JP2694406B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] This invention relates to silver halide color photography.
The present invention relates to a method for processing a photosensitive material. In particular, the replenishment amount is extremely reduced and stable.
Color-A silver halide color that continuously forms photographic images
-It relates to a method for processing photographic light-sensitive materials. [0003] BACKGROUND OF THE INVENTION Generally, silver halide color photographic light-sensitive materials
When processing (hereinafter referred to as photographic material),
Photographic materials to keep composition constant and maintain photographic performance
A fixed amount of development replenisher is replenished per unit area of. The composition of the developing solution is changed by photographic processing and the copying
True performance also changes. For example, the concentration of the color developing agent depends on the reaction.
Concentrated halides that have a suppressive effect
The degree of elution increases from the photographic material due to the reaction. That
Therefore, the activity of the developer changes and becomes inactive if nothing is done.
You. As a method of preventing such inactivation, for example,
Its patent application publication (DE-A) No. 2,007,459, No. 2,0
07,457 and 2,717,674, U.S. Patent (US-A)
 3,647,461, 3,647,462 and 4,186,007 and
Described in European Patent Application Publication (EP-A) 00029722.
ing. These methods are called replenishment method, and replenisher
Is done by replenishing. The substances consumed in the development process are
The desired concentration is maintained by the addition of replenisher,
Sometimes unwanted halide accumulation in the developer
In order to prevent the
A threshold amount of replenisher is added. In this case, the concentration of the halide in the replenisher
Is low, and recently, a replenisher solution containing no halide
Therefore, we have succeeded in reducing the replenishment amount.
As a result of still producing a relatively large amount of overflow liquid
Is brought. Separately, the halide concentration
Replenishment volume is reduced by removing
Less or in some cases the halogen in the overflow solution
Oxides are removed to supplement the deficient components to serve as a replenisher.
As a result, the overflow liquid is reduced.
The method of making is widely used. In the former case, the halide concentration becomes high and the development
As it is suppressed, high activation treatment is applied to eliminate the suppression effect
However, there is a drawback that the amount of drainage is relatively large. In the latter, the device is an ion exchange tower or an electrodialysis tower.
Yes, and generally expensive. In addition, the development composition should always be constant.
Maintenance, such as requiring analytical operations to manage
There is a drawback that the work becomes extremely complicated. Therefore, especially in a minilab, etc.
Low replenishment system (LR system) that can be replenished is one
It is commonly used. However, the drawback of this method is the odor.
Compound has accumulated in a considerably high concentration. As a result,
As mentioned above, in order to overcome the suppression effect, high temperature treatment
Done. In this case, the effect of evaporation cannot be ignored.
The toxic component is concentrated and increased, and the liquid tends to be easily oxidized.
Appears. As a method for solving the drawbacks of these methods
In JP-A-61-70552, the silver halide content is extremely high.
Photographic material with a high silver chloride content
Flow with a low replenishment rate to prevent bromide.
Less elution of ON, resulting in higher bromide ion concentration
Proposing a treatment method that does not require high temperature treatment
Have been. This method is well known in the art.
Bromide is much more effective than chloride in terms of development inhibition.
Therefore, chloride ions, which have a small inhibitory effect, may enter the developer.
It ’s easier to elute,
Achieves low replenishment treatment without high temperature treatment
Can do it. However, according to the research conducted by the present inventors,
The higher the proportion of true material silver chloride, the more conventional development
The performance of the liquid cannot be maintained and the color density will decrease.
By slightly aging the color developing solution,
Therefore, the gradation will change significantly, and moreover the preservative
Of the concentration of sulfite, which is
Even with that, the drawback that the photographic performance changes will appear.
It was found that it could not be put to practical use as it is.
I understood that The present inventors further have the above-mentioned various advantages.
The study was conducted using photographic materials with high silver chloride content.
The maximum density does not increase when processed with conventional color developer
As a result, it may not be possible to achieve processing in a very short time.
Was. Further, when the silver chloride content exceeds 90 mol%, the maximum concentration is reached.
Not only the degree but also the intermediate density does not rise, and sufficient stable development is obtained.
I found that I couldn't. The present inventors have conducted a large number of studies on this cause.
As a result of analysis, it was used with conventional color developing solutions without exception.
The presence of hydroxylamine sulphate
I understood. In the presence of hydroxylamine sulfate,
The greater the proportion of silver chloride in the true material, the greater the suppression of development.
However, it was found that the processing solution was aged continuously
Then, ammoni produced by the decomposition of hydroxylamine
As the proportion of silver chloride increases due to the um ions,
Physical development may be easier and photographic performance may change.
I understand. Therefore, bromide generated in the development reaction by silver chloride
Even if the elution of substances is suppressed, the
The presence of ruamine can stabilize photographic performance.
Is not possible, especially when using continuous
Performance changes due to external factors. Also, with low replenishment processing
Tends to change the sulfite ion concentration in the developer over time
However, the concentration of sulfite in photographic materials mainly composed of silver chloride
It turns out that the photographic performance changes more sensitively. Based on these analyzes, the present inventors have earnestly studied
After repeated research, the photographic material contained silver chloride with a halogen concentration above a certain level.
Conventional silver hydroxide during color development using silver halide grains.
Using a specific compound instead of amine, and more than a certain amount
By treating it with the chloride of
All the disadvantages are solved, and continuous processing of sufficiently high photographic density is possible.
It was discovered that stable and stable photographic density can be obtained
However, the present invention has been accomplished. [0021] OBJECTS OF THE INVENTION The object of the present invention therefore addresses these drawbacks.
Photo performance is always stable even if the replenishment amount is significantly reduced.
It is to provide the processing method obtained by doing. [0022] The above-mentioned object of the present invention is less than that on a support.
And silver halide emulsion having one silver halide emulsion layer
Image-wise exposure of a photographic light-sensitive
It is a color developer containing an ellenedamine color developing agent.
After development, the color developer is continuously replenished with a replenisher.
For processing silver halide color photographic light-sensitive materials
And the silver halide emulsion layer is at least 70
% Of silver chloride containing silver halide grains.
The color developer is a triazinyl stilbene-based optical brightener,
Formulas [BI], [B-II], [B-III] or
A compound represented by [B-IV] and the following general formula [I]
Per liter of the compound represented by
At least 2x10^-2Halogen containing mole chloride
Achieved by the processing method of silver halide color photographic light-sensitive material
Was. Embedded image Where R₁₁, R₁₂, R₁₃And R₁₄Are each
Hydrogen atom, halogen atom, sulfonic acid group, 1 carbon atom
~ 7 alkyl group, -OR_Fifteen, -COOR₁₆,An atom or an alkyl group having 1 to 18 carbon atoms (provided that R is
₁₂R represents -OH or a hydrogen atom, R₁₁Is haloge
Atom, sulfonic acid group, alkyl having 1 to 7 carbon atoms
Group, R₄₃Are hydrogen atom, hydroxyl group, carboxylic acid group or
Represents a phosphonic acid group (including salts thereof) (provided that R is
₃₃~ R₃₆At least two of which are carboxylic acid groups or
Is a phosphonic acid group (including salts thereof), R₃₇~
R₃₉At least two of which are carboxylic acid groups or phosphos
Acid groups (including their salts). [0023] Embedded image Where R₁And R₂Are each an alkyl group (having a substituent
Or a hydrogen atom. Where R₁as well as
R₂Both of which have no substituent at the same time, or an alkyl group or water.
It is never an elementary atom. Also R₁And R₂Forms a ring
May be. The method of the present invention removes exposed silver halide.
Reduce to silver, bleach to oxidize the reduced silver, and
At least one to remove silver salts from the recording material.
Includes development stage. Bleaching and fixing can be bleaching
They can be combined in a known manner such as a white fixing solution. Color development is carried out in an aqueous developing bath.
The temperature of the developer is 25 ℃ to 50 ℃, which is generally used.
Can be kept at normal levels, and silver chloride can
Developed with photographic materials containing more than 1% silver halide grains
It has the advantage of being processed in a fairly short amount of time. In the present invention, a conventional developer is used for the color developing solution.
Instead of droxylamine sulfate, the compound represented by the general formula [I]
The compound is used. Therefore, in the present invention, hydroxylami
It is also important to be free of sulfates. In the general formula [I], R₁And R₂Is the same
Sometimes not a non-substituted alkyl or hydrogen atom,
Alkyl groups (including those having substituents) or
Represents a hydrogen atom, but R₁And R₂The substitution al represented by
The kill groups may be the same or different and each has 1 carbon atom.
~ 3 alkyl groups (including those with substituents) are preferred
New Also R₁  And R₂  Combine to form a ring
Alternatively, a heterocycle such as piperidine or morpholine can be
You may comprise. Hydroxyamine represented by the general formula [I]
Specific compounds of the series of compounds are described in US Pat. No. 3,287,
No. 125, No. 3,293,034, No. 3,2
87,124, etc., the following general formula
Embodiments containing a hydroxyamine compound represented by [I]
Specific examples of compounds are shown below. [0030] Embedded image [0031] Embedded image It is represented by the general formula [I] of the present invention in a color developing solution.
The concentration of the compound used is usually 0.2 g / liter to 50
g / liter, preferably 0.5 g / liter to 30 g /
Liter, more preferably 1 g / liter to 15 g /
Liters. The compound of the present invention represented by the general formula [I]
Is a color-developing material for conventional silver halide color photographic light-sensitive materials.
Hydroxy has been widely used as a preservative in image liquids.
Used in place of luamine sulphate
Of these, for example, N, N-diethylhydroxylamine
Is a black and white solution in a color developer containing a black and white developing agent.
It is known to be used as a preservative for developing agents,
For example, in the reversal method using a color developer containing a coupler
Therefore, the so-called external method for developing color photographic light-sensitive materials
The technology used with Phenidone in the color method is
It is. (See Japanese Patent Publication No. 45-22198). In particular, the compounds of the present invention have a
Even if it is lowered, the stability of the liquid over time is sufficiently high,
The change of the degree can be reduced and the photographic performance can be stabilized as a result.
I found out. According to the invention, the developing bath is replenished with a replenisher.
Be replenished. Overflow preferably occurs slightly
Do not supply the replenisher by another means to correct the evaporation.
Which is not necessary but economically totally overwhelming
Replenishment is reduced to such an extent that low does not occur
Automatically by the drinking method (Birds Fountain)
It is preferable to supply a replenishing solution to and correct it. In this case
The replenisher may be the color developing solution described above, or the color developing solution having a low concentration may be used.
It may be an image liquid. It may be water. In any case, development
It is necessary that the consumption component of the liquid component is sufficiently supplemented
However, in the present invention, among the halides which are the suppressing components,
Elution of highly effective bromide is extremely small, while chloride is
Is significantly increased. However, this chloride is
Copying using a silver chlorobromide emulsion with a high proportion of silver bromide as in the past
In comparison with the true material, which had a large development acceleration effect, silver chloride
Salt is contained in the silver halide photographic material of the present invention having a high ratio.
Compounds have only a very weak inhibitory effect, so
Development effect is obtained if chloride above a certain concentration is added to the developer.
The fruits are stabilized, for example, even if the supplement amount is large,
Even if it is not used, the change in photographic density can be extremely small.
And a compound represented by the general formula [I]
When used in combination, it is a species of photosensitive material with a high silver chloride content.
It is also an improvement of various drawbacks. Based on the above surprising findings
Instead of a low replenishment system with such drawbacks,
With the completion of a low replenishment system with very few changes
is there. Therefore, the bromide ion in the developer of the present invention is preferably
Contains very low concentrations in both replenisher and tank fluids
However, the concentration of bromide ion in the replenisher and tank liquid
Bromide ions in the replenisher solution of substantially the same degree or slightly
It is desirable to keep The silver halide in the photographic material of the present invention is extremely polar.
The amount that is eluted during development that contains a very low concentration of silver bromide
Is extremely small, but the bromide ion concentration changes in the developer
It is necessary to adjust the amount of bromide ion in the replenisher so that
There is an increase in bromide ion, which is concentrated especially by evaporation.
Bromide ion concentration in the replenisher is kept low to prevent
Can be The chloride in the present invention means in a color developing solution.
Any compound that releases chloride ions can be used.
Physical compounds include potassium chloride, sodium chloride,
Examples thereof include lithium chloride and magnesium chloride. Silver halide color reproduction used in the present invention
Halogen used in silver halide emulsion layer of true light-sensitive material
Silver chloride grains must have silver chloride content of 70 mol% or more
It is preferable that it is close to 100%, but silver chloride is 90
If the content is more than 100%, the effect that silver chloride is practically close to 100%
It was found that Especially when silver chloride is 95 mol% or less
In the above case, the effects of the object of the present invention are particularly well achieved.
The amount of developing agent is in the range of 0.5 g to 100 g per liter of developer.
Used, but preferably in the range of 2 to 15 g
You. Color development processing is usually performed in the range of 20 ° C to 80 ° C.
And preferably in the range of 30 ° C to 50 ° C. The pH at which the development is carried out is generally 8 or more, preferably
It is preferably 9.5 or higher. Development is carried out with a pH buffer, a development inhibitor, and an antifoggant.
Stopper, complexing agent for softening water, preservative, development acceleration
Agents, competing couplers, fogging agents, auxiliary developer compounds and
Can be carried out in the presence of a viscosity modifier; research
Disclosure 1754
4, December 1978, Section XXI, Industrial
・ Industrial Oppotunities
Ltd.), Homewell Havant, Hampshire, GrentBri
Issued by tain, and Ullmann's Enchiclopedi del
Ullmans Enzyklpudie der
 technisehen Chemie), 4th edition, 18 volumes, especially in 1979
 See pages 451 and 452 and 463 to 465. Suitable developer composition
Is Grant Haist, Modern
Photographic Processing (Modern Photograp
hie Processing), John Wiley and Sun
(John Oh Wiley and Sans), 1973, Vol. 1 and
Is given to 2. In the present invention, manganese salt or cerium
Color develops when salt is used in combination with the color developer of the invention.
The antioxidant performance of the developer is further improved, and it can be stored over time.
Since it also has another effect of improving the deterioration of the coloring property of
It is more preferably used in the present invention. Manganese salt and cerium according to the present invention
Salt is a manganese ion or a cell when dissolved in a developer.
A compound that releases um ions, preferably used
The following items are listed, but are not limited to these:
is not. Manganese chloride Manganese sulfate Manganese sulfite Manganese bromide Manganese phosphate Manganese nitrate Potassium permanganate Manganese acetate Manganese oxalate Manganese citrate Manganese ethylenediaminetetraacetate Cerium sulfate Cerium nitrate Cerium chloride Cerium carbonate Cerium phosphate Cerium acetate Cerium citrate Cerium oxalate These manganese salts and cerium salts are
Color appearance as form (manganese ion and cerium ion)
Use in the range of 0.1 mg to 100 mg per liter of image liquid
It is preferable that 0.3 mg to 20 mg is present.
And especially 0.5 mg to 10 mg is the effect of the object of the present invention.
From the point of, it is preferably used. Usually, sulfurous acid is used as a preservative in the color developer.
An acid salt is used, but a sulfurous acid is used in the color developer according to the present invention.
Acid salt concentration is 1.6 × 10 per liter of color developer.^-2Mo
Solution of high silver chloride content when used below
Suppresses the decrease in color density that is thought to be caused by physical development
And the decrease in preservative ability was extremely slight.
Therefore, if rapid processing is possible using a photosensitive material containing high silver chloride,
Color developing solution for squeezing or silver halide color using the solution
-Because it is possible to provide a method for processing photographs, in the present invention,
Sulfite concentration in color developer is 1.6 × 10^-2Mol / li
Torr or less is preferably used. Furthermore, this effect
1 × 10 shows better performance^-2Mol / liter or less
And more preferably 4 × 10^-3Mol / liter or less
It is. As the above-mentioned sulfite, sodium sulfite is used.
, Potassium sulfite, sodium bisulfite, calcium bisulfite
And the like. The developer used in the color developer used in the present invention
As a color developing agent, p-phenylene having a water-soluble group is used.
The diamine-based compound satisfactorily achieves the effect of the present invention,
In addition, it is preferably used because it causes less fogging. P-Phenylenediamine Having Water-Soluble Group
The system compound is N, N-diethyl-p-phenylenediami
Para-phenylenediamine system without water-soluble groups
Compared with the compound, the light-sensitive material is less contaminated and the skin
Not only does it have the advantage that the skin won't rash easily,
Particularly in the present invention, the compound represented by the above general formula [I]
In combination with, the objective of the present invention can be efficiently achieved.
Can be achieved. The water-soluble group is p-phenylenediamine.
At least one amino group or benzene nucleus
And a specific water-soluble group,
-(CH_Two )_n -CH_Two OH,-(CH_Two )_m -NHS
O_Two -(CH_Two )_n -CH_Three ,-(CH_Two )_m O- (C
H_Two )_n -CH_Three ,-(CH_Two CH_Two O)_n -C_m H
_{2m + 1}(M and n each represent an integer of 0 or more),-
COOH group, -SO_Three H group and the like are listed as preferable ones.
Can be Color developing agent preferably used in the present invention
Specific examples of the compound are shown below. [0051] Embedded image [0052] Embedded image[0053] Embedded image[0054] Embedded image[0055] Embedded image[0056] Embedded image Among the color developing agents exemplified above, generation of fog is small.
Since it is not present, the preferred No. (A-
1), (A-2), (A-3), (A-4), (A-
6) With the compounds shown in (A-7) and (A-15)
And particularly preferably (A-1). The above color developing agent is usually a hydrochloride or a sulfuric acid.
Used in the form of salt such as salt and p-toluene sulfonate
It is. Coloring having a water-soluble group used in the present invention
The developing agent is usually 1 × 10 per liter of color developing solution.
^-2~ 2 x 10^-1It is preferable to use it in the molar range
However, from the viewpoint of rapid processing, per liter of color developer
1.5 x 10^-2~ 2 x 10^-1A molar range is more preferred. The color developing agent may be used alone or
In combination with two or more kinds, and if desired, a black and white developing agent such as
Phenidone, 4-hydroxymethyl-4-methyl-1-
Used in combination with phenyl-3-pyrazolidone or metol
May be. Further, the above color developing agent is used in a color developing solution.
Instead of adding a color developing agent to the photosensitive material
The color developing agent used in this case is color
Elementary precursors. Representative dye precursor
Examples are those described in JP-A-58-65429 and JP-A-58-24137.
Used, specifically, for example, 2 ', 4'-bismethane
Sulfonamide-4-diethylaminodiphenylami
2'-methanesulfonamide-4 '-(2,4,6
-Triisopropyl) benzenesulfonamide-2-me
Cyl-4-N- (2-methanesulfonamidoethyl) d
Cylaminodiphenylamine, 2'-methanesulfone
Mido-4 '-(2,4,6-triisopropyl) benze
Sulfonamide-4- (hydroxytrisethoxy)
Diphenylamine, 4-N- (2-methanesulfonami
Deethyl) ethylamino-2-methyl-2 ', 4'-bi
Su (2,4,6-triisopropyl) benzene sulfone
Amidodiphenylamine, 2,4'-bismethanesulfone
Namide-4-N, N-diethylaminodiphenylami
4-n-hexyloxy-2'-methanesulfone
Mido-4 '-(2,4,6-triisopropyl) benze
Sulfonamide diphenylamine, 4-methoxy-
2'-methanesulfonamide-4 '-(2,4,6-to
Liisopropyl) benzenesulfonamide diphenyl
Min, 4-dihexylamino-4 '-(2,4,6-to
Liisopropylbenzenesulfonamide) diphenyl
Min, 4-n-hexyloxy-3'-methyl-4'-
(2,4,6-triisopropylbenzenesulfonami
D) diphenylamine, 4-N, N-diethylamino-
4 '-(2,4,6-triisopropylbenzenesulfon
Amide) diphenylamine, 4-N, N-dimethyl
Mino-2-phenylsulfonyl-4 '-(2,4,6-
Triisopropylbenzenesulfonamide) diphenyl
Examples include amines. Addition of the dye precursor to the light-sensitive material
The amount is 100 cm of photosensitive material^Two About 0.5 to 22 mg is preferred
And more preferably 4 to 12 mg. The color developer according to the present invention contains the following general
When the compound represented by the formula [D] is contained, the present invention is
Of the color developing solution
Since it also shows an improving effect on gas oxidation, more preferred use
Can be. [0063] Embedded image (Where R_{twenty one}Is a hydroxyalkyl group having 2 to 6 carbon atoms,
R_{twenty two}And R_{twenty three}Represents a hydrogen atom and an alkyl having 1 to 6 carbon atoms, respectively.
Kill group, hydroxyalkyl having 2 to 6 carbon atoms In the above formula, n1 is an integer of 1 to 6 and X'and Z'are water.
Elementary atom, alkyl group having 1 to 6 carbon atoms or 2 carbon atoms
6 represents a hydroxyalkyl group. ) Preferred of the compound represented by the above general formula [D]
A concrete example is as follows. (D-1) ethanolamine, (D-2) diethanolamine, (D-3) triethanolamine, (D-4) di-isopropanolamine, (D-5) 2-methylaminoethanol, (D-6) 2-ethylaminoethanol, (D-7) 2-dimethylaminoethanol, (D-8) 2-diethylaminoethanol, (D-9) 1-diethylamino-2-propanol, (D-10) 3-diethylamino-1-propanol, (D-11) 3-dimethylamino-1-propanol, (D-12) Isopropylaminoethanol, (D-13) 3-amino-1-propanol, (D-14) 2-Amino-2-methyl-1,3-propane
Diol, (D-15) ethylenediaminetetraisopropanol, (D-16) benzyldiethanolamine, (D-17) 2-Amino-2- (hydroxymethyl)-
1,3-propanediol. These are the compounds represented by the above general formula [D].
The object of the present invention is that the color developing solution is 1 liter.
It is preferably used in the range of 3 g to 100 g per
It is preferably used in the range of 6 g to 50 g. The color developer according to the present invention contains the following general
Contains a compound represented by the formula [B-I] to [B-IV]
In doing so, the effects of the present invention can be better achieved, and
When bleaching or bleach-fixing processing is performed immediately after color development on
Since the bleaching fog that occurs is also improved,
It is more preferably used in light. [0067] Embedded imageWhere R₁₁, R₁₂, R₁₃And R₁₄Is hydrogen source
Child, halogen atom, sulfonic acid group, having 1 to 7 carbon atoms
Alkyl group, -OR_Fifteen, -COOR₁₆, Are hydrogen atom or alkyl having 1 to 18 carbon atoms, respectively.
Represents a group. Where R₁₂Represents -OH or a hydrogen atom
If R₁₁Is a halogen atom, sulfonic acid group, carbon_/R₁₇ An alkyl group having 1 to 7 atoms, -OR_Fifteen, -COOR₁₆, -CON or                                                           ^\R₁₈ Represents a phenyl group. R₁₁, R₁₂, R₁₃And R₁₄Is represented by
The alkyl group includes those having a substituent, such as methyl.
Group, ethyl group, iso-propyl group, n-propyl group, t
-Butyl group, n-butyl group, hydroxymethyl group, hydr
Roxyethyl group, methylcarboxylic acid group, benzyl group, etc.
And also R_Fifteen, R₁₆, R₁₇And R₁₈Is represented by
The kill group has the same meaning as described above, and further includes an octyl group and the like.
Can be mentioned. R₁₁, R₁₂, R₁₃And R₁₄Is represented by
As a phenyl group, a phenyl group, 2-hydroxyphenyl
Group, 4-aminophenyl group and the like. Representative specific examples of the chelating agent of the present invention and
However, it is not limited to these.
No. (B-I-1) 4-isopropyl-1,2-dihydroxy
Sibenzene (B-I-2) 1,2-dihydroxybenzene-3,5
-Disulfonic acid (B-I-3) 1,2,3-trihydroxybenzene-
5-carboxylic acid (B-I-4) 1,2,3-trihydroxybenzene-
5-carboxymethyl ester (BI-5) 1,2,3-trihydroxybenzene-
5-carboxy-n-butyl ester (B-I-6) 5-t-butyl-1,2,3 trihydro
Xybenzene (BI-7) 1,2-dihydroxybenzene-3,
4,6-trisulfonic acid (B-II-1) 2,3-dihydroxynaphthalene-6-
Sulfonic acid (B-II-2) 2,3,8-trihydroxynaphthalene
-6-sulfonic acid (B-II-3) 2,3-dihydroxynaphthalene-6
carboxylic acid (B-II-4) 2,3-dihydroxy-8-isopropylate
Lunaphthalene (B-II-5) 2,3-dihydroxy-8-chloro-na
Phthalene-6-sulfonic acid Among the above compounds, particularly preferably used in the present invention
As the compound, 1,2-dihydroxybenzene-3,
5-disulfonic acid, sodium salt, potassium
It can also be used as an alkali metal salt such as a salt. In the present invention, the above general formula [BI] and
And the compound represented by [B-II] is 1 liter of color developer.
It can be used in the range of 5 mg to 20 g per
10 mg to 10 g, more preferably 20 mg to 3 g
Good results can be obtained. [0072] Embedded image(In the general formulas [B-III] and [B-IV], L is
Ren group, cycloalkylene group, phenylene group, -L₈−
OL₈-OL₈-Or -L₉-ZL₉- Represents R₃₃~ R₄₃Are hydrogen atom, hydroxyl group, and
Bonic acid group (including its salt) or phosphonic acid group (including its salt)
Is included). Where R₃₃~ R₃₆At least of
Two are carboxylic acid groups (including their salts) or phosphonic acids
A group (including a salt thereof), and R₃₇~ R₃₉Little of
At least two are carboxylic acid groups (including their salts) or
It is a sulfonic acid group (including its salt). ) In the above general formulas [B-III] and [B-IV],
An alkylene group represented by L, a cycloalkylene group
And a phenylene group, and L₁ ~ L₁₃Represented by
The len group also includes those having a substituent. Next, these general formulas [B-III] and [B
-IV] is a preferred specific exemplary compound represented by
Listed below. [Exemplified Compound] [B-III-1] Ethylenediaminetetraacetic acid [B-III-2] diethylenetriaminepentaacetic acid [B-III-3] Ethylenediamine-N- (β-hydro
Xyethyl) -N, N ', N'-triacetic acid [B-III-4] Propylenediaminetetraacetic acid [B-III-5] triethylenetetraminehexaacetic acid [B-III-6] cyclohexanediaminetetraacetic acid [B-III-7] 1,2-diaminopropanetetraacetic acid [B-III-8] 1,3-diaminopropan-2-O
Le-tetraacetic acid [B-III-9] Ethyl ether diamine tetraacetic acid [B-III-10] glycol ether diamine tetra
Acetic acid [B-III-11] ethylenediamine tetrapropion
acid [B-III-12] phenylenediaminetetraacetic acid [B-III-13] Ethylenediaminetetraacetic acid dinatto
Lium salt [B-III-14] tetraethylenediaminetetraacetic acid
(Trimethylammonium) salt [B-III-15] tetraethylenediaminetetraacetic acid
Sodium salt [B-III-16] diethylenetriaminepentaacetic acid
Sodium salt [B-III-17] Ethylenediamine-N- (β-hydr
Roxyethyl) -sodium N, N ', N'-triacetate
salt [B-III-18] propylenediaminetetraacetic acid nato
Lium salt [B-III-19] ethylenediaminetetramethylenepho
Sulphonic acid [B-III-20] cyclohexanediaminetetraacetic acid
Sodium salt [B-III-21] diethylenetriaminepentamethyle
Phosphonic acid [B-III-22] cyclohexanediaminetetramethyl
Lenphosphonic acid [B-IV-1] Nitrilotriacetic acid [B-IV-2] iminodiacetic acid [B-IV-3] Nitrilotripropionic acid [B-IV-4] Nitrilotrimethylenephosphonic acid [B-IV-5] iminodimethylene phosphonic acid [B-IV-6] Nitrilotriacetic acid trisodium salt [B-IV-7] Hydroxyethyliminodiacetic acid sodium salt
Salt A compound represented by the general formula [B-III] or [B-IV]
Compounds that are preferably used in the present invention among the compounds
Compounds [B-III-1], [B-III-2], [B
-III-5], [B-III-8], [B-III-19],
[B-IV-1], [B-IV-4] and [B-IV-7] are
No. Furthermore, these general formulas [B-III] or
The compound represented by [B-IV] is equivalent to 1 liter of color developing solution.
It is preferably used in the range of 0.1 to 20 g, especially
From the viewpoint of the object of the present invention, the range of 0.3-5 g is particularly preferable.
Used. The formulas [B-I] to [B-IV] are shown.
These compounds can be used alone or in combination.
May be. Furthermore, citric acid or gluconic acid
Oxycarboxylic acid such as 2-phosphonobutane-1,2,2
Phosphonocarboxylic acids such as 4-tricarboxylic acid, tripoly
Phosphoric acid or polyphosphoric acid such as hexametaphosphoric acid
Other chelating agents may be used in combination. In the present invention, the invention according to the above-mentioned invention is
The color developing solution contains triazinyl represented by the following general formula [III].
The use of stilbene-based optical brighteners causes more fogging.
It is less and preferable. [0078] Embedded image Where X₁ , X_Two , Y₁ And Y_Two Are hydroxyl group and salt
Halogen atom such as elemental or bromine, morpholino group, alkoxy
Si group (eg methoxy, ethoxy, methoxyethoxy
Etc.), aryloxy groups (eg phenoxy, p-sulfur)
Hophenoxy etc.), alkyl groups (eg methyl, ethyl)
Etc.), aryl groups (eg phenyl, methoxyphenyl)
Etc.), amino groups, alkylamino groups (eg methylami
No, ethylamino, propylamino, dimethylamino,
Cyclohexylamino, β-hydroxyethylamino,
Di (β-hydroxyethyl) amino, β-sulfoethyl
Amino, N- (β-sulfoethyl) -N′-methylami
No, N- (β-hydroxyethyl-N′-methylamino
Etc.), arylamino groups (eg anilino, o-, m
-, P-sulfoanilino, o-, m-, p-chloroani
Reno, o-, m-, p- Toluidino, o-, m-, p-
Carboxyanilino, o-, m-, p-hydroxyaniline
Rino, sulfonaphthylamino, o-, m-, p-amino
Anilino, o-, m-, p-anidino, etc.). M is
Hydrogen atom, sodium, potassium, ammonium or lithium
Represents thium. Specifically, the following compounds may be mentioned.
It is possible, but not limited to these. [0080] Embedded image[0081] Embedded image[0082] Embedded image[0083] Embedded image[0084] Embedded image[0085] Embedded imageTriazylsti represented by the general formula [III]
Ruben-based whitening agents are, for example, "Fluorescent Whitening" edited by Chemical Industry Association.
Agent "(issued in August 1976)
Can be synthesized by the method of. These triazinyl stilbene whitening agents
Is 0.2 to 6 per liter of the color developing solution used in the present invention.
It is preferably used in the range of g, and particularly preferably 0.4 to 3
It is in the range of g. The color developer of the present invention comprises a poly (alkylene).
Imine). Poly (alkyleneimine)
Substituted or unsubstituted repeats linked to each other via elementary atoms
It consists of alkylene chain units. These are well-known commercial substances
A typical poly (alkyleneimine) is
The compound shown by [I '] is mentioned. [0089] (Where R₁ ′ Represents an alkylene group having 1 to 6 carbon atoms
Then R_Two 'Represents an alkyl group, n'is 500 to 20,000
Represents an integer. ) R above₁ Having 1 to 6 carbon atoms represented by
The alkylene group may be linear or branched and is preferably carbon.
An alkylene group having 2 to 4 atoms, for example, an ethylene group, a propylene group
Pyrene group, butene group, isobutene group, dimethyl ethylene
Group, ethylethylene group and the like. R_Two Represented by ’
The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms.
Group, for example, methyl group, ethyl group, propyl group, etc.
In addition, a substituent (such as a hydroxyl group) may be further added.
Including those that have. n'is the repeating unit in the polymer chain
And represents an integer of 500 to 20,000, preferably
It is an integer from 500 to 2,000. R₁ 'Is an ethylene group
Poly (ethyleneimine) is most preferred for the purposes of the present invention.
No. The following are used in the color developing solution of the present invention.
Specific examples of poly (alkyleneimine) are shown below, but the present invention
It is not limited to these. Exemplified Compound PAI-1 Poly (ethyleneimine) PAI-2 poly (propyleneimine) PAI-3 Poly (buteneimine) PAI-4 Poly (isobutenimine) PAI-5 Poly (N-methylethyleneimine) PAI-6 Poly (N-β-hydroxyethylethylene
Imine) PAI-7 Poly (2,2-dimethylethyleneimine) PAI-8 Poly (2-ethylethyleneimine) PAI-9 Poly (2-methylethyleneimine) The poly (alkyleneimine) is used in the present invention in a color developer.
Can be used in any amount that can achieve the purpose of
However, 0.1 to 500 g per liter of color developing solution is generally preferred.
And more preferably in the range of 0.5 g to 300 g. The poly (alkyleneimine) of the present invention is
For use with hydroxylamine in color developers
Improves the storage stability of the color developer and increases the concentration of sulfite.
Japanese Patent Laid-Open No. 56-94349
It is described in the report. However, this method is
When a heavy metal is mixed in, the decomposition of hydroxylamine occurs and it is preserved.
Since the stability decreases, it is not sufficient as a technique for improving the homeostasis.
Not only there, but also excellent as a preservative and heavy metal
The present inventors have found that it is a strong preservative against the contamination of genus
Generated diethylhydroxylamine and dimethylhydroxyl
Color developer containing hydroxylamine derivative such as silamine
Coloring of liquid that occurs when used inside and photosensitive material resulting therefrom
Polyalkyleneimine is effective for the problem of contamination of containers and containers
Regarding the solution to
Not listed well. That is, coloring of such liquids and
The problem of contamination of photosensitive materials, containers, etc.
Does not occur with luamine, but with diethylhydroxylamine and diamine
Derivation of hydroxylamine such as methylhydroxylamine
It is a problem that occurs uniquely when using the body,
The existence of the problem itself has never been known, and
Lialkyleneimine is said to solve this problem effectively
It is a surprising effect that is totally unexpected. In the present invention, the processing time of the color developing step
Can be any time, but normally 5 seconds to 5 minutes is used
Can be Usually, the high silver chloride light-sensitive material of the present invention is used for 15 seconds.
Color development time of ~ 60 seconds is used, but color development is 1
When processing for a long time of 50 seconds or more, during large-volume processing and small-volume processing
Since it has the effect of reducing the difference in photographic characteristics during physical processing,
The photo processing characteristics of the imitation lab and the mini lab (small lab) are close.
Therefore, the effect that the photographic characteristics of the market are uniform is exhibited.
Therefore, it is more preferably used. Especially this effect is color development
It becomes remarkable when the process is 180 seconds or more. Replenishment amount is photographic material m^TwoRange of 300 to 10 ml per
However, in order to maximize the effect of the present invention,
 It is a treatment in the range of 150 ml to 30 ml. Especially preferred
It is preferably in the range of 120 ml to 50 ml, most preferably 1
It is processed in the range of 00 ml to 80 ml. In addition, the capacity loss due to evaporation depends on the replenishment rate.
Slightly less than the rate at which developer is carried out of the machine
Set to standard, and the remaining capacity loss is easy automatic replenishment
By adding and supplementing replenisher from the device, you can easily
It has been found that it can be compensated dynamically. In a preferred embodiment, a replenisher solution is prepared.
Put the concentrated and adjusted kit used for
The water replenishing device while controlling the shortage of water by lowering the liquid level
Can be supplied from. In the preferred developer of the invention, benzyl acetate is used.
It is preferable that it is substantially free of rucol. Real here
Benzyl alcohol is not contained qualitatively 2ml / lit
Most preferably not included in the present invention.
New Benzyl alcohol has extremely low solubility and replenishment amount
The liquid is concentrated in the treatment of the present invention with extremely few
Since it is easy to get rid of oil, it may stick to the photographic material due to oil deposition
Tal formation due to oxidation of color developing agents is extremely troublesome
Generate a problem. As described above, the solubility is extremely low.
Put the adjusted concentration kit directly into the developing tank
In such cases, a mechanical mixing device is required and it is extremely complicated.
It will happen. Therefore, the effect of the present invention is maximized.
Benzyl alcohol is an undesirable additive for
I found something. In the present invention, after color development processing,
Although it is processed with a processing solution having fixing ability, it has the fixing ability.
If the processing solution is a fixing solution, bleaching is performed before that.
It is. For the bleaching solution or bleach-fixing solution used in the bleaching process
As a bleaching agent used in, metal complex salts of organic acids are used.
The metal complex salt contains metallic silver produced by development.
Oxidation and conversion to silver halide, and at the same time undeveloped coloring agent
It has the effect of coloring parts and its composition is amino.
Iron with organic acids such as polycarboxylic acid or oxalic acid, citric acid,
Coordination of metal ions such as cobalt and copper. This
Used to form metal complex salts of organic acids such as
The most preferable organic acid is polycarboxylic acid or acetic acid.
Examples include minopolycarboxylic acids. These polycarbs
Acid or aminopolycarboxylic acid is an alkali metal salt,
It may be an ammonium salt or a water-soluble amine salt. Specific examples of these are as follows.
Things can be mentioned. [1] Ethylenediaminetetraacetic acid [2] Diethylenetriamine pentaacetic acid [3] Ethylenediamine-N- (β-oxyethyl)-
N, N ', N'-triacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] cyclohexanediaminetetraacetic acid [7] iminodiacetic acid [8] Dihydroxyethylglycine citric acid (or tartar
acid) [9] Ethyl ether diamine tetraacetic acid [10] Glycol ether diamine tetraacetic acid [11] Ethylenediaminetetrapropionic acid [12] Phenylenediamine tetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra (trimethyi)
Ruammonium) salt [15] Tetrasodium ethylenediaminetetraacetate
salt [16] Diethylenetriamine pentaacetic acid pentanatri
Um salt [17] Ethylenediamine-N- (β-oxyethyl)
-N, N ', N'-triacetic acid sodium salt [18] Propylenediaminetetraacetic acid sodium salt [19] Nitriloacetic acid sodium salt [20] Cyclohexanediamine sodium tetraacetate
salt The bleaching solution used contains the metal complex salt of an organic acid as described above.
In addition to being contained as a whitening agent, it may contain various additives.
it can. As an additive, especially an alkali halide or
Is an ammonium halide such as potassium bromide or sodium bromide.
Reuse of thorium, sodium chloride, ammonium bromide, etc.
Desirable to contain a rotagenizer, metal salt, chelating agent
Good. Also borate, oxalate, acetate, carbonate, phosphate
PH buffers such as, alkylamines, polyethylene oxy
It is known to be added to normal bleaching liquids such as sides
Can be appropriately added. Further, the fixing solution and the bleach-fixing solution are sulphites.
Ammonium, potassium sulfite, sodium bisulfite,
Ammonium bisulfite, potassium metabisulfite, meta
Sulfite such as sodium bisulfite, boric acid, borax, and hydroxide
Sodium, potassium hydroxide, sodium carbonate, carbonate
Lium, sodium bicarbonate, potassium bicarbonate, acetic acid, vinegar
Consists of various salts such as sodium acidate and ammonium hydroxide
PH buffering agents may be used alone or in combination of two or more.
You. Replenishing bleach-fixing solution (bath) with bleach-fixing replenisher
When performing the treatment while doing so, the bleach-fix solution (bath) should be treated with thiosulfuric acid.
Acid salt, thiocyanate or sulfite
OK, make sure that the bleach-fix replenisher contains these salts
The treatment bath may be replenished. In the present invention, a bleaching solution or a bleach-fixing solution is used.
In the bleaching bath or bleach-fixing bath to enhance the activity
Empty the storage tank for the replenisher or bleach-fix replenisher if desired.
You may blow air or blow oxygen.
Or a suitable oxidizing agent such as hydrogen peroxide, bromic acid
You may add salt, persulfate, etc. suitably. In the present invention, from the viewpoint of rapid processing,
A bleach-fixing solution is preferably used, and high silver chloride as in the present invention is used.
When using a light-sensitive material and performing bleach-fix processing immediately after color development
Stain, which is called bleaching fog, is liable to occur in the. This
Therefore, as a result of various studies, the pH of the bleach-fix solution was 4.5 to 6.8.
This range can be solved only by using it in a range.
However, it turned out that it also has the effect of increasing the silver bleaching speed.
Was. In particular, this effect depends on the pH of the bleach-fix solution.
It is good in the case of 5 to 6.3. In the treatment of the present invention, washing or washing allowance
Soluble silver such as fixer and bleach-fixer as well as replacement stabilizer
Silver may be recovered from the processing solution containing the complex salt by a known method.
No. Electrolysis method (French Patent No. 2,299,667), precipitation
Method (JP-A-52-73037, German Patent 2,331,220), Io
Exchange method (JP-A-51-17114, German Patent 2,548,237)
And metal substitution method (UK patent 1,353,805) are effective
Available. Color development processing in the processing method of the present invention
After post-bleaching and fixing (or bleach-fixing) treatment, wash with water.
It can be stabilized without any treatment, or washed with water and then
It may be stabilized. In addition to the above steps, dura, neutralization, black
White development, reversal, small amount water washing process, etc.
Auxiliary steps may be added. Representative of preferred treatment methods
Specific examples include the following steps. (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 → Bleaching / fixing → Washing → Stable (4) Color development → bleach-fix → stable (5) Color development → Bleaching and fixing → First stable → Second stable (6) Color development → washing (or stable) → bleach-fixing → washing
(Or stable) (7) Color development → stop → bleach-fix → washing with water (or stable) (8) Color development → bleaching → washing → fixing → washing → stable (9) Color development → Bleaching → Fixing → Rinsing → Stable (10) Color development → bleaching → washing with a small amount of water → fixing → first stabilization → first
2 stable (11) Color development → bleaching → washing with a small amount of water → fixing → washing with a small amount of water → water
Wash → stable (12) Color development → wash with a small amount of water → bleach → wash with a small amount of water → fix → low
Amount Washing → Washing → Stable (13) Color development → stop → bleach → small amount of water washing → fixing → small amount of water
Washing → water washing → stable Among these steps, the work of (4) to (5)
Is preferably used. Another preferred in the treatment method of the present invention
As one of the embodiments, the color developer of the present invention is over
A bleaching solution that is the process of continuing part or all of the flow solution
Or a method of flowing into a bleach-fixing solution. this
Is a bleaching solution or a bleach-fixing solution for color development according to the present invention.
When a certain amount of solution is flowed in, the bleaching solution or bleach-fixing solution
Reduces sludge generation and more surprisingly bleaching
This is because the efficiency of silver recovery from the fixer is also improved. Further, in addition to the above-mentioned method, a stabilizing solution for the subsequent process is used.
Part or all of the overflow solution of
Especially when it is poured into the fixer, the above effects are particularly well achieved.
You. Specific examples of these are shown in FIG.
The following are listed. At least the silver chloride used in the present invention is used.
A halo containing silver halide grains of 70 mol%
The silver genide emulsion layer has a color coupler. These empty
-Coupler reacts with oxidation products of color developer and does not diffuse
Forming a sexual dye. Color couplers are advantageously non-diffusible
Formed in or closely adjacent to the photosensitive layer
You. Thus the red-light sensitive layer is for example a cyan part
Non-diffusive color couplers that produce color images, typically
Contains phenol or α-naphthol couplers
Can be The green-photosensitive layer is, for example, magenta partial
At least one non-diffusible color cover producing a color image
Pullers, usually 5-pyrazolone color couplers and pigments
Razolotriazole can be included. Blue-photosensitive layer
At least one that produces a yellow partial color image, for example
Non-diffusible color couplers, generally with open chain ketomethylene groups
Can include a color coupler having. Color cap
Ra is, for example, a 6-, 4- or 2-equivalent coupler.
be able to. In the present invention, especially 2 equivalent caps
Ra is preferred. Suitable couplers are disclosed, for example, in the following publications:
Has been done: Agfa's research report (Mitteilungln aus
den Forschungslaboratorien der Agfa), Lefe
Leverkusen / Munchen,
Vol. III. p. 111 (1961) Medium W. Bertz
"Color Coupler" by (W.Pelz) (Farbkuppl
er); K. Venkataraman
 ), “The Chemistry of Synthetic Da
Is "(The Chemirsry of Synthetic Dyes),
Vol. 4, 341-387, Academic Press (Acade
mic Press), (1971); TJ James
(TH James), “The Theory of the For
The Graphic Process "(The Theory of the
Photographic Process, 4th Edition, pp. 353-362; and
Magazine Research Disclosure (Reserch Discl)
osure) No. 17643, Section VII. According to one particularly preferred embodiment, it is usually added.
Fully coupled without benzyl alcohol
A color coupler is used. benzyl alcohol
Is the cap between the oxidized color developer and the coupler.
Printing at a desired speed to form an image dye.
It is commonly used as a phase transfer agent that enables However
However, in practical use, benzyl alcohol
As mentioned above, it has always been a source of trouble, especially in the generation of tar.
Become a source of disability. Used without benzyl alcohol
Suitable couplers are available from DE-A 3,209,710.
Nos. 2,441,779, 2,640,601 and European patent applications
Shown in Publication No. 0067689. A preferred yellow coupler has a structure corresponding to the formula:
With structure: [0117] Embedded image[0118] Embedded imageThe following magenta couplers are particularly preferred. : [0119] Embedded image[0120] Embedded imageThe following cyan couplers are especially preferred. : [0121] Embedded image[0122] Embedded imageAmong the above yellow couplers,
Short processing time when using high-speed reactive yellow coupler
The color development at the time of the
Therefore, in the present invention, the rapid reactivity is improved.
An ero coupler is preferably used. Blue-sensitive silver halide emulsion layer according to the present invention
The fast-reacting yellow coupler used in
It is a yellow coupler with a ring reaction rate of 0.3 or more,
Preferably, the relative coupling reaction rate is 0.5 or more.
It is a low coupler. The coupling kinetics of the couplers are mutually clear.
Two types of couplers M that give different dyes that can be clearly separated
And N are mixed and added to a silver halide emulsion for color development.
The amount of each dye in the color image obtained by
It can be determined as a relative value by measuring. Maximum density (DM) max of coupler M, halfway
In the step, the color development of the density DM,
Let's call it (DN) max and DN, respectively.
For example, the reaction activity ratio RM / RN of both couplers is expressed by the following formula.
Is done. [0127] (Equation 1) In other words, in a silver halide emulsion containing mixed couplers,
It is possible to obtain several colors obtained by color development after exposure at various stages.
Set the DM and DN pairs to two orthogonal axes [0128] (Equation 2) From the slope of the straight line obtained by plotting as
The value of the activity ratio RM / RN can be obtained. Here, various couplers are used by using a certain coupler N.
Obtain the RM / RN value as described above for the puller.
Then the relative value of the coupling reaction rate, that is, the relative coupling
Ring reaction rate values are determined. In the present invention, as the above-mentioned coupler N,
The RM / RN value when the following coupler is used. [0131] Embedded imageThe addition amount of the fast-reactive yellow coupler of the present invention is limited.
However, 1 mol of silver in the blue-sensitive silver halide emulsion layer
2 × 10^-3~ 5 × 10^-1Molar preferred, more preferred
1x10^-2~ 5 × 10^-1Is a mole. The following is a description of the fast-reactive yellow cap of the present invention.
Examples of Ra are given below, but are not limited to these.
No. [0133] Embedded image [0134] Embedded image[0135] Embedded image[0136] Embedded image[0137] Embedded image[0138] Embedded image[0139] Embedded image[0140] Embedded image[0141] Embedded image[0142] [Chemical 38][0143] Embedded image[0144] Embedded image[0145] Embedded image[0146] Embedded image[0147] [Chemical 43][0148] Embedded image[0149] [Chemical formula 45][0150] Embedded image[0151] Embedded image[0152] Embedded image In the present invention, a magenta coupler is used.
From the above-mentioned pyrazolone magenta coupler
A triazole-based magenta coupler is preferably used.
It is. This is after color development using a high silver chloride light-sensitive material.
No bleaching immediately or unexposed during bleach-fix processing
There is a drawback that stain is easily generated in the part, but magenta cap
As a pyrazolotriazole magenta coupler
This defect is not only remedied when it is used, but it is also treated for a short time.
Because the magenta dye density in the highest density area at the time of processing also becomes better
It is. Among the pyrazolotriazole couplers,
The reason why the coupler represented by the following general formula [MI] is preferred.
It is used well. [0154] Embedded image In the magenta coupler represented by the formula, Z is a nitrogen-containing complex
Represents a group of non-metallic atoms necessary to form a ring,
The ring formed may have a substituent. X is a hydrogen atom or an oxidant of a color developing agent.
Represents a group capable of leaving by the reaction of R is a hydrogen atom or
Represents a substituent. The substituent represented by R is not particularly limited.
However, typically, alkyl, aryl, anilino, acyl
Amino, sulfonamide, alkylthio, arylchi
Examples include groups such as o, alkenyl, and cycloalkyl.
In addition to these, halogen atom, cycloalkenyl,
Quinyl, heterocycle, sulfonyl, sulfinyl, phosphoni
Le, acyl, carbamoyl, sulfamoyl, cyano,
Alkoxy, aryloxy, heterocyclic oxy, siloxy
Ci, acyloxy, carbamoyloxy, amino, ar
Kiramino, imide, ureido, sulfamoylami
No, alkoxycarbonylamino, aryloxycal
Bonylamino, alkoxycarbonyl, aryloxy
Carbonyl, heterocyclic thio groups, and spiro compounds
Residues, bridged hydrocarbon compound residues and the like are also included. The alkyl group represented by R has a carbon number of
Those having 1 to 32 are preferable and may be linear or branched. The aryl group represented by R is phenyl
Preferred is a thiol group. The acylamino group represented by R is
Rukylcarbonylamino group, arylcarbonylamino
And the like. As the sulfonamide group represented by R,
Alkylsulfonylamino group, arylsulfonylamido
And the like. An alkylthio group represented by R, an arylthio group
The alkyl component and aryl component in the group o are represented by R above.
And an alkyl group and an aryl group. The alkenyl group represented by R is carbon
Number 2-32, cycloalkyl group having 3 carbon atoms
-12, especially 5-7 are preferable, and the alkenyl group is
It may be linear or branched. As a cycloalkenyl group represented by R,
Preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms. The sulfonyl group represented by R is an alkyl group.
Rusulfonyl group, arylsulfonyl group, etc .; Sulfini
Examples of the alkyl group include alkylsulfinyl group and arylsulfinyl group.
And the like; alkylphosphonyl as the phosphonyl group
Group, alkoxyphosphonyl group, aryloxyphosphonyl group
Group, arylphosphonyl group, etc .;
Killcarbonyl group, arylcarbonyl group, etc .; carbamo
Alkylcarbamoyl group, arylcarbyl group
Vamoyl group, etc .; Sulfamoyl group is alkylsulfur
Famoyl group, arylsulfamoyl group, etc .; Acyl
As the xy group, an alkylcarbonyloxy group, aryl
Carbonyloxy group etc .; as carbamoyloxy group
Alkylcarbamoyloxy group, arylcarbamoyl
An oxy group, etc .; an ureido group is an alkylureido group,
Arylureido group, etc .; as sulfamoylamino group
Is an alkylsulfamoylamino group, arylsulfamoyl
Moylamino groups and the like; heterocyclic groups having 5 to 7 members
Preferably, specifically, a 2-furyl group, a 2-thienyl group,
2-pyrimidinyl group, 2-benzothiazolyl group, etc .; hetero
The ring oxy group preferably has a 5- to 7-membered heterocycle.
For example, 3,4,5,6-tetrahydropyranyl
-2-oxy group, 1-phenyltetrazole-5-oxo
Si group, etc .; as a heterocyclic thio group, a 5- to 7-membered heterocyclic thio group
Groups are preferred, eg 2-pyridylthio group, 2-benzo
Thiazolylthio group, 2,4-diphenoxy-1,3,5
-Triazole-6-thio group and the like;
Limethylsiloxy group, triethylsiloxy group, dimethyl
Butylsiloxy group, etc .; succinimide as the imide group
Group, 3-heptadecyl succinimide group, phthalimide
Group, glutarimide group, etc .;
Pyro [3.3] heptan-1-yl etc .; Bridged hydrocarbon
As a compound residue, bicyclo [2.2.1] heptane-1
-Yl, tricyclo [3.3.1.1^3,7 ] Decan-1
-Yl, 7,7-dimethyl-bicyclo [2.2.1] he
Examples include butan-1-yl and the like. For the reaction with the oxidant of the color developing agent represented by X
Examples of the more removable group include a halogen atom (chlorine
Atom, bromine atom, fluorine atom, etc.), alkoxy, aryl
Luoxy, heterocyclic oxy, acyloxy, sulfonylo
Xy, alkoxycarbonyloxy, aryloxyca
Rubonyl, alkyl oxalyloxy, alkoxy oxy
Zaryloxy, alkylthio, arylthio, heterocyclic thi
O, alkyloxythiocarbonylthio, acylami
No, a sulfonamide, a nitrogen-containing heterocycle bonded by an N atom,
Alkyloxycarbonylamino, aryloxycal
Bonylamino, carboxyl, [0166] Embedded image (R₁ ′ Is as defined above for R, and Z ′ is as defined above for Z.
Yes, R_Two 'And R_Three ′ Is a hydrogen atom, aryl group, ar
It represents a kill group or a heterocyclic group. ) And the like.
Is preferably a halogen atom, especially a chlorine atom. The nitrogen-containing compound formed by Z or Z '.
As the elementary ring, a pyrazole ring, an imidazole ring, a tria ring
Examples of the ring include a azole ring and a tetrazole ring.
As the substituents that may be mentioned, those described above for R are
No. Those represented by the general formula [MI] are further
Physically, for example, in the following general formulas [M-II] to [M-VII]
Is represented by [0169] Embedded imageIn the general formulas [M-II] to [M-VII], R₁ ~ R₈
 And X have the same meanings as R and X described above. Of the general formula [MI], preferred
Is represented by the following general formula [M-VIII]. [0171] Embedded image Where R₁ , X and Z₁ Is R in the general formula [M-I],
Synonymous with X and Z. The formulas [M-II] to [M-VII]
Among the magenta couplers to be used, particularly preferable ones are generally
It is a magenta coupler represented by the formula [M-II]. Formed by Z in the general formula [M-I]
Ring and Z in the general formula [M-VIII]₁ Formed by
Which the ring represented may have, and a general formula [M-I
R in I] to [M-VI]_Two ~ R₈ As below general
Those represented by the formula [M-IX] are preferable. General formula [M-IX] -R¹-SO_Two-R^Two Where R¹ Is an alkylene group, R^Two Is an alkyl group, cyclo
It represents an alkyl group or an aryl group. R¹ The alkylene group represented by is preferably
The number of carbon atoms in the straight chain portion is 2 or more, more preferably 3 to 6
And can be straight-chain or branched. R^Two The cycloalkyl group represented by
Those having 5 to 6 members are preferable. When used for the formation of a positive image, the heterocycle
The above substituents R and R₁ Most preferred as
It is represented by the general formula [MX]. General formula [MX] Where R₉ , R_TenAnd R₁₁Each has the same meaning as R above.
You. Further, the R₉ , R_TenAnd R₁₁Two examples in
For example, R₉ And R_TenAre bonded to a saturated or unsaturated ring (eg
Cycloalkane, cycloalkene, heterocycle)
May also be R on the ring₁₁Bonded with a bridged hydrocarbon compound
It may also constitute a residue. Preferred of the general formula [MX]
Is (i) R₉ ~ R₁₁At least two of them are alkyl
In the case of a group, (ii) R₉ ~ R₁₁One of, for example, R₁₁But water
Elementary atom, the other two R₉ And R_TenCombined with root coal
When forming a cycloalkyl with an elementary atom. Further preferred among (i) is R₉ ~
R₁₁Two of them are alkyl groups and the other one is hydrogen
This is the case of an atom or an alkyl group. When used for forming a negative image, the heterocycle
The above substituents R and R₁ Most preferred as
It is represented by the general formula [M-XI]. General formula [M-XI] R₁₂-CH_Two − Where R₁₂Has the same meaning as R described above. R₁₂Preferred as a hydrogen atom or
Is a alkyl group. The following are typical specific examples of the compounds according to the present invention.
Is shown. [0186] Embedded image[0187] [Chemical 54][0188] Embedded image[0189] Embedded image[0190] Embedded image[0191] [Chemical 58][0192] [Chemical 59][0193] Embedded image[0194] Embedded image[0195] [Chemical formula 62][0196] Embedded image[0197] Embedded image[0198] Embedded image[0199] Embedded image[0200] Embedded image[0201] [Chemical 68][0202] Embedded image [0203] Embedded image[0204] Embedded imageRepresentative Specific Examples of the Compounds According to the Present Invention
Besides, specific examples of the compound according to the present invention include Japanese Patent Application No.
1-9791 specification, pages 66 to 122
Among the compounds, No. 1-4, 6, 8-17, 19-24,
26-43, 45-59, 61-104, 106-121, 1
The compounds represented by 23 to 162 and 164-223 are listed.
it can. Further, the coupler is a journal of the
・ Chemical Society (Journal of the Chemica
l Society), Perkin I (1977), 2047
~ 2052, U.S. Patent 3,725,067, JP-A-59-99437,
58-42045, 59-162548, 59-171956, 60-3
No. 3552, No. 60-43659, No. 60-172982 and No. 60-1907
It can be synthesized with reference to No. 79 and the like. The couplers of the present invention are usually silver halide
1 x 10 per le^-3Mol to 1 mol, preferably 1 × 10^-2Mole
~ 8 × 10^-1It can be used in the molar range. The magenta coupler according to the present invention is
It can also be used in combination with other types of magenta couplers. In the present invention, the cyan coupler
Above all, in the following general formula [C-I] or [C-II],
The cyan couplers shown are preferably used. this is
Do not bleach immediately after color development using high silver chloride light-sensitive material
When performing the bleach-fix process, stains are generated in the unexposed area
Although it has the drawback of being easy,
Specific cyan cyanide represented by the formula [C-I] or [C-II]
This drawback is not only ameliorated when using the puller.
And has the effect of improving the silver bleaching performance of the light-sensitive material.
That's why. [0210] Embedded image Where R₁ , R_Two And R_Four Has a substituent
Represents an aliphatic group, aryl group or heterocyclic group which may be
Then R_Three And R₆ Is a hydrogen atom, a halogen atom, it
An aliphatic group which may have a substituent, an aryl group, or
Represents an acylamino group. Where R_Three Is R_Two Forming a ring with
May be. R_Five Is an alkyl group which may have a substituent
Represent, Z₁ And Z_Two Hydrogen atom or coloring
Represents a group capable of splitting off upon reaction with an oxidant of an image main agent.
m represents 0 or 1. Next, the above general formula [C-I] according to the present invention is described.
Or for details on the cyan coupler represented by [C-II]
Will be described. R₁ , R_Two And R_Four Is an aliphatic group, preferred
Or an aliphatic group having 1 to 32 carbon atoms (for example, a methyl group, a group
Cyl group, tridecyl group, cyclohexyl group, allyl group
Etc.), aryl groups (eg, phenyl groups, naphthyl groups, etc.
Or a heterocycle (eg, 2-pyridyl group, 2-imi
Dazolyl group, 2-furyl group, 6-quinolyl group, etc.)
These are alkyl group, aryl group, heterocyclic group,
Alkoxy group (eg methoxy group, eumethoxyeth
An oxy group, etc., an aryloxy group (eg, 2,4-di
-T-amylphenoxy group, 2-chlorophenoxy group,
4-cyanophenoxy group, etc.), alkenyloxy group
(Eg, 2-propenyloxy group etc.), acyl group
(For example, acetyl group, benzoyl group, etc.), ester
Groups (eg, butoxycarbonyl group, phenoxycarbo group
Nyl group, acetoxy group, benzoyloxy group, butoxy
Sulfonyl group, toluenesulfonyloxy group, etc.)
Mido group (eg, acetylamino group, ethylcarbamoyl group
Group, dimethylcarbamoyl group, methanesulfonamide
Group, butylsulfamoyl group, etc.), sulfamide group,
(Eg, dipropylsulfamoylamino group, etc.),
Imido group (eg, succinimide group, hydantoinyl
Group), a ureido group (for example, a phenylureido group,
Dimethylureido group, etc.), aliphatic or aromatic sulphate
Fonyl group (eg, methanesulfonyl group, phenylsulfur
Honyl group), aliphatic or aromatic thio group (eg.
For example, ethylthio group, phenylthio group, etc.), hydroxy
Group, cyan group, carboxy group, nitro group, sulfo group, ha
It may be substituted with a group selected from a rogen atom etc.
No. R_Three And R₆ Is a hydrogen atom and a halogen atom
Each of them may have an aliphatic group or an aryl group which may have a substituent.
Or represents an acylamino group. Where R_Three Is R_Two With
A ring may be formed. Here, it may have the above substituents.
Examples of the substituent of the R group include the above R₁ , R_Two And R_Four Described in
Solid groups can be mentioned. In the general formula [CI], n is 0 or
Represents 1. In the general formula [C-II], R_Five Is a substituent
Represents an alkyl group which may have
Alkyl group which may have a substituent having a prime number of 2 or more (for example,
For example, ethyl group, propyl group, butyl group, pentadecyl
Group, t-butyl group, cyclohexyl group, cyclohexyl
Methyl group, phenylthiomethyl group, dodecyloxyphene
Nylthiomethyl group, butanamidomethyl group, methoxymeth
(Such as a chill group). General formula [C-I] and general formula [C-II]
At Z₁ And Z_Two Are hydrogen atoms or
Represents a group capable of splitting off upon reaction with an oxidant of a color developing agent.
You. Examples of the group capable of splitting off include a halogen atom.
(Eg, fluorine atom, chlorine atom, bromine atom, etc.),
Lucoxy group (eg, ethoxy group, dodecyloxy group,
Methoxyethylcarbamoylmethoxy group, carboxy group
Ropyroxy group, methylsulfonylethoxy group, etc.),
An aryloxy group (eg, 4-chlorophenoxy group,
α-methoxyphenoxy group, 4-carboxyphenoxy
Groups), acyloxy groups (eg acetoxy groups,
Tradecanoyloxy group, benzoyloxy group, etc.),
A sulfonyloxy group (eg, methanesulfonyloxy
Group, toluenesulfonyloxy group, etc.), amide group (example
For example, dichloroacetylamino group, heptafluorobuty
Lumino group, methanesulfonylamino group, toluenesul
(Honylamino group, etc.), alkoxycarbonyloxy group
(For example, ethoxycarbonyloxy group, benzoloxy
Cycarbonyloxy group, etc.), Aryloxycarboni
Luoxy group (for example, phenoxycarbonyloxy group
), An aliphatic or aromatic thio group (eg ethyl
O group, phenylthio group, titrazolylthio group, etc.)
Mido group (eg, succinimide group, hydantoinyl group
Etc.), aromatic azo groups (eg, phenylazo groups, etc.)
and so on. These leaving groups include photographically useful groups.
You may go out. Preferred R in the general formula [CI]₁
Is an aryl group or a heterocyclic group, a halogen atom, an alkyl group
Group, alkoxy group, aryloxy group, acylamino
Group, acyl group, carbamoyl group, sulfonamide group, sulfur group
Rufamoyl group, sulfonyl group, sulfamide group, oxy group
An aryl group substituted with a carbonyl group or a cyano group
More preferably. In the general formula [C-I], R_Three And R_Two In ring
R is not formed_Two Is preferably replaced or absent
A substituted alkyl group or aryl group, and particularly preferably
A substituted aryloxy-substituted alkyl group, R_Three Is preferred
Or a hydrogen atom. Preferred R in the general formula [C-II]_Four Is
A substituted or unsubstituted alkyl group or aryl group
Is preferably a substituted aryloxy-substituted alkyl group.
You. Preferred R in the general formula [C-II]_Five Is
Alkyl groups having 2 to 15 carbon atoms and units having 1 or more carbon atoms
A methyl group having a substituent, and the substituent is aryl
Thio group, alkylthio group, acylamino group, aryl group
An oxy group and an alkyloxy group are preferred. R in the general formula [C-II]_Five Has 2 carbon atoms
Is more preferably an alkyl group of 15 to 15 carbon atoms
Particularly preferred is an alkyl group of 2 to μ. Preferred R in the general formula [C-II]₆ Is
Hydrogen atom, halogen atom, chlorine atom and fluorine atom
Children are particularly preferred. In general formulas [C-I] and [C-II]
Preferred, Z₁ And Z_Two Are hydrogen and halo respectively
Gen atom, alkoxy group, aryloxy group, acyl group
A xy group and a sulfonamide group. Z in the general formula [C-II]_Two Is halogen
Atoms are preferred, and chlorine and fluorine atoms are particularly preferred.
preferable. When n = 0 in the general formula [C-I],
Z_Two Is more preferably a halogen atom,
Child and a fluorine atom are particularly preferable. General formula [C-I] or [C-II]
Cyan dye forming couplers are usually silver halide emulsion layers
(Especially for red-sensitive emulsion). As the amount of addition
2 x 10 per mol of silver halide^-3~ 5 × 10^-1Mo
Is preferred, more preferably 1 × 10^-2~ 3 x 10^-1
Used in moles. The compounds represented by the general formulas [C-I] and [C-II]
Method for synthesizing cyan couplers described in US Pat. No. 3,772,002
No. 4,334,011, 4,327,173, 4,427,767
Easily synthesized based on the method described in the specification
be able to. Below, general formulas [C-I] and [C-II]
The specific compounds represented by
It is not limited to these. [0229] Embedded image[0230] Embedded image[0231] Embedded image[0232] Embedded image[0233] Embedded image[0234] Embedded image[0235] Embedded image[0236] Embedded image[0237] Embedded image[0238] Embedded image[0239] [Chemical 83]The cyan coupler according to the present invention is usually a silver halide model.
1 x 10 per le^-3Mol to 1 mol, preferably 1 x 10^-2
Mol ~ 8 x 10^-1It can be used in the molar range. In the present invention, the high silver chloride photosensitive material of the present invention is used.
Combined use of nitrogen-containing heterocyclic mercapto compounds
In this case, not only the effect of the object of the present invention is satisfactorily achieved.
And the image produced when the bleach-fix solution is mixed in the color developer.
Another effect is to make the effect on the true performance extremely small.
In order to achieve the effect of
Can be listed as such. Nitrogen-containing heterocyclic mercapto formation according to the present invention
In the compound, the nitrogen-containing heterocycle is an imidazoline ring or an imidazole ring.
Ring, imidazolone ring, pyrazoline ring, pyrazole ring,
Razolone ring, oxazoline ring, oxazole ring, oxa
Zolone ring, thiazoline ring, thiazole ring, thiazolone
Ring, selenazoline ring, selenazole ring, selenazolone
Ring, oxadiazole ring, thiadiazole ring, triazo
Ring, tetrazole ring, benzimidazole ring, benzene
Tutriazole ring, Indazole ring, Benzoxazo
Ring, benzthiazole ring, benzselenazole ring,
Radine ring, pyrimidine ring, pyridazine ring, triazine
Ring, oxazine ring, thiazine ring, tetrazine ring, quinazo
Phosphorus ring, phthalazine ring, polyazaindene ring (eg
Rearzaindene ring, tetrazaindene ring, pentazaine
It is desirable to be selected from such as den ring). Of these, special
Preferred nitrogen-containing heterocyclic mercapto compounds are
Sazole ring, oxadiazole ring, thiadiazole ring,
Triazole ring, tetrazole ring, benzimidazole
Ring, benztriazole ring, pyrimidine ring, triazine
Rings and polyazaindene rings. Hereinafter, mercapto compounds useful in the present invention
Specific examples will be given. [0243] [Chemical 84][0244] Embedded image[0245] Embedded image[0246] Embedded image[0247] Embedded image[0248] [Chemical 89][0249] Embedded image[0250] Embedded image[0251] Embedded image[0252] [Chemical formula 93][0253] Embedded image[0254] Embedded image[0255] Embedded imageThe above compounds are the Journal of Chemical Society
(J. Chem. Soc.) 49, 1748, 1927, Journal
Of Organic Chemistry (J. Org. Che
m. ) 39, 2469, 1965, JP-A-50-89034, 55-79436
Issue 51-102639, Issue 55-59463, Annalen Hemi
-(Ann. Chim.), 44-3, 1954, Japanese Patent Publication No. 40-28496
No., Chemical Berichte (Chem. Ber.) 20, 231, 188
7, USP. No. 3,259,976, Chemical and Pharma
Chemical and Pharmac
eutical Bulletin) (Tokyo) Volume 26, 314 (1978),
Richte der Deutschen Hemischen Goesel
Sdraft (Berichte bar Deutscben Chemischen
Gesellsdraft) 82, 121 (1948), U.S. Pat. No. 2,843,49
1, No. 3,017,270, British Patent No. 940,169, Jar
The Null of American Chemical Society, 44,
It can be synthesized by referring to the method described in 1502-1510 etc.
it can. The above nitrogen-containing heterocyclic mercapto compound (hereinafter
It is simply called a mercapto compound. ) Is, for example, JP-A-51-1
07129, 48-102621, 55-594463, and 59-12
It is described in each gazette of 4333. In the present invention, the mercapto compound is 2
Preferably added to one or more multiple photographic constituent layers
No. The total amount of the mercapto compound used is
Layer structure of silver halide photographic light-sensitive material, mercapto compound
Widely varies depending on the type, amount of silver halide, processing conditions, etc.
Generally, 1m^TwoPer 10^-8Mole-10^-FourMol, preferred
H10^-7Mole-10^-FiveAlthough it is in the molar range, the present invention
However, the total amount added is not limited, and the
Degree of anti-blur and effect of mercapto compound between each layer
Stipulated by the size of. Used in the silver halide emulsion layer of the present invention
The silver halide grains contain at least 70 mol% of silver chloride.
However, the rest may contain bromide or iodide, but is essentially a salt.
Silver iodide is preferable, and the amount of bromide and iodide is very small.
It is preferred that In special cases, the blue photosensitive layer is odorized
A silver halide containing 30 mol% of the product, for example, another two layers
For example, the green and red layers should be about 99% chloride.
Is also one of the preferred embodiments. Silver halide preferred
It is preferably a core-shell particle and has a double layer structure. In one embodiment, the grains have a halide composition.
At least two areas that differ from each other, for example, one core
Consists of at least one shell and at least one
Region B is at least 10 mol% silver bromide, preferably less.
At least 25 mol% silver bromide, but no more than 50 mol% odor
Contains silver halide. Region B is as or around the core
Can exist as a shell. The particles are preferably
It comprises a core encased in at least one region B.
In that case, the region B serves as a shell in the silver halide grain.
Or it can be on the surface of the crystal. In another embodiment, the particles are bromide-lean.
At least one zone having a high content of 10 mol% each
ZBr and has an odor on the surface of silver halide grains.
It has no compound rich zone ZBr. Silver bromide rich zone ZBr in these grains
As a core or as a layer within a silver halide grain
It can exist even if there is a gap. The silver halide emulsion is prepared by a conventional method (for example, one of materials
Single or double inflow with constant or accelerated feed)
Can be prepared. By adjusting the pAg, the double inflow method
Is particularly preferred; Research Disclosure
See No. 17643, Sections I and II. The emulsion can be chemically sensitized. A
Ryl isothiocyanate, allyl thiourea or thio
Sulfur-containing compounds such as sulphates are particularly preferred. Return
The original agent can also be used as a chemical sensitizer, which
For example, Belgian patents 493,464 and 568,687.
Tin compounds as described, and for example Belgian Patent No. 547,3
No. 23, polyamines such as diethylenetriamine or
Is an aminomethylsulfinic acid derivative. Gold, platinum,
Such as palladium, iridium, ruthenium or rhodium
Noble metals and noble metal compounds are also suitable sensitizers.
This chemical sensitization method is the Zeitschrift Fair Bit
Sensaburi Photography (Z. Wiss. Pho
to.)46, Koslovsky, 65-72 (1951)
(R. Koslovsky); see also above.
Research Disclosure No.17643, Section I
See also II. The emulsion is prepared by a method known in the art, for example, a new method.
Trocyanine, basic or acidic carbocyanine,
Ordinary polymethine dyes such as dacyanin and hemicyanine
Dyes, styryl dyes, oxonol and the like,
Can be sensitized; FM Hummer (FM
Hamer） 「Cyanine soybean and relayed
・ Compounds "(The Cyanine Dyes and relate
d Compounds) (1964) Ullmann's Enchiclopedy
・ Dell technischen hemi (Ullmanns Enzyklpa
die der technischen Chemie) 4th edition, 18 volumes, 431 pages
And then, and Research Disclosure N above
See 17643, section IV. The use of customary antifoggants and stabilizers
Can be. Azaindene is a particularly suitable stabilizer,
Tetra- and penta-azaindene are preferred, especially
Those substituted with a droxyl group or amino group are preferred.
Good. Compounds of this kind are described, for example, in Birr's theory.
By Zeitschrift Fair Bissenschri
T. Photography (Z. Wiss. Photo.) 47, 195
2, p.2-58, and the above Research Disclosure
No. 17643, Section IV. The components of the photographic material are combined according to the usual known methods.
Can be incorporated; for example, US Pat. No. 2,322,027
No. 2,533,514, 3,689,271 and 3,764,336
And No. 3,765,897. Ingredients in photographic materials, such as
Pullers and UV absorbers are also in the form of charged latex
Can also be combined with; German Patent Application Publication No. 2,5
See 41,274 and European Patent Application No. 14,921. The ingredients are also
Can be immobilized in the material as a polymer; eg
German Patent Application Publication No. 2,044,992, U.S. Patent No. 3,370,
See 952 and 4,080,211. Conventional layer supports can be used for the material.
, It is, for example, cellulose ester, for example cellulose
An acetate support and a polyester support.
Paper supports are also suitable, and these are for example
Liolefin, especially polyethylene or polypropylene
Can be coated with;
・ Disclosure No. 17643, Section XVII
Teru. An ordinary hydrophilic film forming agent is used for recording materials.
Using as protective colloid or binder for layers
They can be, for example, proteins, especially gelatin, al
An inducer such as formic acid or its ester, amide or salt
Conductor, carboxymethyl cellulose and cellulose monkey
Cellulose derivatives such as fate, starch or its derivatives
Conductive or hydrophilic synthetic binders; also researched above
· Disclosure 17643, shown in Section IX
There are also references to existing binders. The layers of photographic material can be processed in the usual way, for example by epoxies.
Side, heterocyclic ethyleneimine or acryloyl type hard
It can be cured with an agent. Further layers are Germany
Cured by the method according to Patent Application Publication No. 2,218,009
Can produce color photographic material suitable for high temperature operation
You. Also, photographic layers or color photographic multilayer materials are
Or triazine or 1,2-dihydroquinoline
Can also be cured with a curing agent or vinyl sulfone type curing agent
it can. Other suitable hardeners are disclosed in German Patent Application No.
 2,439,551, 2,225,230 and 2,317,672 and
Research Disclosure 17643, section above
XI. [0272] As described above, according to the present invention,
, It does not require additional means such as reprocessing of the color developer.
Economically, it can be made cheaper without deterioration of photographic performance.
Even if the replenishment amount of the image liquid is significantly reduced, the obtained image
Silver halide color copying that can always provide stable and true performance
A method for processing a true light-sensitive material could be provided. [0273] DETAILED DESCRIPTION OF THE INVENTION The present invention will be described below with reference to examples.
Although described physically, the embodiments of the present invention are not limited to these.
It is not something to be done. Example-1 An experiment was conducted with the following color paper, processing solution and processing steps.
Was. [Color paper] polyethylene coated paper
The following layers are coated on the support from the support side in order,
The material was made. [0276] As the polystyrene coated paper,
200-weight polyethylene with an average molecular weight of 100,000 and a density of 0.95
Polyethylene 2 with parts and average molecular weight of 2,000 and density of 0.80
Anatase type titanium oxide is mixed with 0 parts by weight.
 Add 6.8% by weight and weigh it by the extrusion coating method.
170g / m^TwoForm a 0.035 mm thick coating layer on the surface of fine paper
And polyethylene on the back is 0.04mm thick
The one provided with the coating layer was used. Poly on the surface of this support
Pretreatment by corona discharge on ethylene coated surface
After that, each layer was sequentially coated. First layer: a silver halide composition shown in Table 1
A blue-sensitive silver halide emulsion layer consisting of a silver halide emulsion
The emulsion contains 350 g gelatin per mol silver halide,
Sensitizing dye having the following structure per mol of silver halide [0278] Embedded image 2.5 × 10^-FourSensitized with mol (isopro
Pill alcohol), dissolved in dibutyl phthalate
2,5-di-t-butylhydroquinone 20 dispersed
0mg / m^TwoAnd yellow coupler as an example
2 × 10 per 1 mol of silver halide^-1Including mole
Only 300 mg / m of silver^TwoIt is applied so that it becomes. Second layer: dissolved and dispersed in dibutyl phthalate
Di-t-octyl hydroquinone 300mg / m^Two,purple
2- (2'-hydroxy-3 ', 5' as an external line absorber
-Di-t-butylphenyl) benzotriazole, 2-
(2'-hydroxy-5'-t-butylphenyl) ben
Zotriazole, 2- (2'-hydroxy-3'-t-
Butyl-5'-methylphenyl) -5-chlorobenzoto
Riazole and 2- (2-hydroxy-3 ', 5'-
Di-t-butylphenyl) -5-chloro-benzotria
Mixture of sols 200mg / m^TwoGelatin layer containing
Chin 1900mg / m^TwoIt is applied so that it becomes. Third layer: a silver halide composition shown in Table 1
A green-sensitive silver halide emulsion layer consisting of a silver halide emulsion,
The emulsion contains 450 g of gelatin per mole of silver halide,
Sensitizing dye having the following structure per mol of silver halide [0281] Embedded image 2.5 × 10^-FourSensitized with mol dibutyl phthalate
Solvent with a 2: 1 mixture of triclenzel phosphate
Magenta as an example of magenta coupler dissolved and dispersed in magenta
Coupler M-5 is 1.5 × 10 per mol of silver halide.^-1Mo
Containing silver, silver content 280mg / m^TwoIs applied so that
You. As the antioxidant, 2,2,4-trimethyl-
Capping 6-lauryloxy-7-t-octyl chroman
0.3 mol was contained per 1 mol of the lar. Layer 4: Dissolved in dioctyl phthalate
30 mg / m of dispersed di-t-octylhydroquinone^TwoPassing
And UV absorber as 2- (2'-hydroxy-3 ',
5'-di-t-butylphenyl) benzotriazole,
2- (2'-hydroxy-5'-t-butylphenyl)
Benzotriazole, 2- (2'-hydroxy-3'-
t-butyl-5'-methylphenyl) -5'-chlorobe
Nzotriazole and 2- (2'-hydroxy-
3 ', 5'-t-butylphenyl) -5-chloro-ben
500 m of a mixture of zotriazole (2: 1.5: 1.5: 2)
g / m^TwoGelatin amount contained is 1900 mg / m^TwoTo
It is applied so that it becomes. Fifth layer: a silver halide composition of Table 1
A red-sensitive silver halide emulsion layer consisting of a silver halide emulsion,
The emulsion contains 500 g of gelatin per mole of silver halide,
Sensitizing dye having the following structure per mol of silver halide [0284] Embedded image 2.5 × 10^-FiveSensitized with mol dibutyl phthalate
2,5-di-t-butylhydro dissolved and dispersed in
Quinone 150mg / m^TwoAnd cyan couplers and example cyan caps
Lar C'-2 3.5 x 10 per mol of silver halide^-1Mole
Containing, silver amount 280mg / m^TwoIt is applied so that it becomes. Sixth layer: gelatin layer containing 900 mg of gelatin
/ M^TwoIt is applied so that Used for each photosensitive emulsion layer (first, third and fifth layers)
The silver halide emulsion is described in Japanese Patent Publication No. 46-7772.
Prepared by the method described above, and each of them is sodium thiosulfate 5 water
Chemically sensitized with a Japanese product, 4-hydroxy as a stabilizer
-6-methyl-1,3,3a, 7-tetrazaindene,
Bis (vinylsulfonylmethyl) ether as a hardener
And saponin as a coating aid. The above-mentioned light-sensitive material (change silver halide composition)
Stepwise exposure to the following processing steps and processing solutions (color developing solution
Change the preservatives, the comparison is treated with
The maximum concentration of yellow dye in the sample
The ratio to the pear was calculated. Table 1 shows the results. Standard treatment process [1] Color development 38 ° C 1 minute [2] Bleach fixing 38 ° C 1 minute [3] Washing with water 25-35 ° C 1 minute [4] Drying 75 to 100 ° C About 2 minutes Treatment liquid composition   <Color developing tank liquid>   Ethylene glycol 15ml   Potassium sulfite 1.0g   Sodium chloride 3 × 10^-2Mole   Potassium carbonate 30.0g   3-Methyl-4-amino-N-ethyl-N- (β-methane   Sulfonamidoethyl) -aniline sulfate (Exemplary Compound A-1) 5.5 g   Fluorescent brightener (exemplary compound A′-4) 1.0 g   5.0 g of preservatives listed in Table 1   Hydroxyethyliminodiacetic acid 5.0 g   1,2-dihydroxybenzene-3,5-disulfonic acid   -Disodium salt (Exemplary compound BI-2) 0.2 g Add water to bring the total volume to 1 liter and add KOH and H₂SO₄
PH to 10.20. [0289]   <Bleaching and fixing tank liquid>   Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60 g   Ethylenediaminetetraacetic acid 3 g   Ammonium thiosulfate (70% solution) 100 ml   Ammonium sulfite (40% solution) 27.5ml Adjust to pH 7.1 with potassium carbonate or glacial acetic acid.
Add water to bring the total volume to 1 liter. [0290] [Table 1]As is clear from Table 1, milk containing 70 mol% or more of silver chloride.
In the case of a developing agent, it is used as a preservative for the color developing solution.
Using a droxylamine derivative has a low maximum concentration.
It turns out that it is very favorable without lowering. Example-2 The preservatives listed in Table 2 used in Example-1 were added.
Store each color developer for 10 days and store it immediately after preparation.
Same as Example-1 with comparison of color developing solution without pesticide
After developing, the gamma value (density
The value between 0.8 and 1.8) was calculated and the preservative immediately after preparation
The ratio was calculated with pear as a comparison. Table 2 shows the results. [0292] [Table 2]As is clear from Table 2, emulsions containing 70% or more silver chloride
In this case, the hydroxylamine according to the invention as a preservative
It is important to use a derivative even if the color developer is stored.
It can be seen that the mass value does not change and is very preferable. Example (3) As the silver halide emulsion, the emulsion used in Example (1)
No. E was used and the coupler was Y-5, M-5 used in the examples.
And C'-2 were changed to the couplers shown in Table 3
The light-sensitive material used in Example (1) was used. The color developer contains DEHA (exemplified as a preservative.
Implementation using a color developer using the compound (I-1))
It processed according to the process of Example (1). After processing, yellow, magenta and cyan colors
Sakura photoelectric densitometer P for maximum reflection density and minimum reflection density of element
It was measured with DA-65 (manufactured by Konica Corporation). The results are shown in Table 3.
Shown together. [0296] [Table 3]As is clear from Table 3, the fast-reacting yellow coupler (sensitivity
Materials No. 2 to No. 6), represented by the above general formula [MI]
Magenta coupler (sensitizer No. 7 to 13) and the above general formula
Cyancap represented by [C-I] and / or [C-II]
The maximum color density is obtained by using Ra (sensitive material No. 14 to 26)
In the present invention, both the degree and the minimum concentration have been improved.
It turns out to be a preferred coupler. In particular, a fast-reactive yellow coupler,
Magenta coupler represented by the general formula [M-I] and general
A cyan coupler represented by the formula [C-I] or [C-II]
It proves to be particularly preferable when used in combination. Example (4) As the silver halide emulsion, the milk used in Example (1) was used.
Agent No. E and the organic inhibitors shown in Table 4 (each of 1, 3, 5
(Added to the layer) and the color developer is DEHA as a preservative.
And the bleach-fix solution used in Example (1) was developed.
0.5 ml was added per 1 liter of the image liquid, the same as in Example (1)
Gamma value of yellow dye (density 0.8
From the density of 1.8), and add the bleach-fix bath without adding
The ratio was calculated with the addition of 100. The results are shown in Table 4.
Show it. [0299] [Table 4]As is clear from Table 4, the present invention relates to the present invention.
By using a specific heterocyclic mercapto compound
Even if the bleach-fix solution is mixed in the color developing solution, the relative gamma value remains
It was found that the photographic characteristics did not change and stable photographic characteristics were exhibited. Example-5 In Example-1, of potassium sulfite in the color developer
Change the concentration as shown in Table 5, and use the preservative pear to remove potassium sulfite.
The same experiment as in Example 1 was carried out by comparing 1 g / l of the sample.
And perform the development process to measure the maximum density of the yellow dye
And preservative pear with a maximum of potassium sulfite 1g / l
The ratio was calculated assuming that the concentration was 100. Table 5 shows the results. [0301] [Table 5]From Table 5, in the present invention, especially potassium sulfite is colored.
It was found that 1.0 g / liter or less in the developer is preferable.
You. Example (6) Color Developer Nos. 1 to 22 having the following compositions were prepared. (Color developer)   Potassium sulfite 5.0 × 10^-3Mole   Sodium chloride 3.0 x 10^-2Mole   30g potassium carbonate   3-Methyl-4-amino-N-ethyl- (β-methanesulfone   Amidoethyl) -aniline sulfate 5.5 g   Optical brightener (triazinyl stilbene-based 4,4'-diamino   Exemplified Compound A′-10) which is a stilbene-based optical brightener, 2.0 g   Preservatives listed in Table 6 5.0   Compounds listed in Table 6 Addition amount listed in Table 6   Bleach-fixing solution (described in Example (1)) 0.3 cc   Add water to bring the total volume to 1 liter and add KOH and H₂SO₄PH to 10.20 You. Next, the color developing solution shown in Table 6 was used with an opening ratio of 100.
cm^Two/ Liter (for 1 liter of color developer, air
100 cm contact area^Two) Store in a glass container at 38 ℃
After 2 weeks, the tar property of the color developing solution was evaluated. However, the appearance of the liquid is divided into the following four stages.
Was. +++ Large amount of tar generated ++ Tar adhered to the wall (black) + Some tar on the surface − No tar generation [0306] [Table 6] As is clear from Table 6, the preservative (I-1) of the present invention was
Polyhydroxy compound according to the invention (color developer No.
4, 5), aminopolycarboxylic acid (color developer No. 6)
~ 8), or a combination of these compounds with other compounds (N
o. 12 to 17) and added, the tar property is improved.
It has a remarkable improvement effect when used together.
I understand. This improving effect is obtained by using the preservative as a preservative according to the present invention.
Even if the agent (No. 18-22) is changed, the improvement effect as described above
It turns out that the fruit is obtained. Example (7) The color developer (No. 1 to 22) described in Example (6) was added at 50 ° C for 5 ° C.
Close the bottle with a glass bottle and store it in the same manner as in Example (4).
And evaluation was performed. The results are summarized in Table 7. [0308] [Table 7] As is clear from Table 7, the bleach-fix solution contains a very small amount of contamination.
Saved (model running state),
In the preservative (I-1) of the present invention, the polyhydro
Xy compound (color developer No. 4 ', 5'), amino
Licarboxylic acid (color developer No. 6'to 8 '), or
Combined use of these compounds and other compounds (No. 12 'to 1
7 ') addition improves the fluctuation of photographic characteristics after storage.
It has a remarkable improvement effect when used together.
I understand. This improving effect is obtained by using the preservative as a preservative according to the present invention.
Even if the agent (No. 18'-22 ') is changed,
It turns out that a good effect can be obtained. [Example 8] Color developer used in Example 1
The following color developing agent (A-1) is added to the following (B-1) or
When the same experiment was performed after changing to (B-2),
The magenta stain in the exposed area deteriorated by 0.03.
Similarly, the color developing agent (A-1) of Example 1 was used.
Exemplified compounds (A-2), (A-4) and (A-15)
When each was changed and the same experiment as in Example 1 was performed,
Almost similar results were obtained. [0310] Embedded image Example (9) A fluorescent whitening agent in the color developing solution used in Example (1) (exemplification
Compound (A'-4)) was changed as shown in Table (8) below.
Then, development processing was performed according to Example (1). After treatment
The yellow stain in the unexposed area of the cherry blossom photoelectric densitometer PD
It was measured using A-65 (manufactured by Konica Corp.). The result
In addition, it is shown in Table 8. [0312] [Table 8] [0313] Embedded imageFrom Table 8, the triazils represented by the above general formula [III]
Use of tilbene type optical brightener in combination with the processing method of the present invention
Yellow stain is further improved by
You can see that. Reference Example-1 On a paper support laminated with polyethylene,
Layers are coated one by one from the support side to form a silver halide photosensitive material
(Emulsion No. G, H, I and J) were prepared. Layer 1 ... 1.20 g / m²Gelatin, 0.40 g / m²
(Same as silver, the same applies below) Blue-sensitive silver halide emulsion and
0.55 g / m²Dissolved in dioctyl phthalate
1.0 x 10^-3Mol g / m²Yellow coupler (Y
A layer containing -5). Layer 2 ... 0.70 g / m²An intermediate layer consisting of gelatin. Layer 3 ... 1.20 g / m²Gelatin, 0.22 g / m²
Green-sensitive silver halide emulsion of 0.30 g / m²Geo
1.0 × 10 dissolved in octyl phthalate^-3Mol g /
m²Layer containing magenta coupler (M-5). Layer 4 ... 0.70 g / m²Intermediate layer made of gelatin. Layer 5 ... 1.20 g / m²Gelatin, 0.28g / m²
Red sensitive silver halide emulsion and 0.25 g / m²The jib
1.75 × 10 dissolved in chill phthalate^-3Mol g /
m²A layer containing the cyan coupler (C'-2). Layer 6 ... 1.0 g / m²Gelatin and 0.25g / m²
0.32 g / m dissolved in dioctyl phthalate²of
Contains Tinuvin 328 (UV absorber made by Ciba Geigy)
Layer to do. Layer 7 ... 0.48 g / m²Layer containing gelatin. What
As a hardener, 2,4-dichloro-6-hydroxy
-S-triazine sodium in layers 2, 4 and 7
Add 0.017 g per 1 g gelatin respectively
did. The average halogen in the silver halide emulsion
The silver halide composition is shown in Table 9. A picture of the color paper sample thus created is drawn.
After baking and printing, follow the processing steps below with an automatic processor.
It was run. Treatment process (1) Color development 35 ℃ 45 seconds (2) Bleach fixing 35 ℃ 45 seconds (3) Stable washing alternative 30 ° C 90 seconds (4) Dry 60 ° -80 ° C 1 minute 30 seconds The composition of the treatment liquid used is as follows.
You. [Color developing tank liquid]   Potassium bromide Table 9 amount   Potassium chloride Table 9 listed amount   1.0 ml of potassium sulfite (50% solution)   Color developing agent (3-methyl-4-amino-N-ethyl-N-   (Β-methanesulfonamidoethyl) -aniline sulfate 5.0 g   Diethylhydroxylamine (85%) 5.0 g   Triethanolamine 10.0 g   30 g potassium carbonate   Ethylenediaminetetraacetic acid sodium salt 2.0 g Finish with water to 1 liter with potassium hydroxide or sulfuric acid
Adjusted to 10.15. [Color developing replenisher]   Potassium bromide Table 9 amount   Potassium chloride Table 9 listed amount   2.0 ml of potassium sulfite (50% solution)   Color developing agent (3-methyl-4-amino-N-ethyl-N-   (Β-Methanesulfonamidoethyl) -aniline sulfate 8.0 g   Diethylhydroxylamine (85%) 7.0 g   Triethanolamine 10.0 g   30 g potassium carbonate   Ethylenediaminetetraacetic acid sodium salt 2.0 g Finish with water to 1 liter with potassium hydroxide or sulfuric acid
Adjusted to 10.40. [Bleach-fix tank liquid]   Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60.0 g   Ethylenediaminetetraacetic acid 3.0 g   Ammonium thiosulfate (70% solution) 100.0 ml   Ammonium sulfite (40% solution) 27.5ml When the pH is adjusted to 5.50 with aqueous ammonia or glacial acetic acid,
Add water to make the total volume 1 liter. [Bleach-fix replenisher]   Ethylenediaminetetraacetic acid ferric ammonium dihydrate 70.0 g   Ethylenediaminetetraacetic acid 3.0 g   Ammonium thiosulfate (70% solution) 120.0 ml   35 ml of ammonium sulfite (40% solution) Adjust to pH 5.40 with aqueous ammonia or glacial acetic acid and
Set to 1 liter. [Stable tank replacement substitute and replenisher]   5-chloro-2-methyl-4-isothiazolin-3-one 0.02g   2-Methyl-4-isothiazolin-3-one 0.02 g   Ethylene glycol 1.0 g   2-octyl-4-isothiazolin-3-one 0.01 g   1-hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 3.0 g   Bi Cl_Three (45% aqueous solution) 0.65g   Mg SO_Four ・ 7H_Two O 0.2 g   Ammonia water (25% ammonium hydroxide in water) 2.5 g   Nitrilotriacetic acid / trisodium salt 1.5 g Make up to 1 liter with water and add pH 7.0 with aqueous ammonia and sulfuric acid.
And Running processing is carried out by the automatic processor with the above-mentioned color development.
Full of developer tank solution, bleach-fix tank solution and stability tank solution
Every 3 minutes while processing the color paper sample.
Replacement of color development replenisher and bleach-fix replenisher with water as above
The stable replenisher was replenished with a metering pump. The amount of replenishment to the color developing tank is shown in Table 9.
However, as a supplement amount to the bleach-fixing tank, color paper
1 m^TwoPer bleach-fixing replenisher 220ml, the amount of replenishment to the stabilizing tank
Then, 250 ml of the stable replacement solution for washing with water was replenished. The stabilizing bath of the automatic processor is exposed to light.
In the direction of material flow, the first tank to the third tank is a stable tank,
Replenish from the final tank, and overflow liquid from the final tank
In addition, let this overflow flow into the tank at the previous stage.
The raw liquid is also allowed to flow into the tank at the previous stage to make it a multi-tank countercurrent system.
Was. Color development tank Color development replenished in the solution
When the amount of replenisher becomes twice the capacity of the color development tank
Pass the wedge-exposed check sample through the dots and
Measure the maximum color density and determine the maximum color density at the start.
 The activity of the developer was evaluated by obtaining a relative value with 100 being set.
The results are shown in Table 9. [0323] [Table 9]From the above results, the silver halide composition is outside the scope of the present invention (emulsion N
o.G) comparative examples and silver halide compositions are within the scope of the present invention.
The concentration of chloride in the tank liquid is 2 × 10^-2Mol / lit
In the comparative examples below
The true concentration drops sharply, but the silver halide composition and tank
If the chloride concentration in the liquid is within the range of the present invention, the replenishment amount is low.
Even if it is reduced, there is no decrease in photographic density
It can be seen that the performance can be obtained. Reference Example (2) Emulsion N used in Reference Example (1) as a silver halide emulsion
o. Halogenation described in Reference Example (1) except that J was used.
Color development replenisher and tank solution using silver color light-sensitive material
The halide concentration (mol / l) of each is KBr /
KCl = 0.0059 / 0.054 is used for color development
Filling volume is 100 ml / m²Color development with running
Solution, bleach-fix solution, and stabilizing solution.
The pH was changed as shown in Table 10, and the same as in Reference Example (1)
The yellow dye has the minimum reflection density and
The silveriness was evaluated. The minimum reflection density is PDA-65 (Konica
(Manufactured by Co., Ltd.), and desilvering property is measured by a fluorescent X-ray method.
Was. The results are shown in Table 10. [0326] [Table 10] As is clear from Table 10, when the pH of the bleach-fix solution becomes high
If the minimum reflection density and desilvering property deteriorate, and the pH is too low
(Bleach-fixing solution No. 1) The minimum reflection density becomes high. The pH of the bleach-fixing solution is 4.5 to 6.8 (No. 2 to
In 6), both the minimum reflection density and the desilvering property are good.
It can be said that it is a preferable mode for Ming. Reference Example (3) As the silver halide composition, the emulsion NO of Example (1)
The color photosensitive material of Reference Example (1) was used except that (F) was used.
Use the color developer to adjust the halide concentration
The concentration of KBr / KCl in the solution is 0.0017 mol / 0.
The amount of the color developer replenisher is 200 m.
l / m²Color development temperature is set to 38 ℃ and color development processing time
When Table 11 is shown, run in the same manner as in Reference Example (1).
The processing was performed. The running process was carried out in the color developing tank solution.
The amount of color development replenisher replenished is double the tank volume
Processed until Table 11 shows the amount of running processing. The evaluation method is the same as in Reference Example (1).
I went in. Table 11 shows the results. [0332] [Table 11]As is clear from Table 11, when the processing time for color development is short
In particular, especially in 45 seconds or less, depending on the running amount per day
However, while the fluctuation of the photo density is large, it takes 2 minutes.
Changes in photographic density over a processing time of 30 seconds or more, especially 3 minutes or more
Shows small and stable photographic characteristics. Reference Example-4Emulsion adjustment-K 0.3N NaCl and 0.3N in 2.6% gelatin solution
AgNO₃The solution is subjected to simultaneous mixing while adjusting pAg.
More silver chloride emulsion was prepared. PAg based on this emulsion
2N NaCl and 2NAg NO while maintaining 6.8₃
Increase the size to 40 times the volume by adding the solution
Great. The AgCl particles contained 40 mol% of bromide.
Mu Br / Na Cl solution and AgNO_ThreeSolution for simultaneous mixing
More AgBr / AgCl shells were applied. The particles obtained have a mean particle size of 0.58 μm.
Although it is a dispersed emulsion, its AgCl content is
96 mol% and the AgBr content is 4 mol%.
Was. Adjustment of photographic materials Emulsion K was used to prepare the photographic materials shown in the following table. 1. Support polyethylene coated paper 2. Blue photosensitive layer Coupler Y-5 (DBP dispersion) 3. Middle class 4. Green photosensitive layer Coupler M-5 (DOP dispersion) 5. Middle class 6. Red Photosensitive Layer Coupler C-7 (DOP dispersion) 7. Protective layer 8. UV agent-containing layer Hardener and UV absorberThe developing bath has the following composition:   [Tank solution]   800 ml of water   Diethyl-hydroxylamine-sulfate 5 g   Diethylenetriamine pentaacetic acid pentasodium salt 1.5 g   4-Amino-N-ethyl-N- (β-methane-sulfonamide)   -Ethyl-m-toluidine-sesquisulfate (monohydrate) 5.2 g   Potassium sulfite 0.9 g   Potassium chloride 3 g   25 g potassium carbonate   1.5 g potassium hydroxide Make up to 1 liter with water, pH = 10.2 The developing bath is followed by a replenisher solution of 80 ml / m 2.^TwoPercent of
Processed with:   [Replenisher solution]   800 ml of water   Diethyl-hydroxylamine-sulfate 6 g   Diethylenetriamine pentaacetic acid pentasodium salt 2 g   4-Amino-N-ethyl-N- (β-methane-sulfonamide)   -Ethyl-m-toluidine-sesquisulfate (monohydrate) 12 g   1.2 g of potassium sulfite   Potassium chloride 3 g   25 g potassium carbonate   Potassium hydroxide 13 g Make up to 1 liter with water, pH = 12.3 The bleach-fix bath had the following composition:   [Tank solution]   700 ml of water   20 g of sodium sulfite   Ammonium thiosulfate 100 g   Ethylenediamine-tetraacetic acid sodium-iron salt 45 g   9 g potassium carbonate Make up to 1 liter with water, pH = 7.0 To make the bleach-fix bath replenisher,
It was just 800 ml. [0340]   [Stabilizer]    o-phenylphenol 0.3 g   1-hydroxyethylidene 1,1-diphosphonic acid 0.5 g   Ammonia water 3 g The volume was adjusted to 1 liter with water and adjusted to pH 7.8. Stabilizer and stable
The same replenisher was used. [0341]Comparison For comparison, the same photographic material was always used with a conventional developer.
It was developed by the development processing method for use. [0342]   [Developer, tank solution]   800 ml of water   Benzyl alcohol 14ml   Ethylene glycol 7ml   Hydroxylamine sulfate 1.5 g   Diethylenetriamine pentaacetic acid potassium salt 1.5 g   4-Amino-N-ethyl-N- (β-methane-sulfonamide)   Chill-m-toluidine-sesquisulfate 5.2 g   2.5 g potassium sulfite   2.5 g sodium chloride   33 g potassium carbonate   0.8 g potassium hydroxide Make up to 1 liter with water, pH = 10.2 The developing solution was prepared by adding the following replenisher solution to 80 ml / m 2.^TwoOf
Replenished with:   [Replenisher solution]   800 ml of water   Benzyl alcohol 18ml   Ethylene glycol 9ml   Hydroxylamine sulfate 4 g   Diethylenetriaminopentaacetic acid potassium salt 2 g   4-Amino-N-ethyl-N- (β-methane-sulfonamide)   -Ethyl-m-toluidine-sesquisulfate 6.5 g   Potassium sulfite 5.0 g   2.5 g sodium chloride   33 g potassium carbonate   1.8 g potassium hydroxide Make up to 1 liter with water, pH = 10.5 The bleach-fix bath is as described above. The sample and the photographic material developed after the developer was adjusted
2000m over 30 days^TwoMaximum emission of sample developed after processing
The color density was measured, but the sample treated with the developer of the present invention was copied.
The true concentration of each of the developers immediately after preparation and after continuous processing
And changed little. Also overflow
I know that it is possible to process economically very stably.
Was. Also, of course, it does not contain benzyl alcohol.
Therefore, no tar was found in the developing tank.
Was. On the other hand, in a comparative experiment, the
A significant decrease in color density was observed due to the presence of amine.
In addition, the concentration changes significantly after that, and stable processing is performed.
I couldn't do it. Also, because of benzyl alcohol
It was recognized that remarkable tar formation was observed. Reference Example-5 As an additional experiment, halo containing silver bromide in various ranges.
A silver genide photographic light-sensitive material was processed with the color developer of the present invention.
As a result, the silver halide contains less than 10 mol% of bromide.
If it does not occur, try developing at maximum to develop
No elution of bromide was observed in the liquid. Actual la
I tried to quantify bromide in the tunning solution.
Proven.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram showing a specific mode in which a part or all of a processing solution is flowed into another tank in the processing of a silver halide color photographic light-sensitive material according to the present invention. Is.

   ────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Yoko Matsushima               No. 1 Sakura-cho, Hino City, Tokyo Konica stock               In the formula company                (56) References Japanese Patent Publication 6-100807 (JP, B2)                 Patent 2607082 (JP, B2)

Claims (1)

(57) [Claims] A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support is imagewise exposed, and then developed with a color developing solution containing at least a p-phenylenediamine type color developing agent, and the color development is carried out. In the method for processing a silver halide color photographic light-sensitive material, the solution is continuously processed while replenishing a replenishing solution, the silver halide emulsion layer contains silver halide grains containing at least 70 mol% of silver chloride, The color developing solution is a triazinyl stilbene-based fluorescent whitening agent, represented by the following general formulas [BI] and [BI].
I], [B-III] or [B-IV] and a compound represented by the following general formula [I], and a halogen containing at least 2 × 10 ⁻² mol of chloride per liter of color developer. Processing method of silver halide color photographic light-sensitive material. Embedded image [In the formula, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each a hydrogen atom, a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms (including those having a substituent),
O _Including); including those with _{R 15,} R _{16, R 17} and _{R 18} are each a hydrogen atom or an alkyl group having 1 to 18 carbon atoms (substituent) _{(wherein, R 12} represents -OH or a hydrogen atom In this case, R ₁₁ is a halogen atom, a sulfonic acid group, or an alkyl group having 1 to 7 carbon atoms. A phenyl group (including a substituent), L is an alkylene group (including a substituent), a cycloalkylene group (including a substituent) or a phenylene group (having a substituent) the _{containing), - L 8 -O-L} 8
_{-O-L 8} - or -L ₉ R _{33 to} R ₄₃ each represent a hydrogen atom, a hydroxyl group, a carboxylic acid group or a phosphonic acid group (including salts thereof) (provided that at least two of R _{33 to} R ₃₆ are carboxylic acids). An acid group or a phosphonic acid group (including salts thereof), and at least 2 of R _{37 to} R ₃₉
One is a carboxylic acid group or a phosphonic acid group (including salts thereof). ] [Chemical 2] In the formula, R ₁ and R ₂ each represent an alkyl group (including those having a substituent) or a hydrogen atom. However, both R ₁ and R ₂ are not an alkyl group having no substituent or a hydrogen atom at the same time. R ₁ and R ₂ may form a ring. 2. 2. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the color developing solution contains substantially no benzyl alcohol.