 7-sil
Oxy group, carbamoyloxy group, sulfonyloxy group
, alkylthio group, arylthio group, heterocyclic thio group,
Examples include sulfone 7-mido group, and further specific examples include
U.S. Patent No. 3,741,583
No. 425, Japanese Patent Publication No. 48-36894, Japanese Patent Publication No. 1977-1
No. 0135, No. 50-117422, No. 50-130
No. 441, No. 51-10884], No. 50-1203
No. 43, No. 52-18315, No. 53-105226
No. 54-14736, No. 54-48237, No. 54-48237, No. 54-14736, No. 54-48237, No.
No. 55-32071, No. 55-65957, No. 56-
No. 1938, No. 56-12643, No. 56-2714
No. 7, No. 59-146050, No. 59-166956
No. 60-24547, No. 60-35731, No. 60-24547, No. 60-35731, No.
60-3573 listed in each publication.
Ru. In the present invention, the general formula (C1) or (CI)
Among the cyan couplers represented by the following general formula (Cln
), (CIV) or (CV)
- is more preferable. /- ring, lower margin General formula (CII[) I General formula (CI'/) H General formula (CV) General formula (cm'+, R1 is substituted or unsubstituted)
-yl group (particularly preferably phenyl group). When the aryl group has a substituent, the substituent is:
-5O2R halogen atoms (e.g. fluorine, bromine, chlorine)
etc.), -CF*, -No□, -CN, -COR6, -
At least one substituent selected from COORa, -5O20R is included. Here, R6 is an alkyl group, preferably having 1 to 20 carbon atoms.
alkyl groups (e.g. methyl, ethyl, terL-butyl)
alkenyl groups, preferably carbon
Alkenyl groups with a prime number of 2 to 20 (e.g. 7lyl group, hepta
Decenyl group"!?), cycloalkyl group, preferably 5
~7 shell ring groups (e.g. cyclohexyl group, etc.), aryl group
(e.g. phenyl group, tolyl group, naphthyl group!9i)
and R2 is a hydrogen atom or a group represented by R6 above.
be. General formula (7 er/-el cyan coupler represented by C[[])
Preferred compounds include those in which R4 is substituted or unsubstituted phenyl;
cyano, nitro as a substituent to the phenyl group.
b, -5O2R8 (R is an alkyl group), halogen atom
, a trifluoromethyl compound. In the general formulas [C■] and [Cv], R5 is alkyl
group, preferably an alkyl group having 1 to 20 carbon atoms (e.g.
methyl, ethyl, tert-butyl, dodecyl, etc.), a
alkenyl group, preferably alkenyl group having 2 to 20 carbon atoms
(e.g. allyl, oleyl, etc.), cycloalkyl groups,
Preferably a 5- to 7-shell ring group (e.g. cyclohexyl etc.), a
lyl group (e.g. phenyl group, tolyl group, naphthyl group, etc.)
), heterocyclic group (nitrogen atom, oxygen atom, or sulfur
A 5- to 6-shell heterocycle containing 1 to 4 atoms is preferable.
, for example, furyl group, chenyl group, benzothiazolyl group, etc.
). Said R. , R7 and the general formula [c■] and (CV)
An arbitrary substituent can be further introduced into R5,
Specifically, the general formula (Cl) and &' (C Tl
) can be introduced into R2 or R,
Substituents such as And, as a substituent, halogen
Preferred are carbon atoms (chlorine atoms, fluorine atoms, etc.). In general formulas (CI[I), (CIV) and (CV)
TeZ and R. are respectively represented by the general formula [(1) and (Cn) and
have similar meanings. of the ballast group represented by R,
A preferred example is a group represented by the following general formula (CVI).
Ru. General formula (CVI) In the formula, J represents an oxygen atom, a sulfur atom, or a sulfonyl group.
, k represents an integer from O to 4, beans represent O or 1, k
is 2 or more, two or more R1s exist. are the same or different
R, may be a linear or branched chain having 1 to 20 carbon atoms.
represents a substituted alkylene group such as a branch, and an aryl group.
,R,. represents a -valent group, preferably a hydrogen atom, a halo
Gen atoms (e.g. chromium, bromine), alkyl groups, preferably
or a straight chain or branched alkyl group having 1 to 20 carbon atoms (
For example, methyl, t-butyl, t-pentyl, t-octyl
dodecyl, bentatecyl, benzyl, 7-enethyl
etc.), aryl groups (e.g. phenyl group), polycyclic rings
group (preferably a nitrogen-containing heterocyclic group), an alkoxy group, preferably
Preferably, it is linear or +i branched and has 1 to 2 carbon atoms. alkoxy groups (e.g. methoxy, ethoxy, 1-butyl
ruoxy, octyloxy, decyloxy, dodecyloxy
groups such as xy), aryloxy groups (such as 7-enoxy),
), hydroxy, acyloxy, preferably alkyl
carbonyloxy group, 7-arylcarbonyloxy group (
For example, acetoxy group, benzoyloxy group), carboxy
cy, alkyloxycarbonyl group, preferably carbon number 1
~2o direct or branched fluoroxycarbonyl
aryl group, aryloxycarbonyl group, preferably 71
Pheasant carbonyl, alkylthio group, preferably carbon number 1
~20, acyl group, preferably straight 1r having 1 to 20 carbon atoms
I or branched fulkylcarbonyl group, acyl 7mi7 group
, preferably a linear or 5>branched alkyl having 1 to 2 carbon atoms.
Chylcarboxamide, benzenecarboxamide, sulfona
Mido group, preferably a straight or branched chain having 1 to 20 carbon atoms
Furkylsulfonamide group or benzenesulfonamide
group, carbamoyl group, preferably straight from carbon WL1 to WL20
chain or branched furkyl 7-minocarponyl group or phenyl group
7minocarbonyl group, 77moyl group, preferably
Direct M or branched flukylaminosul having 1 to 20 carbon atoms
Displays a fonyl group or a phenyl7minosulfonyl group. Next, cyanka represented by general formula (CI) or (CII)
Examples of specific compounds for pullers are shown below, but are not limited to these.
do not have. The following margins [Compound examples] C-I 2H5 C-13 C-14 CI. 1Otllll C-26 C-27 H C7H6 C-38 C-41 I -SO 0H is H H 0 ■ H H CJ. C-68 0■ 0■ H (CH2)20C,H. O H Rule C-84 C-85 H Jin H1 (t) CJIs 0CH2CH20CH3 is C-99 These cyan couplers are synthesized by known methods.
For example, U.S. Pat. No. 2,772,162;
No. 3,758,308, No. 3,880.6f31, No. 3,880.6f31, No. 3,880.6f31, No.
No. 49124゜396, No. 3,222,176, UK
Patent No. 975,773, Patent No. 8゜011.693, Patent No. 8
, No. 011,694, JP-A No. 47-21139, No. 5
No. 0-112038, No. 55-163537, No. 56
-29235, 55-99341, 5B-11
No. 6030, No. 52-69329, No. 56-5594
No. 5, No. 56-80045, No. 50-134644
, as well as British patent 1. oll, No. 940, U.S. Pat. No. 3,
No. 446,622, No. 3,996,253, Japanese Unexamined Patent Publication No. 1973
No. 6-65134, No. 57-04543, No. 57-2
No. 04544, No. 57-204545, Patent Application No. 1983-
No. 131312, No. 56-131313, No. 56-1
No. 31314, No. 56-131309, No. 58-13
No. 1311, No. 57-149791, No. 56-130
No. 459, JP-A-59-146050, JP-A No. 16695
No. 6, No. 60-24547, No. 60-35731,
Synthesized by the composite force method described in No. 60-37557 etc.
can do. In the present invention, represented by the general formula (CI) or CCU)
The cyan coupler may be used within a range not contrary to the purpose of the present invention.
Therefore, it can be used in combination with a conventionally known cyan coupler.
I can do it. Also, the formulas (C1) and (C1l)
An uncoupler can also be used. The silicon according to the present invention represented by the general formula [Cl3 or (Cn)]
When an uncoupler is contained in a silver herodenide emulsion layer
is usually about 0.005 to 2 mol per mol of silver halide.
, preferably in a range of 0.01 to 1 mol. Silver halide coating for color photographic light-sensitive materials
The hydrophilic binder used to
However, high-molecular polymers may also be used, and membrane
Swelling rate T1/2 must be less than 25 seconds
. The B-opening speed T of the binder is determined by the known method in this technical field.
can be measured according to any known method, e.g.
・7 Otogura by Green (A, Green) et al.
Fitzke Science and Engineering (P
Hot, Sci. Eng-) + 19'! + No. 2, 124-129
Using a swellometer (swelling membrane) of the type described on page
TX can be measured using a color developer at 30°C for 3 minutes.
Saturates 90% of the maximum swollen film thickness reached when treated for 5 seconds
The film thickness is defined as the time it takes to reach this % film thickness.
Ru. The membrane swelling rate Ty2 is due to the hardening of gelatin as a binder.
It can be adjusted by adding agents. As hard i3'l, aldehyde type, anoridine type (e.g.
For example, PB Report 19,921, US Patent 2,950
゜No. 197, No. 2,964,404, No. 2.98:1
, No. 611, No. 3,271゜175, Special Publication No. 46-4
0898, JP-A No. 50-91315, etc.
), isoxazolime series (e.g., U.S. Pat. No. 3,32
No. 1,323, epoxy systems (e.g.
Patent No. 3,047,394, West German Patent No. 1,085°66
No. 3, British Patent No. 1,033,518, Special Publication No. 1973-3
5495 etc.), vinyl sulfone type (e.g.
For example, PE report 19,920, West German patent 1,100
, No. 942, No. 2゜337.412, No. 2,545,
No. 722, No. 2,635,518, No. 2゜742.3
No. 08, No. 2,749,260, British Patent No. 1,251
,091, U.S. Patent No. 3,539,644, U.S. Patent No. 3,4
90,911 etc.), acryloyl groups (e.g.
For example, as described in U.S. Pat. No. 3.640.720),
Carboimides (e.g., U.S. Pat. No. 2,938,89
No. 2, No. 4,043,818, No. 4.061,499
(described in Special Publication No. 46-38715, etc.), Tori
Anon series (for example, West German Patent No. 2,410.973,
No. 2,553,915, U.S. Patent No. 3,325,287
, those described in JP-A-52-12722, etc.), polymers
molds (e.g. British Patent No. 822,061, U.S. Patent No. 3,
No. 623,878, No. 3゜396, No. 029, No. 3,
No. 226.234, Special Publication No. 47-18578, No. 18
No. 579, No. 47748896, etc.),
Other maleimide-based, acetylene-based, methanesulfonic acid esters
Stell-based and N-methylol-based hardeners used alone or in combination
Can be used in combination. As a useful combination technique, the example
West German Patent No. 2,447,587, 2°505.74
No. 6, No. 2,514.245, U.S. Patent No. 4,047,
No. 957, No. 3,832,181, No. 3,840,3
No. 70, JP-A-48-43319, JP-A No. 50-6308
No. 2, No. 52-127329, Special Publication No. 48-3236
Examples include combinations described in No. 4 and the like. The binder of the photographic constituent layers used in the color photographic material of the present invention
the membrane swelling rate T3A is 25 seconds or less,
The smaller the value, the better, but if the lower limit is too small, the membrane will not harden.
A time of 1 second or more is preferable as failures such as scrubber 2ch etc. may easily occur.
Yes. More preferably 2 seconds or more and 20 seconds or less, particularly preferably
preferably 15 seconds or less, most preferably 10 seconds or less. 2
If it is longer than 5 seconds, desilvering performance, that is, bleach-fixing performance deteriorates.
However, especially when using a low molecular weight ferric acid complex salt,
Even if it is a ferric complex salt of an organic acid with polymer 1, the concentration used is high.
Sometimes the deterioration is premature. 7', The bleaching process of the present invention is based on the above general formula [I] or [■].
However, typical examples include the following:
I can list such a life, but it is not limited to this.
It's not. [Exemplary compound] (f-11(1-21 (+-3) (1-・t) (15)
([-6)C)+2cOO)I
C112CII2C)12COOII(1
-13) (f -
14)N-15)
< 1-16) (1-17)
(+ -18)C112C112COOH (1-25) (+
-26) CII□C'112COOH (1-27) (r
-28) (1-29)
(r −30)II
H(+-37)
(1-38)(n-1)
(If -2)ss
5s(n-3)
(■-4) (II-5)
(II-6) (1-7)
(II-8) (■-9)
(n-10) (It-11)
(It-12) (■ -13)
([1-14)(n −1
5) (II-16)(
II-17) (It
-18) Oll 011
(II-20) ([1-21) (II-22) (II-23) (■ -24) (II-25) S ++3c Nil CNil N1-I CN
HC11i (If-27) (II-28) 11□N-C5NIINIIC5-N112 (II-2
9) ([1-30) ([1-31) (It-32) (II-33) ; [1-34) +12N C5NII(Clh)2NHCS N
il2([1-35) H2N-CSIJII (CI+2) 4Nllc
s -Nl12 (low 36) 11□N C3NII (CI+2)5NHC3N1
12 (II-37) (II-38) (II-39) (It-40) (■ ~41) (II-42) S (It -43) (II-44) (II-45) (II - 46) (It-47) (n-48) S (■-49) (■-50) (It-51) (II-52) (n-53) (II-54) (II-55) (Low 57) (II-58) (It-59) (II-60) (II-61) (II-62) (n-63) S (II-64) (II-65) (II-66) Nl- 67> C113N=C-5-C=N-C1li11I S Na Na (Rho 68) C2115N=CS C=N C2+1511
II S Na Na (II-69) (It-70> (n-71) DI-72) ([1-73) (It-741 ([1-75) CH3NIICH2012NIICSCII□C112
CH2COOH(n-76) (n-77) (II-78) (II-82) (II-83) (II-84> (II-85) (I[-88) (n-88) (II- 89) (n-90> (II-91) (If-92) (n-93> (■-94) (II-95) (n-96) II (■-97) (■-98) (If -99) (n-100) ([[-101) (II-102) O ([-103) ([-104) (II-105) ([l-106) (II-107) (I[- 108) II (II-110) (n -111) (n -1
12) (n -113) (I
t -114) (It -115)
(II-116) (IT-1171(n-
118) (n-119) (II-1
20) (II-121) (I
I-122)S ([1-12:11)
([-124) ([1-125)
([-126>([1-+27)
(Rho 128) (n -129)
(II-130)
S (II-131) (II
-132)S (II -133) (I
[-134) l1s (II -135) (I
I-136) (Rho 137)
(U-138) (II-139)
([-140)(II-141)
([1-142)(II
-143) (n-144) 1l (n-145) (II-146) H (II-147) 1l (II-148) (n-149) (It-150) (II-152) (II-153 ) (n-155) (■ -156) (II -157) (n-158) 82N-CI(2CH2-5H (II[-3) (III-4) (III-5) )100C-CII2CII2・5t (([1-6) +10, ゝ-CIICII□5it 110c112' (I[l -7) (1-8) (ill -9)
(III-11) CI13 C1+3([1-1
2) LCI. C112C)12-5l+ (lit -15) ([[l
-16) (II -17) (I
II-18)L し1I3 (III-19) (III-
20) (lit-21) (II
I-22) C112C12-Sl+ (1-23) (III-24
)([[l-25) (1-2
13) (Ill-27) H (III-28> ([1-29) (Ill-30
)(I[l −31) (I[
1-32>(I[l-33) (Ill-34) (III-35) ([1-36) (IV-1) H3 (IV-2) ■ H3 (IV -3) (N-4> (■-5) H3 H3 (V-1) (V-2)<y-
3) (V-4) (V-5>
(V-6) (V-7)
(V-8) (V-9)
(V-10) (V-11)
(V-12)OH011 (V-13) (V-14)rl
l, l (V -15) (V -1,6)
(V -17) (V -18) (
V-19) (V-20)(
V-21) (V-22
) (V −23) (V −
241 (V-25) (V-
26) (V-27) (V
-28) (V -29)
(V-30) (V-31)
(V-32) (V-33)
(V-34) (V-35
) (V -36) (V
-37) (V -38)(V
-39) (V-40) (V-41) (V -42) (V -43) (V -
44) (V -45) (
V-46) (V-47)
(V-48) (V-49)
(V-50) (V-51)
(V -52) (V -53>
(V-54)ll3 (V-55) (V-
56) (V-57) (V
-58>(V -59)
(V-60) (V-61)
(V-62) (V-63)
(V-64) (V-65)
(V-66) (V-67)
(V-68) (V-69)
(V-70) (v-71)
(V-72) (V-73)
(V −74>(V −75)
(V-76) (V-77
) (V −78>N)1
2NH□ (V −79> (V −
go) NH2N112 (V -81> (V-8
2) NH2CH. (V-83) (V-84)
(V-85) (V-86) (V
-87) (V -88)(V
-89) (V -90)(
V-91) (V-92)
C)12C1l□N)1,(CH2n3NII2(V
-93) (V -94)(V
-95) (V -96)N1
12 N11z(V-9
7) (V -981(V
-99> (V -100)(
CH2)iNth (C1l.)4N
H2 (V -101) (V
-102) II C2 h(V -103) (V -
104) (V -105) (
V -106) (V -107) H2 (V -108) (V -109) (V -110) (■ -111) (V -112) (V -113) (V -114) (V-115) (V -116) (V -117) (V -118) (V-119) SH5H (V-120) (V -121> (V -122) (V -123) (V -12
4) (V −125) (V −
126) (V-127)
(V-128) (V-129)
(V-130) (V-131)
(V −132>(V −133>
(V-134)Nl2
5H (V-135)
(V -136)03Na (V -137) (V -1
38) (V -139) (V
-140) (V-141)
(V-142) (V-143)
(V-144) (V-145)
(V-146) (V-147)
(V -148>(V -149)
(V-150) (V-151)
(V -152) (v -153)
(V -154) (V 155)
(V-156)H (V-157) (V-158)(
V -159) (V -160>N
ll (V -1 [31) (V -16
2) (V -163) (V -1
64) (V -165) (V -
166) (V -1137) (V
-168) SRNll2 (V -169) (V -170)
(V -171) (V -172
)N) one (V -173) K (V -174) (V -175
) (V -176) N = N I H (V -177) (V -178
) (V -179) N = NH (V -180) (V -1
81) (V -182) (V
-183) (V -184) N = N 1! N,, N-CH2C)I2SO,N)I. %, /H (Vl-1) (Vl-2) (V
l −3) (Vl −4) (
Vl-5) (Vl-6) (Vl-7>
(W-8) (W-9)
(Vl-10>(Vl-11) (Vl
-12> (W-13) (Vl-14)
(W-15) (Vl-16) (Vl-
17) (W-18) (Vl-19
)(■-20) (Vr-21)
(W-22) (Vl-26> (Vl-27
) (■-28) (■-29) (V
r -30) (Vl -31) (Vl-32
) (Vl-33) (Vl-3
4) (Vl-35) (Vl-3
6) Below margin (■-2) ,SC)1,CI(,N<CIl,C
)l, CO2CH3)2CH2CH2CO2C)13 (■-3) +5CH2CH2NHCH2CI
I2C1l□5O3H)2(■-4)+5CH2CH2
N("20H2ONCIl,ClI2CN" H (■-6) (SC)1,CIl,N(oH"H0
H'). CH2CHCl3 0■ (■-16> )ISC112CIhNCH
2CII2CONI12CI. (■-17) HSCLCH2NHCLCI
I20H (■-19) HSCLCLNCI
hCLN (CLhCH. The above compounds are described, for example, in British Patent No. 1,138.842.
, JP-A-52-20832, JP-A No. 53-28426,
No. 53-95630, No. 53-104232, No. 5
No. 3-141632, No. 55-17123, No. 60-
No. 95540, U.S. Patent No. 3,232゜936, U.S. Patent No. 3,
No. 772.020, No. 3,779,757, No. 3,8
93゜858 etc., it can be easily
Can be synthesized. 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 (pretreatment solution, especially preconditioning bath) prior to the bleach chamber N 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, Prelude 1! J, present in the solution, and in the bleach-fix solution
It may be brought in depending on the photographic material being processed, or
Silver halide color photographic material is pre-processed during manufacturing.
When processing in a pretreatment bath or bleach-fixing bath,
You may also use a method of making it exist. These bleach accelerators of the present invention may be used alone or in combination.
A bleach-fixing solution or a bleach-fixing solution may be used in combination with the bleaching accelerator.
or the baths that preceded them (pretreatment liquids, especially prefixing treatment).
In general, the amount added to each processing solution is per IQ of each processing solution.
Good results are obtained in the range of about 0.01 to 100 g. deer
However, in general, when the amount added is too small, the bleach preservation effect is
If the amount is too small or the amount added is too large, it will cause precipitation.
may contaminate silver halide color photographic materials processed by
0.05 to 5 per 1Ω of processing liquid.
0g is preferable, more preferably 0° per treatment liquid
05-15. It is. The bleach accelerator of the present invention is applied to a bleach-fixing bath and/or a bleach-fixing bath.
(pretreatment bath, especially prefixing treatment bath)
In some cases, it may be added and dissolved as is, but water, alkali
Yes, yes! It is common to add it by pre-dissolving it in M etc.
, methanol, ethanol, acetone, etc. as necessary.
Even if it is dissolved and added using a growth solvent, its bleach-fixing effect remains
There is no effect on the fruit. 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. ), Shikashi, 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-18) Cobalt sulfate (A-19) Cobalt acetate (A-20) Cerium sulfate ( A-21) Magnesium chloride (A-22) Magnesium sulfate (A-23) Magnesium acetate (A-24) Barium chloride (A-25) Calcium nitrate (A-26) Barium chloride (A-27) Barium acetate ( A-28) Barium nitrate (A-29) Strontium chloride (A-30) Strontium acetate (A-31) Strontium nitrate (A-32) Manganese chloride (A-33) Manganese sulfate (A-34) Manganese acetate (A-34) -35) Lead acetate (A -36) Lead nitrate (A -37) Titanium chloride (A-38) fJSiλ-z chloride (A -39) Zirconium sulfate (A-40) Zirconium nitrate (A -41) Ammonium vanadate (A-42)
Ammonium metavanadate (A-43) tungsten
Sodium tungstate (A-44) ammonium tungstate
(A-45) Aluminum chloride (A-46) Aluminum sulfate (A-47) Aluminum nitrate (A-48) Yttrium sulfate (A-49) Yttrium nitrate (A-50) Yttrium chloride (A-51) Samarium chloride (A-52>Samarium bromide (A-53) Samarium sulfate (A-54) Samarium acetate (A-55) Ruthenium sulfate (A-56) Ruthenium chloride These metal compounds of the present invention may be used alone or ,2
More than one species can also be used together. This amount of metal ion
0.0001 mol to 2 mol per IQ of the liquid used.
Preferably, particularly preferably in the range of 0.001 mol to 1 mol.
It is surrounded. The bleaching accelerator of the present invention is represented by the general formulas [I] to [■].
Among them, R1%R2, Rko, R4, R5, R
・8, R@, A%B, D%Z%Z', R%R71
and R and R', R2 and Rco, R4 and R5, and (
Heterocyclic residue formed by /Q%Q゛, amine 7 group, 71
The 7-l group, fluganyl group, and alkylene group are each substituted.
may have been done. The substituent is an alkyl group, an alkyl group,
Ryl group, alkenyl group, cyclic furkyl group, aralkyl group
group, cyclic alkenyl group, halogen atom, nitro group, sia
group, alkoxy group, aryloxy group, carboxy group
, alkoxycarbonyl group, aryloxycarbonyl group
group, sulfo group, sulfamoyl group, carbamoyl group,
Silami/group, heterocyclic residue, arylsulfonyl group,
Alkylsulfonyl group, 7 alkylamides, nofurkyl group
Amino group, anilino group, N-furkyanilino group, N-
Aryloxy group, N-7 sylanily7 group, hydroxy
Examples include groups. Moreover, the above R1 to R5, R-
The furkyl group represented by R9, Z', R, R' is also substituted.
It may have a substituent, and the substituent includes those listed above.
Of these, all groups except alkyl groups are included. The bleach-fix solution of the present invention contains an organic acid ferric complex as a bleaching agent.
containing a salt (hereinafter referred to as the organic acid tt42 iron complex salt of the present invention).
be possessed. As an organic acid forming the organic P12 ferric complex salt of the present invention
The following are representative examples. (1) Diethylenetriaminepentaacetic acid (MW = 393.
27) (2) Diethylenetriaminepentamethinephosphone
Acid (H = 573.12) (3) Cyclohexane-7mi-7tetraacetic acid (MW = 364
．． 35) (4) Cyclohexane diamine
Sulfonic acid (MW = 58.231 (5) Triethylenetetraminehexaacetic acid (MW = 364
．． 35) (6) ) Liethylenetetramine hexamethylene
Phosphonic acid (M = 710.72) (7) Glycol ethernoamine acetic acid (MW = 3)
80゜(8) Glycol ethernoamine tetramethylenepho
Sulfonic acid (MW = 524.23> (9) 1,2-diaminopropanetetraacetic acid (MW = 306
．． 27) (10) 1,2-Diami7-propane tetramethylene
Phosphonic acid (MW = 450.15) <11) 1.3-7 aminop-a pan-2-ol tetraacetic acid
(H= 322.27) (12) 1,3-diaminopropan-2-ol tetramethyl
Renphosphonic acid (H = 466, 15) (13) Ethylene
Cyamino-orthohydroxyphenylacetic acid (H14=
360.37) (14) Ethylenenoaminediorthohyroxyphenyl
Methylene phosphone a (M = 432.31) (15)
Ethylenediamine tetramethylenephosphonic acid (MW=43
6.13) (16) Ethylenenoaminetetraacetic acid (MW = 292.2
5) (IT) Nitri-a triacid (H= 191.14>(
18) Nitrilotrimethylenephosphonic acid (MW=29
9゜(19)Imi/Gomi acid (MW= 133.10
) (20) Imi7-symethylenephosphonic acid (M = 205
．． 04) (21) Methylimi 7-diacetic acid (MW = 147
．． 13) (22) Methyliminodimethylene phosphophone fi
(MW = 219° (23) human axyethyl imi 7
diacetic acid (NW = 177,'18) (24) hydroxy
Ethyliminodimethylenephosphonic acid (M) l = 249
．． 10) (25) Ethylene-7minetetrabrobionic acid (MW=
348.35) (26) Hydroxyethylglydinone (M14= 16
3.17) (27) Nitrilotripropionic acid (HA=
233.22) (28) Ethylenediaminediacetic acid (M
W = 176.17) (29) Ethylene-7minnopro
Bionic acid (MW; 277゜ P11 acid @ diiron complex of the present invention)
Salt is not limited to these, but any salt can be selected from these.
One type can be selected and used, and two types can be used if necessary.
It is also possible to use a combination of the above. Among the organic acids forming the ferric salt of the organic acid of the present invention, particularly preferred are
Preferred examples include the following. (1) Diethylenetriaminepentaacetic acid (MW = 393.
27) (3) Cyclohexanoamitsutetraacetic acid (MW=
364.35) (5) Triethylenetetraminehexaacetic acid (
MW = 494.45) (7) Glycol ether Noah
Minshi vinegar 1'%l (H= 380゜(9) 1.2-
Sifumi/Furohan 4 vinegar al (MW=306.27) (
11) 1,3-diaminopropan-2-ol western acetic acid (
MW = 322.27) (13) Ethylenediaminenoorthohydroxy 7-dyl
Acetic acid (MW=360.37) (16)! Tyrenoamine di/tetra vinegar a (MW=292.
25) (19) Iminoni vinegar fi (H=133.10) (
21) Methyliminodiacetic acid (MW = 147.13) (
23) Hydroxyethyliminodiacetic acid (MW = 177
．． 16) (25) Ethylenediaminetetrapropionic acid
(M-=348.35) (26) Hydroxyethylglycidine ('t41A=
163.17) (27) Nitrilotripropionic acid (M
M = 233.22) (28) Ethylenediaminediacetic acid
(MW-176,17) (29) Ethylene') 7 Mitsu
9p If Hir N1! (M11 = 277゜ main source
Ming's organic acid ferric complex salt is a free acid (hydrogen total 1, sodium
Alkali metal salts such as aluminum salts, potassium salts, lithium salts,
or ammonium salts, or water-soluble amine salts, e.g.
Used as triethanolamine, etc., but preferably
Potassium, sodium and ammonium salts are used
Ru. If at least one of these PIS diiron complex salts is used,
However, two or more types can also be used in combination. Its usage
can be selected arbitrarily, depending on the amount of silver in the photosensitive material to be processed and
It is necessary to select it depending on the silver halide composition, etc. In other words, it is best to use 0.01 mol or more per IQ of the liquid used.
Preferably, more preferably used at 0.05 to 1.0 mol
be done. In addition, for replenishment fluid, in order to reduce the concentration and replenishment
; Can be used as a replenisher by concentrating it at once.
is desirable. The bleach-fix solution of the present invention is used at pl (2.0 to 10.0).
pH is preferably 3.0 to 9.5, more preferably pH 3.0 to 9.5.
, most preferably used in pi (4,0-9.0
. It is preferable that the treatment temperature is 80°C or lower.
More preferably 55°C or less, most preferably 45°C
Use the following methods to prevent evaporation, etc. Bleach-fixing processing time is 8
It is preferably within minutes, more preferably within 6 minutes. The bleach-fixing solution of the present invention can be used as a bleaching agent as described above.
Contains various additives along with light organic acid fjG2 iron complex salt
be able to. Specially used as an additive that contributes to bleach-fixing properties.
to alkali halide or ammonium halide, e.g.
Potassium bromide, sodium bromide, sodium chloride, odor
ammonium chloride, ammonium iodide, sodium iodide,
It is desirable to contain potassium iodide, etc.
Solubilizing agents such as ethanolamine, acetylacetone, and
Sulfonocarboxylic acid, polyphosphoric acid, organic phosphonic acid,
dicarboxylic acids, polycarboxylic acids, alkylamines, polycarboxylic acids,
Add to ordinary bleaching solutions such as lyethylene oxide.
Those that are known 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
A special bleach-fixing composition consisting of sewage? II etc. can also be used.
I can do it. 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 thiosulfate, 7 ammonium thiosulfate
Umu no Yosa Thiosulfate, Senioshin7rinyo Potassium, Thiosulfate
Sodium anthate, ammonium heptaphosphate, etc.
ocyanates, 1,000 ureas, thioethers, high concentrations of bromides
Typical examples include chloride, iodide, etc. These establishments
The agent is 5 g/Q or more, preferably 50 g/Q or more, more preferably
Preferably, it can be used in an amount that can dissolve 70g/Q or more.
Ru. The bleach-fix solution of the present invention contains boric acid, borax, and sodium hydroxide.
potassium hydroxide, sodium carbonate, potassium carbonate
, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate
Various pH41 buffers such as aluminum, ammonium hydroxide, etc.
Alone or two! I! Contain a combination of the above
I don't mind. Furthermore, there are various optical brighteners and foam sharpeners.
It is also possible to contain a protective barrier and abrasive. Hido again
Roxylamines, hydranone, sulfites, isomeric bisulfites
Storage of salts, bisulfite adducts of aldehydes and ketone compounds, etc.
Constant agents, other additives, methanol, trimethylform
Contains organic solvents such as amide and trimethyl sulfoxide as appropriate.
Patent Application No. 50-51803
Heavy metals with a vinylpyrrolidone core as seen in the specification
It is desirable to add a compound or a copolymer. Additives added to the bleach-fix solution of the present invention to promote white paper fixing properties
Preferred compounds include tetramethylurea and triphosphate.
listus methylamide, ε-caprolactam, N-methyl
Pyrrolidone, N-methylmorpholine, tetraethylene
Rifur monophenyl ether, acetonitrile, glycol
Coalmore methyl ether and the like can be mentioned. 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, rinsing, or shutting down, the main
May be subjected to bright bleach-fixing treatment. Most preferably 1 fat record
The method of the present invention is performed after pre-fixing treatment after color development as shown in FIG.
It is a bleach-fixing process, and in this case, the pre-fixing process is
In addition, the bleach accelerator of the present invention may be included. The bleach-fixing process of the present invention is a stable process without washing with water.
It can also be washed with water and then stabilized.
. In addition to the above steps, dura mater, neutralization, black and white development, decontamination, small amount
Various auxiliary processes are added as necessary, such as a water washing process.
Good too. Typical examples of preferred processing power methods include:
The following steps are included. (1) Color development → bleach fixing → washing with water (2) color development → bleach fixing → washing with a small amount of water → washing with water (3) color development
Development → Bleach-fixing → Washing → Stable (4) Color development → Bleach-fixing
→ Stability (5) Color development → Bleach fixing → 1st stability → 2nd stability (6)
Color development → washing with water (or stable) → bleach fixing → washing with water (or stable)
(7) Color development → Pre-fixing → Bleach fixing → Washing (8) Color development
Image → Pre-fixing → Bleach-fixing → Stable (9) Color development → Pre-fixing →
Electrical conductivity → 1st stability → 2nd stability (10) Color development → Stop → Bleach-fix → Washing → Stability These
The effects of the present invention are more noticeable in the treatment steps of
Therefore, <3), (4), (5), (8) and (9)
The following treatment steps are more preferably used in the present invention. And most preferably (4), (5), (8) and (
This is the processing step 9). Various Kuroiso metal salts are added to the bleach-fix solution of the present invention.
It is preferable. These Kuroiso metal salts can be used as various chelates.
It is also preferable to add the metal complex after forming the metal complex with the agent.
This is a new method. The bleaching constant 'rIe of the present invention may contain chelating agents other than the present invention.
and/or a ferric complex salt thereof may be added. But long
The ferric complex salts other than the present invention are 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.
What is preferable is as described above, and in this case, bleaching is constant:
It is most preferable that the liquid XI also contains 7 white accelerated cutting.
This is the law. However, it cannot be contained in either one of them.
You can just fill it in. Add bleach accelerator only to pre-fixer
If the bleaching agent is removed from the pre-fixer, the bleaching agent is
It is carried into the bleach-fix solution by color photographic materials and becomes effective.
It will show results. In the bleach-fix solution, iron complex salts generated in the bleach-fix solution are
Oxidation treatment may be performed to convert the reduced form back to the oxidized form.
Preferably, the oxidation treatment includes, for example, air oxidation treatment.
degree is used. The air oxidation process is automatic (1st generation).
) In the processing tank of the white liquid tank and white liquid tank.
Forced acid that performs oxidation treatment by forcibly mixing air bubbles into contact with each other.
refers to the oxidation process, in which the liquid surface naturally comes into contact with air and is oxidized.
This method is usually called an air lane.
air pumped out from a device such as a condenser
An air distributor is installed to increase the oxidation efficiency.
A diffuser with fine pores, such as
Make the diameter as small as possible to increase the contact area with the liquid and
When air bubbles pumped into the liquid from the bottom of the tank come into contact with the processing liquid.
Therefore, it is preferable to carry out oxidation because the oxidation efficiency is high.
. This airage treatment is mainly carried out 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 the airage sink 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 China, it is usually said that the overage T range is 3.
There is no need to think about this, so air ventilation is maintained throughout the processing time.
You may also use strong efflegicin intermittently.
It can be done in any way you like. however
The smaller the air bubble diameter, the better the efficiency.
Plush etc. prevents contamination with other liquids, which is preferable.
It can be said to be a method. In addition, in the present invention, when the automatic processor is stopped,
Perform 1 pyrage treatment and stop the airage treatment during processing.
The method is also a preferred method. Also, the airage sink is
The liquid may be conducted separately by directing it outside the tank. Air as mentioned above
Regishin is disclosed in Japanese Patent Application Publication Nos. 49-55336 and 51-98.
Shower described in No. 31 and No. 54-95234
Using a combination of one-way type, spray one-way type, Noet spray method, etc.
and West German Patent (OLS) 2,113,65
The method described in No. 1 can also be used. Silver halide color photographic material used in the present invention
The total amount of silver coated is based on the colloidal silver filter layer and the colloidal silver layer.
The value includes the ration prevention layer, and is 80t*t11
'dI11'' or less, in which case the effect of the present invention is exhibited.
be done. Preferably 60 mg/d+a'', particularly preferably
Is it 50I111? Effective when /dta2 or less
Ru. In terms of photographic performance, 2011111/dm2 or higher
ffi amount is preferable and exhibits the effects of the present invention. Photographic constituent layers of the silver halide color photographic light-sensitive material of the present invention
Film thickness (gelatin film thickness) refers to the photographic constituent layers excluding the support, i.e.
At least a subbing layer, an antihalation layer, and an intermediate layer.
3 emulsion layers, 1 filter layer, 11 layers etc.
The total thickness of the hydrophilic colloid layer, which is the total thickness of the dried photographic structure.
It is the thickness of the stratification. The thickness is measured using a micrometer.
However, in the present invention, a total of 17 photographic constituent layers are 25
μl or less, preferably 22 μl or less, especially 20 μl
It is less than a duck, most preferably less than 18 μm. photographic performance
From the viewpoint of
do. The silver halide emulsion layer of the present invention contains at least
also contains 0.5 mol% silver iodide grains, but silver halide particles
Sensitivity and photographic properties of color photographic materials and bleaching properties of the present invention
In order to maximize adhesion performance, silver iodide must have photographic properties and
0.5 mol % to 25 mol % is preferable from the viewpoint of bleaching and bleach-fixing properties.
Yes. In the present invention, when it exceeds 25 mol%, photographic characteristics
Although the properties are more preferable, the bleach-fixing properties are significantly reduced.
cormorant. In the present invention, more preferably 2 mol% to 20 mol%
% silver iodide. Black colloid for antihalation used in the present invention
The silver dispersion layer is the support surface of the silver halide color photographic light-sensitive material.
visible range for incident light from the emulsion surface or from the emulsion surface.
(especially red light) has a sufficiently high optical density
. Also, from the emulsion side of silver halide color photographic light-sensitive materials,
It has a sufficiently low reflectance for incident light. The black colloidal silver dispersion layer is
If so, it is desirable that the colloidal silver be of sufficiently fine particles.
, if the colloidal silver is sufficiently fine-grained, the absorption will be yellow to yellow-brown.
Because the optical density for red light does not increase, there is a certain
As a result, these silver particles
Silver halide emulsions are susceptible to physical development using
It is thought that the bleach-fixability at the boundary between the layers deteriorates. In particular, the silver halide emulsion layer contains at least 0.5 mol% iodine.
In cases containing silveride grains, especially the halo closest to the support.
Silver iodide grains with a silver emulsion layer of at least 0.5 mol %
When the bleach-fixing property is
multilayer halogen having 381 or more silver iodide-containing emulsion layers.
Because silver oxide is prominent in color photographic materials,
It is estimated that the effects of the present invention will be particularly significant at this time. In the present invention, the effects of the present invention are particularly effectively exhibited.
When processing a sensitive material containing a core-shell emulsion,
For some core-shell emulsions, see Japanese Patent Laid-Open No. 5
Although it is described in detail in No. 7-154232, etc., it is preferred that
New silver halide color photographic materials contain halogen in the core.
Silver iodide composition is 0.1 to 20 mol%, preferably 0.
．． Silver halide containing 5 to 10 mol%, and the shell has no odor.
Silver chloride, silver chloride, silver iodobromide, silver chlorobromide, or these
It consists of a mixture. Particularly preferably, the shell consists of silver iodobromide or silver bromide.
This is a halogenated plate cut. 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.
The total coated silver amount is 8 (hH/dm2 or less).
, preferably 60nB/d+s2, most preferably 5
0mg/dm2 or less, and the photograph excluding the support
The film thickness of the true constituent layer (gelatin film thickness) is 25μIII or more,
Preferably 1 to 22μII+, more preferably 20μm,
In particular, it is 18 μm or less. especially the core and/or shell
silver halide grains containing silver iodide, silver bromide, salt
From silver oxide, silver chlorobromide or iodobromide, or a mixture thereof
The silver halide grains of No. 1111 have a specific J7 size shell.
containing silver iodide by hiding the core using
It takes advantage of the ability of silver halide grains to achieve high sensitivity, and
The point is that it hides and hides the disadvantageous properties of particles. Halogenated ffl t with the above specific /7 shell
Is a silver halide emulsion with one child monodisperse? Included in cutting
These shells are covered with silver halide grains as a core.
It can be manufactured by overturning it. In addition, when the shell is silver iodobromide, the relationship between silver iodide and silver bromide is
It is preferable that the ratio is 20 mol% or less. To make the core a monodisperse silver halide grain, pAg is
The desired size is obtained by the Gubrunoent method while keeping it constant.
particles can be obtained. Also highly monodisperse halo
The production of silver generator emulsion is described in JP-A-54-48521.
The method described can be applied. How to do that
In a preferred embodiment, potassium iodobromide gelatin is used.
halogenating an aqueous solution of ammonium silver nitrate and an aqueous ammonium silver nitrate solution.
The addition rate was changed over time into the gelatin aqueous solution containing ff1 type particles.
S) by changing and adding it as a function between!
It is to attend. At this time, the time function of the addition rate, pt
By appropriately selecting l, pAH1 temperature, etc.
A monodisperse silver halide emulsion can be obtained. single
The particle size distribution of a dispersible emulsion is almost a normal distribution, so the standard deviation
The difference is easily determined. From now on, if we define the width of the distribution (%) by the relational expression, then the absolute J of the coverage
The breadth of distribution needed to meaningfully regulate the
Those with the following lit dispersibility are preferable, and more preferable.
is less than 10%. 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. That is,
The thickness is limited to a narrow range defined by these upper and lower limits.
determined. Such a shell is soluble in soluble halogen compounds.
Monodisperse the silver solution using the double-noe method.
It can be formed by depositing it on the sexual core. For example, an average grain size of 1 μm containing 2 mol% silver iodide in the core.
Using substantially monodisperse silver halide grains of □,
．． With 2 mol% silver iodobromide as a shell, the coating thickness is
According to experiments with various changes, for example, 0.85 μm/! 7
monodisperse halogen by this method
The covering power of silver oxide particles was 1 degree. this,
Physically developable material containing a solvent that makes silver halide/f arsenic 28 squares
When treated with a certain processing solution and observed with a scanning electron microscope, the
It was found that the silver filament was not coming out. this
lowers the optical C degree and further reduces the covering power.
It suggests that it be lowered. There, the developed silver filament
Considering the particle morphology, the surface is
As a result of reducing the thickness of the silver bromide shell, the shell
The thickness is the absolute thickness regardless of the average grain size of the core.
At 0.8 μm or less (preferably 0.5 μm) or less
A good number of developed ffl filaments are produced and sufficient
optical density will occur, and the ability of the core to achieve high sensitivity will be impaired.
It turns out there isn't. 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 thickness limit is 0.01 μI.
is preferred. Furthermore, due to the highly monodisperse core with a distribution width of less than 10%
As confirmed, the preferred shell thickness is 0.01-0.06
The most preferable thickness is 0.03 μm or less.
Ru. The developed silver filament described above is sufficiently generated and the optical density is
The high sensitivity of the core is taken advantage of.
A sensitizing effect occurs, and rapid developability and fixability occur.
The thickness is regulated as above by a highly monodisperse core
shell, and silver halide set of core and shell
This is due to the synergistic effect between the shell thickness.
If it can satisfy the requirements, it will constitute the shell)
Silver lodenide is iodine, silver bromide, silver chloride or salt odor.
Silver oxide or mixtures thereof can be used. Among them, compatibility with the core, performance stability, storage stability, etc.
Preferably silver bromide, iodobromide, or a mixture thereof
It is a thing. The light-sensitive silver halide emulsion used in the present invention has a core and a
When silver halide precipitates of shells and shells are formed, and when grains grow.
Or, after the growth is completed, it is converted into various metal salts or metal complex salts.
Therefore, doping may be applied. For example, gold, platinum,
Lanium, Illinoum, Lonoum, Bismuth, Cadmiu
metal salts or complex salts such as metal salts, metal salts, and combinations thereof.
Applicable. In addition, excess halogen produced during the preparation of the emulsion used in the present invention
Gen compounds, by-products, or unnecessary nitric acid
Salts, ammonium and other salts, and compounds may be removed.
stomach. The removal method is the same as that commonly used in general emulsions.
Use the del water washing method, dialysis method, coagulation precipitation method, etc. as appropriate.
be able to. Furthermore, the emulsion used in the present invention is not applied to a general emulsion.
Various chemical sensitization methods can be applied. Namely, activated gelatin; water-soluble gold salt, water-soluble platinum salt, water-soluble
water-soluble palladium salts, water-soluble rhodium salts, water-soluble iridium
Noble metal sensitizers such as salts; sulfur sensitizers; selenium sensitizers;
For chemical sensitizers such as amines, reduction sensitizers such as stannous chloride, etc.
Can be chemically sensitized singly or in combination.
Ru. Furthermore, this silver halide can be optically enhanced in the desired wavelength range.
I can feel it. Particular restrictions on optical sensitization methods for emulsions
For example, zeromethine dyes, mo/methine dyes, and trimethine dyes.
Cyanine dyes such as methine dyes or merocyanine dyes
alone or in combination with optical sensitizers such as
Sensitivity) Can be optically sensitized. These techniques are described in U.S. Patent No. 2,688,545.
, No. 2,912,329, No. 3,397.060,
No. 3,615,635, No. 3,628,964, English
National Patent No. 1,195,302, National Patent No. 1,242゜588
, No. 1,293,862, West German Patent (OLS) 2,0
No. 30,326, No. 2,121,780, Special Publication No. 1973
-4936, No. 44-14030, etc.
Ru. The selection depends on the wavelength range to be sensitized, sensitivity, etc. of the photosensitive material.
Depending on the purpose and use, it is possible to set the number to more or less. The silver halide emulsion used in the present invention further includes
In forming silver halide grains, core grains are
Silver halide, which is qualitatively monodisperse silver halide grains
By coating the core particles with a shell using an emulsion.
, monodisperse silver halide milk with almost uniform shell thickness
However, such substantially monodisperse
The silver halide emulsion can be used with its grain size distribution unchanged.
However, two or more types of monodisperse emulsions with different average grain sizes can be used.
Blend at any time after particle formation to achieve a predetermined gradation.
It may also be prepared and used. The silver halide emulsion used in the present invention has a wide distribution.
20% or less: x1!1 shell to monodisperse core
Can it be obtained by coating? At a rate equal to or higher than L agent,
The present invention is applied to all silver halide grains contained in the emulsion.
Those containing silver halide grains are desirable. But that
In addition, halogens other than the present invention may be used within a range that does not impede the effects of the present invention.
It may also contain silver germide grains. Halogen other than the present invention
Silver compound may be of core-shell type or other than core-shell type.
It can be monodisperse or polydisperse.
But that's fine. In the silver lodenide emulsion used in the present invention
The silver halide grains contained in the emulsion are at least
Preferably, 65% by weight is the silver halide grains of the present invention.
Indeed, almost all of them are silver halide grains of the present invention.
It is desirable that In the present invention, the silver halide emulsion contains at least 0.5 mol of silver halide emulsion.
Milk containing tabular silver halide grains containing % iodized nails
This includes cases where it is an agent. That is, the halogen of the present invention
The emulsion of the present invention used in the silver emulsion layer is
The silver oxide grains are the legalized silver Coanel grains.
, ■ Be legalized silver tabular silver halide grains (if applicable)
Legalized silver tabular silver halide grains are core-shell type.
However, it may be of other types. ), ■before
Any of the embodiments of IA, such as being a mixture of ■ and ■.
However, it is included in the present invention. Below, legalized silver tabular silver halide grains will be explained.
Ru. The particle diameter of the tabular halogenated particles is 5 times or more the particle thickness.
Preferably. The tabular silver halide grains are manufactured by JP-A-Sho.
No. 58-113930, No. 58-113934, No. 5
No. 8-127921, No. 58-108532, No. 59
-99433, No. 59-119350, etc.
It can be manufactured by a general manufacturing method, and the present invention includes
Come on, color stain and ii! 'it? 7? to f
For the most effective, the particle diameter is 5 times or more the particle thickness, preferably
5 to 100 times, particularly preferably 7 to 30 (9 is used)
It's good to be there. Furthermore, the particle diameter is preferably 0.3 μIII or more, and 0.5 to
A thickness of 6 μm is particularly preferred. These flat plates
The silver halide grains are comprised of at least one layer of sub-halogen emulsion.
It has one or more layers containing at least 5 offl amount%.
The desired effects of the present invention can be obtained more favorably when processing photosensitive materials.
Almost all of them are plate-like halogenated metals.
Particularly favorable effects can be achieved when silver particles are present.
do. When the tabular silver halide grains are core-shell grains
is particularly useful. Then, the core-shell particle is
In this case, the requirements mentioned above for the core shell are also satisfied.
It is preferable. Generally, tabular silver halide grains have two parallel faces.
Therefore, "thickness" in the present invention refers to
Two parallel planes forming h1 of tabular silver halide grains
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
Silver iodobromide is preferably 0.5 to 10 mortars.
More 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, in an atmosphere with a relatively high r'Ag value of pB rl, 3 or less.
When jV-platelet silver halide grains account for 40% or more by weight in an ambient atmosphere,
while maintaining the same pBr value.
Growing seed crystals while simultaneously adding silver and halogen solutions
It can be obtained by No new crystal nuclei are generated during this grain growth process.
It is desirable to add the silver and halogen solution accordingly. The size of tabular silver halide grains is determined by temperature control and solvent
Selection of type and amount, particles - silver salt used during formation, and halo
Adjustments can be made by controlling the addition rate etc.
It can be arranged. During 5z production of tabular silver halide grains, if necessary,
Silver halide l: By using shaving, grain size,
Particle shape (diameter/17 ratio, etc.), particle size
The growth rate of cloth and particles can be controlled. The amount of silver halide solvent used is lXl0-'- of the reaction solution.
1,0frL amount%katJP*L<, Special 1: I
Xl0-'-I Xl0-'ffl amount% is preferred. For example, an increase in the amount of halogen solvents used and 61 halogens.
It is possible to make the silver oxide grain size distribution monodisperse and increase the growth rate.
I can do it. On the other hand, along with the amount of silver halide solvent used
There is also a tendency for the thickness of silver halide grains to increase. The halogenated kite solvents used include ammonia, nitrogen,
Examples include ethers and thioureas. Thioe
Regarding the technology, see U.S. Pat.
See No. 3,790,387, No. 3,574,628, etc.
It can be considered. To accelerate grain growth during tJl production of tabular silver halide grains.
salt solution (e.g. 8 g NO. aqueous solution) and halide solution (e.g. K[lr aqueous solution), which is added to
The preferred method is to increase the addition rate, amount, and concentration of
commonly used. 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, JP-A-55-1
See descriptions in No. 42329, No. 55-158124, etc.
can do. Tabular silver halide grains are chemically sensitized if necessary.
be able to. Regarding the 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 a combination thereof is preferred. The layer containing tabular silver halide grains contains tabular silver halide grains.
The silver halide grains are compared to all the silver halide grains in the layer.
Preferably, it is present in a weight ratio of 40% or more, particularly 60% or more.
Delicious. The thickness of the layer containing tabular silver halide grains is 0.5μ
It is preferable that the weight is between 5.0μ and 1.0μ and 3.0μ.
It is even more preferable that there be. Also, the coating amount of tabular silver halide grains (for one side)
is preferably 0.58/m” to GH/In2,
More preferably, it is 1 g/12 to 58/m2. Other configurations of the layer containing tabular silver halide grains,
For example, binders, hardeners, antifoggants, halogenated
Silver stabilizers, surfactants, spectral sensitizing dyes, dyes, UV
There are no particular restrictions on the line absorber etc., for example, Rese
arcl+D 1sclosure1768.22
Please refer to the description on page 28 (December 1978)
can. Next, from the layer containing the tabular silver halide grains,
Silver halide emulsion layer present on the outer llllll (surface side)
(Hereinafter referred to as the upper silver halide emulsion layer)
I will explain it. Silver halide grains used in the upper silver halide emulsion layer
is a high-sensitivity film used for normal direct X#it film.
Silver halide grains are preferably used. The shape of silver halide grains is spherical or polyhedral.
or a mixture of two or more of these is preferable.
. In particular, spherical particles and V/or diameter/thickness ratio are 5 or less.
Polyhedral particles have a total ratio of 60!5 to 1: (, IIi ratio)
It is preferable that The average particle size is 0.5μIfi to 3μIn.
Preferably, ammonia and thioether are added as necessary.
It can be grown using solvents such as tel, thiourea, etc.
Ru. Silver halide grains are produced using gold sensitization method or sensitization method using other metals.
, or reduction sensitization method, or sulfur sensitization method, or these two
High sensitivity is achieved by the sensitization method using the above combination.
It is preferable that For other configurations of the upper emulsion layer, tabular halogenated
As with the layer containing silver particles, there is no particular restriction, and the above Re
! +earcl+ D 1 closure 176 volumes
You can refer to the description.゛Also, the emulsion used in the present invention is disclosed in JP-A-53-10372.
No. 5, No. 59-1: 13540, No. 59-16254
Containing epitaxially bonded silver halide grains described in No. 0 etc.
It is also preferable to have it. The silver halide emulsion of the present invention may be used depending on the purpose.
Various additives may be included. For example, azaindenes, triazoles, tetrazoles
, imidazoliums, tetrazolium salts, polyhydro
Stabilizers and antifoggants such as xyl compounds; aldehyde-based,
Azirinone series, inoxazole series, vinyl sulfone series
, acryloyl type, carboimide type, maleimide type,
Hardening agents such as methanesulfonic acid ester type and triazine type
;bennol alcohol, polyoxyethylene compounds, etc.
Development accelerator; chroman type, claman type, bisphenol
image stabilizers; Wanx, high
Glycerides of higher fatty acids, higher alcohols of higher fatty acids
There are lubricants such as esters. Also, as a surfactant
Coating aids, permeability improvers for processing liquids, antifoaming agents, etc.
or for controlling various physical properties of photosensitive materials.
Anionic, cationic, and non-ionic materials are available.
Alternatively, various species of both sexes can be used. Especially the bleaching ability
It is preferable for these surfactants to elute into the processing solution containing the
That's a good thing. Noacetyl cellulose is an antistatic agent.
styrene perfluoroalkyl sonorum maleny
) coffl coalescence, sulfene-9hydric maleic acid copolymer
Coalescence and 1)-Ami/benzenesulfo/acid reaction product
Lucari salt etc. are effective. As a matting agent, polymethac
Methyl lylate, polystyrene and alkali soluble polymers
-, etc. Furthermore, it is also possible to use fluid-like 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 latin binders.
Styrene-male is used as a thickener.
Sodium inric acid copolymer, alkyl vinyl ether male
Examples include inic acid copolymers. In the silver halodef color photographic material of the present invention, milk
In order to prepare the hydrophilic Floyd layer coating solution for one week,
Hydrophilic colloids used include gelatin and derivative gelatin.
Graft polymers of tin, gelatin and other polymers,
Own of albumin, casein, etc., hydroxyethyl
cellulose, carboxymethylcellulose, etc.
base derivative, 1-starch derivative, 1-starch derivative, polyvinyl alcohol,
+11 for polyvinyl alcohol, polyacrylamide, etc.
- or synthetic hydrophilic product of copolymer 7-
Includes: As a support for the silver halide color photographic light-sensitive material of the present invention
For example, glass plates, cellulose acetate, cellulose
carbon nitrate or polyethylene terephthalate, etc.
Polyester film, polyamide film, polycarbonate
Bonate film, polystyrene film, etc.
, as well as conventional reflective supports (e.g. baryta paper, polyethylene
Coated paper, polypropylene synthetic paper, with reflective layer
, or a transparent support combined with a reflector), and these
The support is appropriately selected depending on the intended use of the photosensitive material.
. Silver halide emulsion layer used in the present invention and its
Other photographic composition layers can be applied by dipping, air coating, etc.
Various coatings such as doctor coating, curtain coating, hopper coating, etc.
A fabric method can be used. Also, U.S. Patent Nos. 2,761,791 and 2,941,8
Using the simultaneous coating method of two or more layers according to the method described in No. 98,
I can do it because I am there. 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
Colors such as those containing yellow couplers in combination
- All you have to do is apply the methods and materials used for photosensitive materials.
stomach. Silver halide color to which the bleach constant rI solution of the present invention can be applied
Photographic light-sensitive materials contain a coloring agent.
type development method (U.S. Patent No. 2,376.679, U.S. Patent No. 2,8
01.171), color formers are included in the developer.
External development method (U.S. Pat. No. 2,252.7] No. 8)
, No. 2,592,243, No. 2, 590, 970
(see No.) may also be used. In addition, color formers are available in this industry.
Any commonly known material can be used. For example,
As an uncoloring agent, naphthol or 71/-L (
Based on 11rI structure, Indian animation is possible by coupling.
active as a magenta coloring agent.
The skeleton structure is a 5-pyrazolone ring with a methylene group.
The yellow color former is activated methylene nails.
(benzoylacedoanilide with pivalyl acetate)
Those with acylacedoanilide structure such as toanilide
etc., with or without a substituent at the coupling position.
You can use any of the following. In this way, as a coloring agent,
Both so-called 2-equivalent couplers and 4-equivalent couplers
Applicable. Black and white developers that can be used in the processing of the present invention are commonly known.
Processing of light-sensitive materials in silver halide color photography
What is called the black and white first developer used in
,',R is used for processing white photographic materials.
, contains various additives that are generally added to black and white developers.
It can be tightened. A typical additive is 1-phenyl-3-pyrazolide.
developing agents such as methane, methol and hydroquinone;
Preservatives like sulfates, thorium hydroxide, sodium carbonate
Accelerators consisting of alkalis such as aluminum, potassium carbonate, bromide
Potassium, 2-methylbenlimigsol, methylben
Inorganic or organic inhibitors such as tuthiazole, po
Water softeners such as lyphosphates, trace amounts of iodides and
Name a surface overdevelopment inhibitor consisting of a capto compound.
I can do it. Color developer used in processing with bleach-fix solution of the present invention
The Hoya family 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
Phenolic and I)-phenylenenoamine derivatives
included. Because these compounds are more stable than the free state,
Commonly used in salt form, e.g. hydrochloride or sulfate
It will be done. In addition, these compounds are generally used in color developer IQ.
It is preferably used at a concentration of about 0.1 g to about 30 g.
Preferably, more preferably 11 pieces and about 1g to about 15.
Use at a concentration of Examples of the 7-minophenol developer include 6-7minophenol.
Phenol, p-ami7phenol, 5-ami7-2-
Hydroxytoluene, 2-ami/-3-hydroxytoluene
ene, 2-hydroxy-3-ami/-1,4-tumethyl
Contains benzene, etc. A particularly useful aromatic PjS primary amine color developer is N. N-dialkyl-11-phenylenediamine, 1 compound
and the alkyl speaker V phenyl group is substituted
Or, it may not be substituted. Among them, a particularly useful compound is N,N-noethyl
-p-phenylenediamine W salt, N-methyl-1)-
Phenylenenoamine hydrochloride, N,N-tumethyl-p
7z nylennoamine m[X, 2-7 minnow 5-(N-e
thyl-N-dodecyl 7mino)-toluene, N-ethyl-
N-β-methanesulfonamidoethyl-3-methyl-4
-7mino7niline sulfate, N-ethyl-N-β-hydro
xyethylamine/aniline sulfate, 4-7mi/-3-mi
Chil-N,N-diethylaniline sulfate, 4-ami7-
N-(methoxyethyl)-N-ethyl-3-methylani
Phosphorus-p-)renin sulfo*-)Y? 'wokyo R' thing
I can do it. A particularly useful color developing agent in the present invention is Amitsuno Kojo
Para having at least one water-soluble group (hydrophilic group) in
It is a phenylenenoamine color developing agent.
The following compounds are typical developing agents.
However, the present invention is not limited thereto. (1) C2115C21LNllSO2CI! . \/' (6) C1l, C2)1, Otl'''N' N1)2 (7) IOC211, C2LOi゛゛ゝ8'' Nl+. (8) c4II9C1It-3o-tl゛Skin 10) If C112COOHH2 (11) C2H3(CIhC)120)2C1b゛
\/ Fight (14) C2+(S (CH2CH20)2CJ
s\/' H2 Color developing agents particularly useful in the present invention are
As a base -(CI!2)nc, 1120L (CH2
CHSO2(CIl,)ncII, -(CIl□)
It is a compound having each group of no(CH2)ncIl,
, Specific compounds include (1), (2) of the above specific examples,
(3), (4), (6) and (7) are mentioned. however
m and n are integers of 0 to 6, preferably O to 5.
Ru. The paraphenylenenoamine color developing agent described in the present invention 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 color separation developer is the aromatic 1a amine color developer.
In addition to the color developer, various
ingredients such as sodium hydroxide, sodium carbonate, charcoal
Alkaline agents such as potassium chloride, alkali metal sulfites,
alkali metal bisulfite, alkali metal thiocyanate,
Alka 1j=j [halides, bennor alcohol,
Diethylenetriaminepentaacetic acid, 1-hydroxyethylide
Water softeners and thickeners such as 1,1-nophosphonic acid, etc.
can be optionally included. The pH of this color developer
is usually 7 or more, most commonly about 10 to about 13
It is. The bleach-fixing solution according to the present invention is suitable for color paper, color
Negative film, color box film, color for slides
Reversal film, color reversal film for movies, color for TV
- Emulsion of the present invention for reversal films, reversal color papers, etc.
It can be applied to silver halide color photographic materials using
However, especially when the total application amount is 50+oH/dm2 or more,
For processing high-sensitivity color photographic materials containing silver iodide as described below.
most suitable. [Examples] 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 For high-sensitivity silver halide color photographic light-sensitive materials in the industry,
Following the layer structure adopted in the
From the support side, apply the norcidine prevention layer and the red-sensitive layer.
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 monodispersed high-sensitivity silver halide emulsion layer is placed on the outermost side of the blank emulsion layer.
Arranged. That is, the sample was prepared according to the following, but the amount of coated silver was kept constant.
Adjust the film thickness by changing the amount of gelatin so that the dried film)
A sample was prepared. Coating weight is approximately 100+
ag/den2 and 50+oH/dm2, membrane swelling rate
T and L42 were all adjusted to 18 seconds. 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.
Disperse 0.8 g of black colloidal silver in 3 g of gelatin.
An anti-halation layer was applied. Layer 2: Middle layer made of gelatin. (Dry film thickness 0.8
μde) Layer 3... bow, 5g low sensitivity red photosensitive odor 1 silver milk
agent (g■; 6 mol% L 1.9. gelatin and 0
．． 96 g of exemplary coupler C-2 of the invention, 0,028 g
1-hydroxy-4-(4-(1-hydroquine-8-
7cetamido 3,6-disulfo-2-su7tylazo)
7eth/xy]-N-[δ-(2,4-di-amylphene)
Butyl 1-2-su7tamide nonodium (
Hereinafter referred to as colored cyan coupler (cc-i))
0.4 g of dissolved trifrenol phosphate (hereinafter referred to as
A low-sensitivity red-sensitive halogen containing TCP)
Silver emulsion layer. Layer 4...1.1g of high-sensitivity red-sensitive silver iodobromide emulsion (to
ε■; 8 mol%), 1,2. of gelatin and 0.41
g cyan coupler (C-2), 0.02611 color
O, '15 with dissolved cyan coupler (CC-1)
High-sensitivity red-sensitive halogenated compound containing TCP of Fi
Silver emulsion layer. Layer 5...0.08g of 2,5-not-t-octyl high
Droquinone (hereinafter referred to as anti-fouling agent (HQ-1))
Dissolved 0,04. Dibutyl 7 tallate (hereinafter referred to as DB
P) and 1.2B gelatin.
layer. Layer 6: Bow, 6g of low-sensitivity green-sensitive silver iodobromide emulsion (heg
I; 15 mol%), 1.78 gelatin and 0.30
．． 1-(2,4,6-)lichlorophenyl)-3-[
3-(2,4-no-L-amylphenoxyacetamide
) Benzamide 1-5-pyrazolone (hereinafter referred to as mazen)
0.20g of 4゜4-
Methylenebis-11-(2,4,6-)lichlorophenylene
)-3-[3-(2,4-not-t-amylphenoquine)
acetamido)benzenamide 1-5-pyrazolone (below)
Bottom, magenta coupler (referred to as M-2)), 0.066
g of 1-(2,4,6-)lichlorophenyl)-4-
(1-su7tylazo)-3-(2-chloro-5-octa
Decenylsuccinimide anilino)-5-pyrazolone (
(hereinafter referred to as colored magenta coupler (CM-1))
Contains 0.3g of TCP in which three types of couplers are dissolved.
A low-sensitivity green-sensitive silver halide emulsion layer. Layer 7: Bow, 5Fi high-sensitivity green-sensitive silver iodobromide emulsion (to
g1; 11 mol%), 1.9 g of gelatin and 0.0
93g magenta coupler (M-1), 0.094g
Magenta coupler (M-2), 0.049g colored
0,128 in which magenta coupler (CM-1) was dissolved
High-sensitivity green-sensitive silver denide milk containing TCP
agent layer. Layer 8...0.2g yellow colloidal silver, 0.2g contamination
0 and 11 in which the inhibitor (HQ-1) was dissolved. DBP and
One layer of yellow filter containing 2.1 g of gelatin. Layer 9...0.95. low-sensitivity blue-sensitive silver iodobromide emulsion (
(gl: 6 mol%), 1.9 g of gelatin and 1.
84g of Q -(4-(1-bentrue-2-phenyl-
3,5-dioxo-1,2,4-tri7zolidinyl)]
-]α-pivaloyru2-chloro5[γ-(2,4'
-No monoamyl 7ethyl 7oxy)butanamide 1acetyl
Nilide (hereinafter referred to as yellow coupler (Y-1))
Low sensitivity blue light containing 0.93g of DBP dissolved in
silver halide emulsion layer. Layer 10...1.2g of highly sensitive monodisperse blue-sensitive silver iodobromide
Emulsion (^, I mol %), 2.0 g of gelatin and
0 in which 0.46B of yellow coupler (Y-1) was dissolved.
, high-sensitivity blue-sensitive halogen containing 23g DBP
Silver emulsion layer. Layer 11: Second protective layer made of gelatin. /112...first protection containing 2.3g of gelatin
layer. The dry film thickness of the photographic constituent layers of the finished sample was 35 μm each.
, 27μm, 25μm, 20μ+n, 18μω.
Met. This was designated as Sample No. 1 to 5. However, Hare
GX RL and black colloidal silver content of anti-yong layer
and gelatin intermediate layer and yellow filter layer membrane
The thickness was not changed at all. Further samples according to the present invention contained in layers 3 and 4
Samples in which coupler C-2 was replaced with C-70 (in descending order of film thickness)
No. 6 to 10), samples changed to C-31 (No.
No to 1, 11 to 15), comparative cyan coupler (1)
Replaced samples (Similarly No. 16 to 20) and comparative shear
Samples replaced with coupler (2) (Similarly, No. 21-2
5) was created. Furthermore, samples No. 1 to 25 had the same composition.
Using an emulsion and increasing the amount of hardener to increase the film swelling rate T to 3
A sample was also created in which the time was delayed to 5 seconds. Processing process is color development 3 minutes 15 seconds, ) 7 self-sufficiency 1 minute to 30 seconds
minutes, the first stability was 2 minutes, and the second stability was 30 seconds. In addition, each treatment was performed at 37.8°C, and each treatment liquid was as follows.
A treatment solution prepared according to the prescription was used. [Color development instructions] Potassium carbonate 30g Sodium sulfite
Thorium 2.08 Hydroxylua
Mine sulfate 2.0g1-hydroxyethyl
Den-1,1-nophosphonic acid (60% aqueous solution) 1.0° odor
Potassium chloride 1.2g chloride mug
Nessium 0.6g Sodium hydroxide
3.4gN-ethyl-N-β-
Add 4.6g of hydroxyethyl-3-methyl-4-aminoaniline sulfate water
Adjust to pH 10.1 with sodium hydroxide.
did. [Bleach-fix solution] Ethylenenoaminetetraacetic acid noammonium salt 7.58 ammonium/polymer
Ferric recarboxylic acid complex salt (C added according to Table 2) Ammonium sulfite (50% solution) 10.0
g Ammonium thiosulfate (70% solution Q) 20
Add 0.0g water to make 1(1), and with ammonium hydroxide
pi (1 g to 7,5!
Rho-2-methyl-4-inchazolin-3-one 1.08 ethylene
Add Glecol 1.0g water to IQ
Then, adjust the pH to 7.1 with 1ml of potassium hydroxide! ! Arranged
. [Second stable solution] Formalin <37975 solution) 7
．． Add 0mQ water to complete one story. Ethylene as 7-minopolycarboxylic acid in bleach-fix solution
Treated with aminetetraacetic acid ferric complex salt. bleach accelerator
Using exemplified compound (1), 0.7g was added per IQ.
. The bleach-fixing completion time at that time was measured. Also, processing
For the later samples, high temperature at 70°C and 50% relative humidity was used.
Forced deterioration test due to temperature and xenon arc lamp irradiation (1,5
Forced deterioration test using
This was repeated every other day for 4 weeks. Measure the cyan dye concentration of each sample around 1.5 using an optical densitometer.
Measured with PDA-65 (manufactured by Konishiroku Photo Industry Co., Ltd.),
Fading rate or less margin 0 magazine comparison cyan coupler (2) From the results in Margin Table 1 below, as has been known in the past, the present invention
Even using a cyan coupler of this type will reduce the shear to some extent.
The fading of the dye can be suppressed, but in addition, it is a constituent feature of the present invention.
A certain film thickness is 25 μm or less, and the film swelling rate T1/2 is 2
cyan dye by being added to the emulsion layer for less than 5 seconds.
It is clear that the effect of suppressing discoloration is maximized.
. Note that the use of the cyan coupler of the present invention involves bleach-fixing treatment.
There is also no effect on the desilvering performance in
. Example 2 Sample No. 4, 9.14.19 and
and 24 (both membranes) ￥20μl11) H swelling rate T
Same as Example 1 using samples with % changed to 20 seconds.
and the bleach-fixing process of Example 1.
CNK-4N (manufactured by Konishiroku Photo Industry Co., Ltd.)
Replaces bleaching and fixing steps in film processing formulations
The treated material was colored cyan in the same manner as in Example 1.
The fading rate of the element was determined. The results are shown in Table 2.
-Table 2 The results in Table 2 show that compared to conventional bleaching and fixing treatments, this method
It is better to carry out a bright bleach-fixing process to obtain the cyan color according to the present invention.
Effect of suppressing fading of cyan dye by using a puller
It is clear that this can be achieved significantly. Also, in Example 1
When viewed together with the results, the surprising effects of the present invention are
This will only be achieved if the requirements for NIT formation are met.
is well understood. Example 3 Samples No. 4, 9.14.19 and 24 of Example 1
Using a sample with a membrane swelling rate T1/2 of 10 seconds, Example 1
The organic acid ferric complex salt of the bleach-fix solution was changed as shown in Table 3.
and treated in the same manner as in Example 1 to suppress fading of the cyan dye.
I saw the effect. The results are shown in Table 3. -・, From the results in Table 3 below, the molecular weight of the organic acid ferric complex salt was varied.
Even if the cyan coupler of the present invention is used
The amazing effect of preventing cyan dye fading is fully demonstrated.
It is clearly seen that the desilvering performance is not deteriorated. Example 4 During the treatment steps in Example 1, the first stabilization step was carried out for 3 minutes and 15 minutes.
Example 1 was repeated by changing the water washing process for 2 seconds, but the cyanide
Exactly the same good results were obtained regarding inhibition of dye fading.

Claims (13)

[Claims] (1) It has a photographic constituent layer including blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers, and the red-sensitive silver halide emulsion layer has the following general formula [C I ] or [CII] A halogenated compound containing a cyan coupler represented by the following, the total thickness of all photographic constituent layers excluding the support is 25 μm or less, and the film swelling rate T1/2 of the binder in the photographic emulsion layer is 25 seconds or less 1. A method for processing a silver halide color photographic material, which comprises, after imagewise exposure and development of the silver color photographic material, processing the material with a bleach-fix solution containing at least one ferric organic acid complex salt. General formula [C I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [CII] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Y is -COR_2, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ , -SO_2R_2
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -CONHCOR_2 or -CO
NHSO_2R_2 (R_2 represents an alkyl group, alkenyl group, cycloalkyl group, aryl group or heterocyclic group, R_3 represents a hydrogen atom, alkyl group, alkenyl group, cycloalkyl group, aryl group or heterocyclic group, R
_2 and R_3 may be combined with each other to form a 5- to 6-membered ring. ), R_1 represents a ballast group, and Z
represents a hydrogen atom or a group that can be separated by coupling with an oxidized product of an aromatic primary amine color developing agent. ] (2) The method for processing a silver halide color photographic material according to claim 1, wherein the silver halide color photographic material has a black colloidal silver antihalation layer. (3) The silver halide color photographic light-sensitive material according to claim 1 or 2, characterized in that the total coating amount of silver in the silver halide color photographic light-sensitive material is 50 mg/dm^2 or less. Processing method. (4) Claim 1, characterized in that the membrane swelling rate T1/2 of the binder in the photographic emulsion layer is 20 seconds or less.
A method for processing a silver halide color photographic light-sensitive material according to item 1, 2 or 3. (5) The silver halide color photographic photosensitive material according to any one of claims 1 to 4, wherein the silver halide contains at least one layer of silver iodide in an amount of 2 mol % or more and 25 mol % or less. How materials are processed. (6) The silver halide color photographic light-sensitive material according to any one of claims 1 to 5, characterized in that a pre-fixing process having a fixing ability is performed immediately before the bleach-fix solution and after the development process. processing method. (7) The following general formula [
7. The method for processing a silver halide color photographic light-sensitive material according to claim 6, which comprises a compound selected from [I] to [VII]. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [IV] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [V] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [VI] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [VII] ▲ Mathematical formulas, chemical formulas, Tables etc. are available▼ [In the above general formula, Q is a heterocycle containing one or more N atoms (
Represents the atomic group necessary to form a 5- to 6-membered unsaturated ring (including those with at least one fused ring), and A is ▲Mathematical formula, chemical formula, table, etc.▼, ▲Mathematical formula, chemical formula ,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼ or n_represents a monovalent heterocyclic residue (including those with at least one 5- to 6-membered unsaturated ring fused to it),
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 has 1 to 6 carbon atoms.
represents an alkyl group, cycloalkyl group, aryl group, heterocyclic residue (including those to which at least one 5- to 6-membered unsaturated ring is fused) or an amino group, and R^
2, R^3, R^4, R^5, R and R' are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amino group, and an acyl group having 1 to 3 carbon atoms. , represents an aryl group, or an alkenyl group. However, R^4 and R^
5 may represent -B-SZ, or R, R', R^2
and R^3, R^4 and R^5 may each be cyclized with each other to form a heterocyclic residue (including those to which at least one 5- to 6-membered unsaturated ring is fused). good. R^6 and R^7 each represent ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R^9 is an alkyl group Or -(CH_2)n_8SO_3^■ (However, R^
When 8 is -(CH_2)n_8SO_3^■, l is 0
Or represents 1. )G^■ is an anion, m_1 or m_
4 and n_1 to n_8 are each an integer of 1 to 6, m
_5 represents an integer from 0 to 6, and R^8 represents a hydrogen atom, an alkali metal atom, a numerical formula, a chemical formula, a table, etc., or an alkyl group. However, Q' has the same meaning as Q above. D
represents a simple bond, an alkylene group or vinylene group having 1 to 8 monoprimes, and q represents an integer of 1 to 10. A plurality of D's may be the same or different, and the ring formed together with the sulfur atom may be further fused with a 5- to 6-membered unsaturated ring. X
' is -COOM', -OH, -SO_3M', -CON
H_2, -SO_2NH_2, -NH_2, -SH, -
CN, -CO_2R^1^6, -SO_2R^1^6,
-OR^1^6, -NR^1^6R^1^7, -SR^
1^6, -SO_3R^1^6, -NHCOR^1^6
, -NHSO_2R^1^6, -OCOR^1^6 or -SO_2R^1^6, and Y' is ▲mathematical formula, chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
or represents a hydrogen atom, 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. are available▼, and R^1^6 is a lower alkyl group , R^1^9 is -NR^2^0R^2^1, -OR^2^2 or -SR
represents ^2^2, R^2^0 and R^2^1 represent a hydrogen atom or a lower alkyl group, and R^2^2 represents R^1^8
Represents an atomic group necessary to connect with 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 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]▲There are mathematical formulas, chemical formulas, tables, etc. Yes ▼ [5] HS-CH_2CH_2-COOH [6] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [7] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [8] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ 9]▲There are mathematical formulas, chemical formulas, tables, etc.▼ [10]▲There are mathematical formulas, chemical formulas, tables, etc.▼ [11]▲There are mathematical formulas, chemical formulas, tables, etc.▼ [12]▲There are mathematical formulas, chemical formulas, tables, etc. ▼ [13] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [14] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [15] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [16] ▲ Mathematical formulas, chemical formulas, tables, etc. ▼ [17] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [18] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [19] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [20] ▲ Mathematical formulas, chemical formulas, There are tables, etc. ▼ [21] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [22] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [23] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [24] ▲ Mathematical formulas, There are chemical formulas, tables, etc. ▼ [25] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [26] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [27] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [28] HSCH_2CH_2NHCH_2CH_2O
H [29]▲There are mathematical formulas, chemical formulas, tables, etc.▼ or [30]▲There are mathematical formulas, chemical formulas, tables, etc.▼ (13) The method for processing a silver halide color photographic material according to any one of claims 1 to 12, wherein the bleach-fix solution contains a ferric complex salt of the following organic acid. (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) ethylenecyamine di-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