JP2711319B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial applications]   The present invention relates to a silver halide color photographic light-sensitive material (hereinafter referred to as a photosensitive material).
Material development method)
The dye concentration is low even if color development processing is performed for a short time.
Images that are consistently obtained and have excellent storage stability in dark places
And use a stabilizing solution with a small replenishing amount without washing with water.
The present invention relates to an anhydrous washing stabilization method which can be performed. (Prior art)   Processing of color photographic materials is basically color development and removal.
It consists of three steps, silver and water washing.
Any of the bleach-fixing steps in which bleaching and fixing are performed in the same bath
Become. Recently, the stabilization process is called instead of the washing process.
Colorless development, bleach-fix, stable
Processing comprising three steps of processing is actively performed.   The silver halide exposed in color development is reduced
Aromatic primary amines oxidized at the same time as silver
The main agent reacts with the coupler and reacts with indoaniline, india
Form phenol and azomethine dyes
It is well known to form color photographic images by   These color photography systems generally use
A color developing solution containing a non-diffusible coupler in the emulsion layer
Develops with the color developing agent inside, but diffuses into the color developing solution
Photo of coupling reaction with water-soluble coupler
Methods of raising it in a material are also known.   Also, couplers to be included in photosensitive materials are generally
Can be dispersed in a water-insoluble high-boiling organic solvent and added.
Thus, non-diffusion is provided.   In this method, a high molecular weight alkyl side chain is dispersed in the coupler.
Rather than making it non-diffusible,
It is considered to be advantageous in terms of realism, preservation of color purity images, etc.
Generally done.   Aromatic color developing solutions for processing such photosensitive materials are aromatic.
Primary amine color is a developing agent and poorly soluble organic solvent
(Solvent with a log P of 0.4 or more)
You. The most widely known organic solvents of this kind are:
Poorly soluble alcohol, image forming with color developing agent
To promote the reaction with the coupler, i.e. the coupling reaction
Used to increase the efficiency of This kind of alcohol
Are often referred to as "development accelerators" or "development boosters".
be called. U.S. Patent No. 2,304,925 or 3,814,606
As seen in the specification, benzyl alcohol is particularly
It is advantageous for the purpose.   Short-time color developing agent in oil balls with couplers dispersed
Between the developer bank and the
Relatively large amount of color developing agent in swollen gelatin coating
Is considered to promote color development
Of poorly soluble alcohols, namely benzyl alcohol
The use of substances such as oil in the photosensitive material being processed
Because of the high concentration of color developing agent in gelatin,
It has the disadvantage that the residual density is also high, and preserves dye images.
It was the biggest cause of poor stability.   What further highlighted and emphasized this problem was the processing time
Is the recent speed-up process in which the total of
Another major cause is that a large amount of washing water is supplied,
The rinsing process, in which the material was cleanly cleaned, was photo processed
Stabilization process that is removed from the
Is being replaced by water treatment.
You. These anhydrous washing stabilization treatments are described in JP-A-58-14834.
Nos. 58-105145, 58-134634, 58-18631
And Japanese Patent Application Nos. 58-2709 and 59-89288.
Is described in detail.   In each of these methods, a gelatin film in a photosensitive material is used.
In the color developing agent or coupler dispersed oil
Thoroughly wash the scattered color developing agent to reduce the residual concentration.
Storage stability of the dye image
There is a problem of remarkable deterioration.   Yet another problem is that benzylal
Poorly soluble solvents such as Kohl can
Poor solubility of compounds has caused difficulties for a long time
Came. For example, when preparing a developer, benzyl alcohol
Dissolution tends to be very slow and thorough forced agitation
It requires stirring and heating of dissolved water.   If benzyl alcohol remains partially insoluble,
Several days because the color developing agent is distributed and dissolved in high concentration in the part
It is serious because it is oxidized later and sees the generation of “tar”
It will cause obstacles.   Include benzyl alcohol in color developer
One solution is to use a solvent other than water with a log P of less than 0.4, e.g.
Diethylene glycol or polyethylene
To add renimine, triethanolamine, etc.
More known is a method of solubilizing benzyl alcohol
ing.   This method is described in U.S. Pat.No. 3,574,619.
Have been. Further, the disadvantages of solvents such as benzyl alcohol
Is to reduce the solubility of the color developing agent in the solution.
The concentration of the color developing agent in the color developer cannot be increased sufficiently
However, development is not accelerated as expected and speeding up is incomplete
That is what it is.   A particularly important issue is the advantage of labor saving.
Low replenishment requires less replenishment
In the case of a developer containing coal, a developer that can be dissolved in a replenisher
There is a limit to the amount of color developing agent and it cannot be concentrated beyond a certain amount
On the point.   Coupling using such benzyl alcohol
In addition to increasing the speed of forming dye images,
As a method, a color developing agent is contained in the color photosensitive material.
At a minimum, process at a pH higher than that of a normal developer and coat with gelatin.
Silver development with high pH and high color developing agent concentration in the film
A method for increasing the reaction rate is also known.   Therefore, color photographic materials that do not contain ordinary color developing agents
Processing with a high pH color developer.
Therefore, faster development processing is expected.   However, poorly soluble solvents such as benzyl alcohol
Have an appropriate pKa value using the pH of the developer containing
Using a compound, for example, developing at pH 11
As mentioned above, the color developing agent cannot be concentrated.
In addition, the color development reaction is not accelerated as expected
However, for certain photosensitive materials,
Well, even if the dye concentration is reduced
It was half-hearted. Furthermore, using this processing solution
Continuous processing results in a gradually lower maximum dye concentration
And the effect of accelerating development has been practically lost.
In addition to the continuous processing,
The gamma of the tomometry curve increases, and the resulting image can be enhanced
It has unavoidable disadvantages.   A particularly significant drawback of these treatment methods is that recent processing
With the rise of small-volume processing labs due to decentralization,
From an economic and pollution point of view, in addition to simplifying the work of
As with the stabilization process, the replenisher and waste solution are used for the color developer.
There is a growing need to reduce the amount, such as benzyl alcohol
In developing solutions containing poorly soluble solvents, these needs
The answer is that rich and low replenishment cannot be performed.   Also, in such a small-volume processing laboratory,
The replenishment interval of the replenisher is also relatively long, and the evaporation and concentration of the developer
Preservation of developer due to shrinkage or prolonged stagnation time
There is a great deal of concern about stability.
Should be a problem. (Object of the present invention)   Therefore, the object of the present invention is firstly a rapid and continuous process.
Color photographic exposure that can obtain a stable dye image even if
The second object is to provide a method for processing materials.
Eliminates processing, protects water resources, and is useful for processed photographic materials
A color that is safe and has excellent storage stability with no harmful processing chemicals remaining.
-To provide a processing method for obtaining photographs.
Is easy to dissolve and color
Fourth, a true processing method is provided.
In order to provide a processing method capable of rich and low replenishment,
Fifth, even if the small amount processing is continued for a long time,
To provide a stable treatment method without the generation of tools, sludge, etc.
It is to be.   Other objects of the present invention will be apparent from the following description of the present invention.
Let's be. [Means for solving the problem]   In order to achieve the above-mentioned object of the present invention, the present inventors
As a result of various investigations, it was confirmed that the emulsion was substantially composed of a silver chlorobromide emulsion.
Silver halide color photographic light-sensitive having silver halide emulsion layer
The material is formed from a material represented by the following general formula (I) or (II).
1.5 × 10 color developer^-2More than mol / l, water and other than water
Solvent having a log P of less than 0.4 (where P is n-octano
And the partition coefficient for water and water. ) And the capacity
The ratio of the volume of the solvent having a logP of 0.4 or more is 0.003 or less,
Compounds with logP less than 0.4 and pKa of 10.3 or more are 0.05 mol or more
Use a color developer with pH ≥ 10.3
To be achieved by processing within 120 seconds.
It was issued.   The present invention relates to a specific developing agent, a specific developer solvent, a specific
PH of developer, compound with specific pKa and specific halogen
Can be obtained only by a combination of silver halide emulsions,
When using conventional benzyl alcohol, color development
Efficient processing and quick processing is
Enhances the penetration of the developing agent into the dispersed and contained oil spheres,
And thioether and thiocyanic acid as physical development accelerators
A silver dissolving agent such as a salt is added as a development accelerator.
Thus, the coupling reaction is considered rate-limiting.
If this is the case, add a compound with a high pKa value and increase the pH.
Color development reaction quickly and continuously for a long time
It was surprising that we were able to do so stably.   The color developing agent according to the present invention has the following general formula (I) or
(II).  R in the formula (I)₁, R_TwoIs a hydrogen atom, a halogen atom or C
_1-5A linear or branched alkyl group or C_1-5of
Table 1 shows the alkyl group substituted with the alkylsulfonamide group.
I forgot.   R_ThreeIs -R₃₁−NHSO_Two−R₃₂And R₃₁Is a lower alkylene group
, R₃₂Is methyl, ethyl, n-propyl, i-pro
Represents pill, n-butyl, sec-butyl and t-butyl groups.
You.   In addition, R in the formula (II)₁′, R_Two'Is a hydrogen atom, a halogen atom
Or C_1-5Represents a linear or branched alkyl group.   R '₃Is a hydrogen atom, C_1-5Alkyl group, hydro
C with a xy group₁~₅And n is an integer
is there.   One or more color developing agents according to the present invention may be used in combination.
Can be used.   The present inventors have found that a general primary amino color developing agent is acidic.
The color developing agent of the present invention in spite of better lateral solubility
Conversely, the higher the pH, the higher the solubility
Finding specificity and using it, water and non-water
A high-pH developer consisting of a solvent with a log P of 0.4 or less has already been provided.
However, a compound having a pKa of 10.3 or more according to the present invention is used in an appropriate amount.
The development reaction is further accelerated, and
Decrease in Dmax and rise in γ observed during long-term continuous treatment
Scaling, that is, high contrast of the image or generation of tar
Solving the problems is equally surprising.
Was. That is, this makes it possible to obtain extremely efficient development acceleration.
This can be done when no compound with a pKa of 10.3 or more is added.
That was surprising.   The present inventors have developed a color developing agent represented by the general formula (II).
The drug is a poorly soluble alcohol, such as benzyl alcohol.
Its solubility increases markedly with decreasing content,
On the other hand, a color developing agent represented by the general formula (I)
Primary amino color developing agent has better solubility toward acidic side
Above a certain pH, on the contrary, the higher the pH, the better the solubility
For high pH without poorly soluble solvents such as alcohol
The color developing agents of the invention are known to dissolve at extremely high concentrations.
I found it.   The present inventors have used this, substantially water and non-water
A high pH developer consisting of a solvent with a log P of less than 0.4 has already been provided.
However, a compound having a pKa of 10.3 or more according to the present invention is used in an appropriate amount.
The development reaction is further accelerated, and
Decrease in Dmax and rise in γ observed during long-term continuous treatment
Scaling, that is, high contrast of the image or generation of tar
Solving the problems is equally surprising.
Was. That is, this makes it possible to obtain extremely efficient development acceleration.
Compared to the case where no compound having a pKa of 10.3 or more is added.
Developing agent can be reduced, and washing process is performed.
No stabilization even if its residual in color photographic material
The amount is also lower than when benzyl alcohol is used.
Can be further reduced, and the replenishment amount is small and stable.
Can reduce the adverse effect on image storability
And the replenishment of the developer can be reduced.
Was.   Details of these effects are unknown, but specific at a specific pH
When a compound having a pKa value of
OH^-Penetration rate is higher than when no compound is added
It is known that the benzyl alcohol
Addition of poorly soluble solvents such as
The higher the pH, the greater the pH of the developer of the present invention.
Considering that the drug has good solubility, benzyl alcohol
Understand that buffer effect is small at high pH
it can.   In addition, when substantially no benzyl alcohol is contained
Is due to the pH buffering properties of compounds with a pKa of 10.3 or higher.
OH in the membrane^-Penetration into gelatin membrane as well as increased concentration
Of the surplus effect that the concentration of developing agent
Therefore, simply increasing the pH of the developing solution or simply
OH in gelatin film with buffer^-More than just increased concentration
Is presumed to have been obtained.   On the other hand, the effect of preventing tar
The tar produced by the oxidation of
Considering the above-mentioned pH buffering effect,
Use a compound that is extremely soluble in water with a log P <0.4
Also has the advantage of not forming oxidation centers such as crystal nuclei
However, details are unknown.   In addition, among the compounds having a pKa of 10.3 or more, the log P is 0.4 or more.
Is insoluble or precipitates after prolonged storage
Etc. occur, which is not preferable.   When an inorganic base such as an amphoteric metal is used, log P
Is less than 0.4, the storage stability may be poor.
Can be easily solved by using a suitable complexing agent.
You.   As used herein, "substantially silver chlorobromide emulsion"
A small amount of silver iodide may be contained in addition to silver chlorobromide.
For example, 0.3 mol% or less, more preferably 0.1 mol% or less
The lower silver iodide may be contained.   However, in the present invention, silver iodo-free silver chlorobromide milk is used.
Agents are most preferred.   Silver halide color photographic texture processed by the present invention
At least one of the photosensitive emulsion layers of the optical material is substantially
May be composed of a silver chlorobromide emulsion.
Preferably comprises a silver chlorobromide emulsion. The silver chlorobromide is
The shorter the mole% of silver bromide is, the shorter the color development time is
90 mol% or less silver bromide content
Is preferable, and 70 mol% or less and 40 mol% or more are most preferable.
Results. Furthermore, the smaller the amount of silver applied, the shorter the time
1g / m^TwoThe following are particularly good
0.8g / m^TwoBelow, further 0.7g / m^TwoMaximum when
The effect is obtained. Color development processing is 30 ° C or more, 120 seconds or less
Below, preferably 33 ° C. or higher, 120 seconds or lower, particularly preferably 3 ° C.
3 ° C or more, 90 seconds or less, most preferably 33 ° C or more and 60 seconds or less
Process at 30 ° C or more for 150 seconds or more.
When it is performed, the storage stability of the dye deteriorates. Especially the temperature
The processing time is important.
The dark fading property is remarkably reduced, which is not preferable. Processing temperature is dye
To end development in a short time rather than to maintain heat stability
If it is 30 ° C or higher and 50 ° C or lower,
The higher the value, the shorter the processing time.
It is better not to be too high from the qualitative point, 33 ° C or higher, 45 ° C or lower
It is desirable to process below.   In the present invention, it is not preferable that the log is added to the developer.
What is a solvent with P of 0.4 or more? Aliphatic alcohol, aliphatic glycol ether, alicyclic
Alcohol or aromatic alcohol, of which
It has 5 to 20 carbon atoms.   As a specific example   Benzyl alcohol logP = 1.10   o-hydroxybenzyl alcohol logP = 0.73   Cyclohexanol logP = 1.23   2-benzyloxyethanol logP = 0.41   Anisyl alcohol logP = 0.70   1-pentanol logP ≧ 0.4   Phenylethyl alcohol logP = 1.36   p-tolyl carbinol logP = 1.36   n-butanol logP ≧ 0.4   Phenol logP ≧ 0.4   p-hydroxybenzyl alcohol logP ≧ 0.4   Benzylamine logP ≧ 0.4   Diethylene glycol monobutyl ether logP = 0.41 And so on.   In addition, solvents having a logP of less than 0.4 include aliphatic alcohols.
And C4 to C4 such as organic acids.
When a highly functional functional group is present, it has 5 or more carbon atoms and a logP of 0.
It may be less than 4 and is not particularly limited, but specific examples and
Then   Acetic acid   ethanol   acetone   Propionic acid   Propanol   ethylene glycol   Diethylene glycol   Triethylene glycol   Triethanolamine   Diethanolamine And the like.   Log P according to the present invention is the distribution factor of n-octanol / water.
This is a value obtained from the number P. The P value is obtained from the following equation.
The logarithm of the P value obtained in this way is log P value.
These values have been widely used in the field of concentration medicine. log
P-values are based on Chemical Review, 19
Log P in the table described in Vol. 71, No. 6, pp. 555-613.
You can also know by oct. For example, "Ecology
By the calculation method described in Gaku, Vol. 6, pp. 3-11.
Can be obtained, but it is preferable to use the measured value
And particularly preferably measured using n-octanol
Preferably, a value is used.   In the present invention, a compound represented by the general formula (I) is particularly preferable.
Color developing agents are alcohols bonded to aromatic nuclei or amino nitrogen.
Has at least one killsulfonamidoalkyl substituent
And specifically And the like.   In the present invention, the starting compound represented by the general formula (II) is preferred.
The color developing agent is more preferably ▲ R^′ ₂▼ has 1 carbon
To 4 alkyl groups;^′ ₃▼ is hydrogen or carbon number
1-4 alkyl groups, particularly preferably^′ ₁▼
Is an alkyl group having 1 to 4 carbon atoms, most preferably
^′ ₃▼ is an alkyl group having 1 to 4 carbon atoms, specifically, And the like, but the effect of the present invention is more effectively exhibited
In order to obtain the compound (II-1), (II-2), (II-
3), (II-4), (II-5), (II-11), (II-1)
2), (II-13) and (II-14) are preferred, and particularly preferred.
(II-1), (II-2) and (II-3).   Two or more of the above color developing agents can be used in combination.   These color developing agents include hydrochloride, sulfate, phosphate, p-toluene.
Used in the form of salts such as ruene sulfate.   The pH of the color developing solution of the present invention is preferably 10.3 or more.
It is preferably at least 10.50, particularly preferably at least 10.75.
The limit is related to the fog of the photographic emulsion, but in general, the higher the
Particularly preferably used in the range of 10.8 to 13 is particularly preferably used.
It is.   In the present invention, the solubility of the color developing agent in water is remarkable.
Due to the high amount, the amount used should be at least 1.5 × 10
^-2It is preferable to use a mole, more preferably 1.5 to 1
5 × 10^-2Used in the molar range.   In addition, this makes it possible to concentrate the replenisher, resulting in a 250 ml / m^Two
Below, preferably 150ml / m^TwoThe following low replenishment is possible
Thus, labor for preparing and filling the replenisher was saved. These
Ming's substituted paraphenylenediamine derivatives are available in the journal
  Of American Chemical Society 73, 3
It can be easily synthesized by the method described on page 100 (1951).   The color developing solution of the present invention has a bromide ion concentration of 5 × 10 5^-3Mo
Or more, but in the present invention, the bromide content is high.
This is preferable because the amount of replenishment can be reduced as much as possible. Conventional development method
It is said that bromide suppresses the development reaction and the lower the better, the better.
The combination of the color photographic light-sensitive material of the present invention and a developing solution
In the color photographic light-sensitive material of the present invention, a blue-sensitive emulsion layer
3 or more layers including each of the light-sensitive emulsion layer and the red-sensitive emulsion layer
In a color photographic light-sensitive material, the film thickness is 13μ when dried.
m or less, preferably 12 μm or less, particularly preferably 10 μm
The effects of the present invention are maximized when:   The processing method of the photographic light-sensitive material of the present invention relates to the above-mentioned present invention.
It is possible to use a color developing solution containing an unusual color developing agent.
It is possible. In addition, other various people including bath treatment
Method, for example, a spray method in which a processing liquid is sprayed, or processing
Wep method by contact with carrier impregnated with liquid
Or various processing methods such as a developing method using a viscous processing liquid.
However, the processing steps are essentially color development and bleaching.
It preferably comprises three steps of fixing and stabilizing.   In the color developing solution used in the present invention, more usually
Various components added, such as sodium hydroxide,
Alkaline agents such as sodium carbonate, alkali metal sulfite
Salt, alkali metal bisulfite, alkali metal thiocyan
Phosphate, alkali metal halide, polystyrene sulfonate
Fonic acid, water softener, ethylene glycol, diethylene
Glycols, triethanolamine, thickeners and
An image accelerator and the like can be optionally contained.   As an additive other than the above added to the color developing solution
Is a bromide such as potassium bromide or ammonium bromide,
Alkali iodide, nitrobenzimidazole, mercapto
Benzimidazole, 5-methyl-benzotriazole
Or 1-phenyl-5-mercaptotetrazole
Compounds for high-speed treatments, stain inhibitors, slurries
Antioxidants, preservatives, layer effect promoters, chelating agents, etc.
is there.   Aminopolycarboxylic acid is used as the chelating agent in the developer.
Salts and organic phosphonates are mainly used.   The pH of the stabilizing solution alternative to washing in the present invention makes the present invention more effective.
In order to achieve the desired result, preferably in the range of 5.5 to 10.0
Is more preferably in the range of pH 6.3 to 9.5, especially
The pH is preferably in the range of 7.0 to 9.0. Water washing alternative of the present invention
It can be contained in a stabilizing solution. pH adjusters are generally known
Use any of the known alkaline or acid agents
it can.   The present invention requires a small amount of replenishment of a stabilizing bath with a water washing alternative stabilizer.
In this case, the effect is great, and the replenishment amount is
Range of 1 to 50 times the amount brought in from the previous bath per unit area
Is preferable, and the effect of the present invention is within a range of 2 to 20 times.
This is particularly noticeable.   The treatment temperature of the stabilization treatment is 15 ° C to 60 ° C, preferably 20 ° C.
The range of ℃ to 45 ℃ is good. In addition, the processing time is also from the viewpoint of quick processing.
The shorter the time, the better, but usually 20 seconds to 10 minutes,
Most preferably, it is 1 minute to 3 minutes.
In the case, processing time is shorter in the former tank, and processing time is
Is preferably long. Especially 20% to 50% increase of the front tank
It is desirable to process them sequentially in the processing time. Stability according to the invention
No washing treatment is required after the
Rinse by small amount of water in time, surface cleaning, etc. are required
Can be performed arbitrarily according to   In the stabilization process according to the present invention, the replacement
When using a multi-tank counter current method,
It is preferable to supply to the bath and overflow from the previous bath
New Of course, it can also be processed in a single tank. The above compound
As a method for adding the substance, add it as a concentrated liquid to the stabilization tank.
To the stabilizing bath
Add the above compound and other additives and substitute them with water
There are various methods such as whether to use a supply solution for a stable replenisher
May be added by any addition method.   Conventionally, photosensitive material is processed with a bleach-fix solution after color development.
And then treat it with a water-wash alternative stabilizing solution.
As a result of the continuous treatment,
The specific gravity at 24 ° C of the washing substitute stabilizer becomes 1.002 or more
And the unexposed area tends to be contaminated,
According to Ming, the occurrence of contamination under these conditions has been significantly improved.
Be good.   In the present invention, processing with a bleach-fix solution and subsequent
Instead of qualitatively washing with water, it is treated with an alternative stabilizing solution for washing.
I.e., treatment with a stabilizing solution instead of washing directly after the bleach-fix bath
This processing step has been known in the past.
After the bleach-fix bath is used, it is washed with water and treated with a stabilizing solution.
It is completely different from the step of performing.   Thus, in the present invention, the treatment with the stabilizing solution is a drift.
Stabilization immediately after processing with white fixer
Specifies a stabilization process that does not perform a regular water washing process.
The treatment solution used for the stabilization treatment is called a washing substitute stabilizing solution.
The treatment tank is called a stabilizing bath or a stabilizing tank.   In the present invention, when the number of the stabilization tanks is 1 to 5,
The effect is great, particularly preferably 1 to 3 tanks.
Is preferably 9 tanks or less.   A bleaching solution usable in the bleach-fixing solution used in the present invention.
Whitening agents are metal complex salts of organic acids. The complex salt is an aminopoly
Carboxylic acid or organic acid such as oxalic acid or citric acid
And metal ions such as copper and copper. like this
Best used to form metal complexes of various organic acids
Preferred organic acids include polycarboxylic acids.
These polycarboxylic acids or aminopolycarboxylic acids are
Lucali metal salt, ammonium salt or water-soluble amine salt
It may be. Specific examples of these are as follows:
Can be mentioned. [1] Ethylenediaminetetraacetic acid [2] diethylenetriaminepentaacetic 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 sake
Lithic acid) [9] Ethyl ether diamine tetraacetic acid [10] glycol ether diamine tetraacetic acid [11] Ethylenediaminetetrapropionic acid [12] phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Tetraethylenediaminetetraacetate (trimethyl
Ruammonium) salt [15] tetrasodium ethylenediaminetetraacetate
salt [16] diethylenetriaminepentaacetic 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] Sodium cyclohexanediaminetetraacetate
salt   These bleaching agents are 5-450 g /, more preferably 20-2 g
Use at 50g /. The bleach-fixing solution contains no more than the bleaching agent described above.
Contains a silver halide fixing agent outside and a preservative if necessary
A liquid having a composition containing a sulfite is applied. Ma
Also, ethylenediaminetetraacetate (III) complex salt bleach
Like the other silver bromide fixing agents described above, such as ammonium bromide
A bleach-fix solution having a composition in which a small amount of a halide is added,
Or conversely, large amounts of halides such as ammonium bromide
Bleach-fix solution composed of the components added to
Iron (III) complex diaminetetraacetate bleach and large amounts of bromide
Set consisting of a combination with a halide such as monium
Specific bleach-fixing solutions can also be used. Said c
Hydrogen chloride other than ammonium bromide
Acid, hydrobromic acid, lithium bromide, sodium bromide, bromide
Potassium, sodium iodide, potassium iodide, ammonium iodide
Ni or the like can also be used.   As the silver halide fixing agent contained in the bleach-fix solution
Is opposite to silver halide used in normal fixing processing.
Compounds that form water-soluble complex salts in response, for example, thiosulfuric acid.
Potassium, sodium thiosulfate, ammonium thiosulfate
Thiosulfate, potassium thiocyanate, thiocyan
Thio such as sodium citrate, ammonium thiocyanate
Representative examples include cyanate, thiourea, and thioether.
Things. These fixing agents can be dissolved at 5g / or more
Use in amounts in the range, but generally use at 70g-250g /
You.   In addition, boric acid, borax, sodium hydroxide are used as the bleach-fixing solution.
, Potassium hydroxide, sodium carbonate, potassium carbonate,
Sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate
And various pH buffers such as ammonium hydroxide
Or a combination of two or more,
Furthermore, various optical brighteners, defoamers and surfactants
A sexual agent may also be included. Also hydroxyla
Bisulfite adduct of min, hydrazine and aldehyde compounds
Preservatives, etc., and organic chelation of aminopolycarboxylic acids, etc.
Agent or nitro alcohol, nitrate   Photographic composition of the silver halide color photographic light-sensitive material of the present invention
The layer contains a dye (AI dye) that decolorizes with a water-soluble or color developing solution.
And the AI dye is oxo.
Nol dye, hemioxonol dye, merocyanine dye
And azo dyes. Among them, oxonol dyes,
Hemioxonol dyes and merocyanine dyes are useful.
is there. Examples of AI dyes that can be used include UK Patent 584,609
Nos. 1,277,429, JP-A-48-85130, and 49-99620
Nos. 49-114420, 49-129537, 52-108115
Nos. 59-25845, 59-111640, 59-111641
No. 2,274,782, 2,533,472, 2,956,87
No. 9, 3,125,448, 3,148,187, 3,177,078,
3,247,127, 3,260,601, 3,540,887, 3,5
Stabilizers such as Nos. 75,704 and 3,653,905, methanol,
Organic solvents such as methylsulfonamide and dimethylsulfoxide
A medium or the like can be appropriately contained.   The bleach-fix solution used in the present invention includes JP-A-46-280,
JP-B-45-8506 and JP-B-46-556, Belgian Patent No. 770,9
No. 10, JP-B-45-8836, JP-B-53-9854, JP-A-54-71
Various bleaching described in 634 and 49-42349
Accelerators can be added.   The pH of the bleach-fix solution is used at 4.0 or higher.
Used at H5.0 or more and pH 9.5 or less, desirably pH 6.0 or more and pH
Used below 8.5, and furthermore the most preferred pH is 65
The processing is performed in the range from 8.5 to 8.5. Processing temperature is less than 80 ℃
3 ° C. or higher, preferably 5 ° C., higher than the temperature of the processing solution in the color developing tank
Although it is used at a temperature lower than
Use it with less departure. Nos. 3,718,472, 4,071,312, and 4,070,352
What is described can be mentioned.   These AI dyes are generally used in two moles per mole of silver in the emulsion layer.
× 10^-3~ 5 × 10^-1It is preferable to use a mole, more preferably
Or 1 × 10^-2~ 1 × 10^-1Use moles.   The crystals of silver halide grains can be either normal crystals or twins.
The ratio between the [1.0.0] plane and the [1.1.1] plane may be arbitrary.
Things can be used. Furthermore, these silver halide grains
Even if the crystal structure is uniform from inside to outside,
Inside and outside have different layered structure (core-shell type)
It may be something. Also, these silver halides are latent
Even if the image is mainly formed on the surface,
It may be of a forming type. Further tabular silver halide
Particles (see JP-A-58-113934 and JP-A-59-170070)
Can also be used.   In the present invention, rapid processing and stability of image dye can be improved.
In particular, the silver halide grains are
It is qualitatively monodisperse and a core shell emulsion is preferred. This
These are either acidic, neutral or ammonia methods.
May be obtained by the preparation method described above.   Also, for example, seed particles are made by an acid method,
Grown by the fast ammonia method to a specified size
It may be a method of growing. Grow silver halide grains
Control the pH, pAg, etc. in the reaction vessel
For example, halogens described in JP-A-54-48521
Silver ions and halides in proportion to the growth rate of silver halide grains
It is preferable that ions are sequentially and simultaneously injected and mixed.   The preparation of silver halide grains according to the present invention is as described above.
It is preferable to carry out. Including the silver halide grains.
Having a silver halide emulsion as defined herein.
Say.   These silver halide emulsions contain active gelatin;
Sensitizers such as allylthiocarbamide, thiourea, cystine
Selenium sensitizers; reduction sensitizers such as No. 1
Tin salt, thiourea dioxide, polyamine, etc .; noble metal sensitizer
For example, gold sensitizers, specifically potassium aurithiocyane
, Potassium chloroaurate, 2-aurothio-3
-Methylbenzothiazolium chloride or the like
Ruthenium, palladium, platinum, rhodium, iridium
Sensitizers of water-soluble salts such as
Lopaladate, potassium chloroplatinate and nato
Lithium chloroparadate (some of these are
Acts as a sensitizer or fog inhibitor depending on the size
I do. ) Alone or in combination as appropriate (for example,
Sensitizer and sulfur sensitizer, gold sensitizer and selenium sensitizer
Combined use) and may be chemically sensitized.   The silver halide emulsion according to the present invention contains a sulfur-containing compound.
Add and chemically ripen, before this chemical ripening, during ripening, or
After aging, at least one type of hydroxytetrazaindene
Of nitrogen-containing heterocyclic compounds having
At least one kind may be contained.   The silver halide used in the present invention has a desired light sensitivity.
In order to impart photosensitivity to the wavelength range, an appropriate sensitizing dye is used.
5 × 10 for 1 mole of silver logenide^-8Mol ~ 3 x 10^-3Mole
It may be added for optical sensitization. Various sensitizing dyes
And sensitizing dyes of one kind or
Can be used in combination of two or more. In the present invention
Examples of sensitizing dyes that are advantageously used include, for example,
Can be mentioned.   That is, sensitizing dyes used in blue-sensitive silver halide emulsions
As, for example, West German Patent 929,080, US Patent 2,231,6
No. 58, No. 2,493,748, No. 2,503,776, No. 2,519,001
Nos. 2,912,329, 3,656,959, 3,672,897,
No. 3,694,217, No. 4,025,349, No. 4,046,572, UK
Patent Nos. 1,242,588, JP-B-44-14030, JP-B-52-24844
And the like. Also green sensitivity
As sensitizing dyes used in silver halide emulsions, for example,
For example, U.S. Patents 1,939,201, 2,072,908, and 2,739,149
No. 2,945,763, British Patent 505,979, etc.
Cyanine dye, merocyanine dye or complex
Anine dyes can be mentioned as typical examples.
You. In addition, sensitization used in red-sensitive silver halide emulsions
As the dyes, for example, U.S. Pat.Nos. 2,269,234 and 2,270,3
No. 78, No. 2,442,710, No. 2,454,629, No. 2,776,280
Cyanine dyes and merocyanine colors as described in
And complex cyanine dyes as typical examples.
I can do it. Furthermore, U.S. Pat.No.2,213,995,
2,493,748, 2,519,001, West German Patent 929,080, etc.
Cyanine dyes and merocyanine dyes as described
Or a complex cyanine dye in a green-sensitive silver halide emulsion or
It can be advantageously used for a red-sensitive silver halide emulsion.   These sensitizing dyes may be used alone,
May be used in combination.   The photographic light-sensitive material of the present invention may contain cyanine or
Spectral sensitization method using a single or combination of Russianin dyes
Optical sensitization may be performed in a desired wavelength range.   Typical examples of particularly preferred spectral sensitization methods include:
For example, benzimidazolocarbocyanine and benzoxazo
JP-B-43-4936 concerning combination with locarbocyanine
No. 43-22884, No. 45-18433, No. 47-37443,
Nos. 48-28293, 49-6209, 53-12375, JP
52-23931, 52-51932, 54-80118, 58-1
No. 53926, No. 59-116646, No. 59-116647, etc.
Method.   Also, a carbocyanine having a benzimidazole nucleus and
Concerning combinations with other cyanines or merocyanines
As for example, JP-B-45-25831, JP-B-47-11114,
47-25379, 48-38406, 48-38407, 45-3
No. 4535, No. 55-1569, JP-A No. 50-33220, No. 50-385
No. 26, No. 51-107127, No. 51-15820, No. 51-135528
No. 52-104916 and No. 52-104917.   In addition, benzoxazolocarbocyanine (oxa
Rubocyanin) and other carbocyanines
Examples thereof include JP-B-44-32753 and JP-B-46-11627.
No., JP-A-57-1483, relating to merocyanine
For example, Japanese Patent Publication Nos. 48-38408, 48-41204 and 50-
No. 40662, JP-A-56-25728, JP-A-58-10753, JP-A-58-9
No. 1445, No. 59-116645, No. 50-33828, etc.
You.   Also, a combination of thiacarbocyanine and another carbocyanine
For example, Japanese Patent Publication No. 434932/1972,
43-4933, 45-26470, 46-18107, 47-87
No. 41, JP-A-59-114533, etc.
Or dimethine merocyanine, monomethine or trimethine
JP-B-49-6207 using cyanine and styryl dye
Can be advantageously used.   These sensitizing dyes are used in the silver halide emulsion of the present invention.
To add the dye solution in advance, for example, methyl alcohol
, Ethyl alcohol, acetone, dimethylform
Amides or fluorinated alcohols described in JP-B-50-40659
Dissolved in a hydrophilic organic solvent such as a polyester.   The timing of addition is at the beginning of the chemical ripening of the silver halide emulsion.
During ripening, it can be at any time at the end of ripening, and in some cases
It may be added to the step immediately before the emulsion coating.   Each of the silver halide emulsion layers according to the present invention has a cap.
Reacts with the oxidized form of the color developing agent to form a dye.
A compound that can be formed can be contained.   Various couplers that can be used in the present invention
Yellow coupler, magenta coupler and cyan cap
Can be used without any particular restrictions. These mosquitoes
The puller may be a so-called two-equivalent type or a four-equivalent type.
It may be a puller, or a combination with these couplers
It is also possible to use diffusible dye releasing couplers
is there.   As the yellow coupler, closed ketomethylene is used.
Active point called compound, so-called 2-equivalent coupler
-O-aryl substituted coupler, active site -o-acyl substitution
Coupler, active site hydantoin compound substituted coupler, active
Urazole Compound-Substituted Couplers and Active Site Succinates
Acid imide compound substituted coupler, active site fluorine substituted coupler
-, Active site chlorine or bromine substituted coupler, active site -o
-Yellow couplers with effective sulfonyl substituted couplers
Can be used as Available yellow coupler
As specific examples, U.S. Pat.Nos. 2,875,057 and 3,265,506
Nos. 3,408,194, 3,551,155, 3,582,322,
3,725,072, 3,891,445, West German Patent 1,547,868
No. 2,219,917, West German Application No. 2,261,361, West German Application No. 2,41
4,006, British Patent 1,425,020, JP-B-51-10783,
JP-A-47-26133, JP-A-48-73147, JP-A-51-102636,
No. 50-6341, No. 50-123342, No. 50-130442, No. 50
-21827, 50-87650, 52-82424, 52-115
No. 219, No. 58-95346, etc.
Can be.   The magenta coupler used in the present invention
Pyrazolone, pyrazolotriazole, pyrazo
Linobenzimidazole and indazolone compounds
Can be mentioned. These magenta couplers are
Like low couplers, not only 4 equivalent couplers, but also 2 equivalents
It may be a quantitative coupler. Specific of magenta coupler
Examples are U.S. Patents 2,600,788, 2,983,608,
062,653, 3,127,269, 3,311,476, 3,419,3
No. 91, 3,519,429, 3,558,319, 3,582,322
No. 3,615,506, 3,834,908, 3,891,445,
West German Patent 1,810,464, West German Patent Application (OLS) 2,408,665
No. 2,417,945, 2,418,959, 2,424,467,
JP-B-40-6031, JP-A-51-20826, 52-58922
No. 49-129538, No. 49-74027, No. 50-159336
No. 52-42121, No. 49-74028, No. 50-60233,
No. 51-26541, No. 53-55122, Japanese Patent Application No. 55-110943, etc.
Can be mentioned.   Further useful cyan couplers used in the present invention
For example, phenolic and naphthol couplers
-And the like. And these cyan caps
Is only a 4-equivalent coupler like the yellow coupler
Instead, a 2-equivalent coupler may be used. Cyan coupler
As specific examples of U.S. Pat.Nos. 2,369,929 and 2,434,272
No. 2,474,293, 2,521,908, 2,895,826,
3,034,892, 3,311,476, 3,458,315, 3,4
No. 76,563, No. 3,583,971, No. 3,591,383, No. 3,767,41
No. 1, No. 3,772,002, No. 3,933,494, No. 4,004,929,
West German Patent Application (OLS) Nos. 2,414,830 and 2,454,329
No.48-59838, No.51-26034, No.48-5055, No.51
-146872, 52-69624, 54-90932, 58-95
No. 346, Japanese Patent Publication No. 49-11572, etc.
Can be.   In the silver halide emulsion layer of the present invention and other photographic constituent layers
Has a non-diffusible DIR compound, colored magenta or cyan
Caps such as couplers, polymer couplers, and diffusible DIR compounds
A puller may be used in combination. Non-diffusible DIR compound, color
For the magenta or cyan coupler, the applicant has
Japanese Patent Application No. 59-193611, polymer couplers
Is described in Japanese Patent Application No. 59-172151 by the present applicant.
Each can be referenced.   The above coupler that can be used in the present invention is a photographic composition of the present invention.
The method of adding to the layer is the same as before, and
The amount of silver added is not limited, but 1 × 10^-3
To 5 mol, more preferably 1 × 10^-2~ 5 × 10
^-1It is.   The silver halide color photographic light-sensitive material of the present invention further comprises
Photographic additives can be included, such as
Listed in Research Disclosure Magazine No. 17643
Antifoggants, stabilizers, UV absorbers, color contamination prevention
Agent, fluorescent whitening agent, color image fading inhibitor, antistatic agent, hardening
Agents, surfactants, plasticizers, wetting agents, etc. can be used
You.   In the silver halide color photographic light-sensitive material of the present invention,
Hydrophilic colloids used to prepare emulsions include:
Gelatin, derivative gelatin, gelatin and other polymers
Proteins such as graft polymers, albumin, and casein;
Hydroxyethyl cellulose derivative, carboxymethyl
Cellulose derivatives such as cellulose, starch derivatives, polyvinyl chloride
Nyl alcohol, polyvinyl imidazole, polyacryl
Mono- or copolymer synthetic hydrophilic polymers such as luamide
Etc. are included.   A support of the silver halide color photographic light-sensitive material of the present invention;
For example, baryta paper, polyethylene coated paper, poly
Propylene synthetic paper with reflective layer or reflector
Transparent support for use, for example, a glass plate, cellulose acetate
Or cellulose nitrate or polyethylene tereph
Polyester film such as tarate, polyamide fill
System, polycarbonate film, polystyrene film
And other ordinary transparent supports.
No. These supports are appropriately used depending on the purpose of use of the photosensitive material.
Selected.   Silver halide emulsion layer used in the present invention and its
For other photo component layers, dipping and air
Various applications such as doctor application, curtain application, hopper application
A coating method can be used. U.S. Patent 2,761,79
Simultaneous application of two or more layers by the method described in No. 1 and 2,941,898
A coating method can also be used.   In the present invention, the coating position of each emulsion layer is arbitrarily determined.
be able to. For example, for photosensitive materials for full-color photographic paper
In the case, a blue-sensitive silver halide emulsion is sequentially formed from the support side.
Layer, green photosensitive silver halide emulsion layer, red photosensitive halide
It is preferable to arrange the silver emulsion layer. These photosensitive
The silver halide emulsion layer may be composed of two or more layers.
Good. And all these photosensitive emulsion layers are substantially salt
The effect of the present invention is remarkable when a silver bromide emulsion is used.   In the light-sensitive material of the present invention, an appropriate thickness according to the purpose.
It is optional to provide an intermediate layer of
Layer, anti-curl layer, protective layer, anti-halation layer, etc.
Various layers can be used in appropriate combination as constituent layers
You. In these constituent layers, the emulsion as described above is used as a binder.
Use the same hydrophilic colloid that can be used for the layer
In the emulsion layer as described above.
Contains various photographic additives that can be used
Can be   The pKa according to the present invention is obtained by expressing the acid dissociation constant Ka on a logarithmic scale.
And the Lange's Handboo
k of Chemistry, 11th Edition.Edited by John A. Dea
n.McCGRAW HILL BOOK COMPANY, 1973), pages 5-12 to 5-
According to 13.   According to the present invention, log P is less than 0.4 and pKa is 10.3 or more.
Examples of the compound include the following. (B-1) Sodium aluminate NaAlO_Two (B-2) Sodium silicate Na_TwoO ・ nSiO_Two(N = 0.5
Inorganic bases such as 4) (B-3) Phosphate (B-4) Borate Monosaccharide pKa C_Two  (Geose)     (B-5) Glycol aldehyde                                            pKa C_Three  (Triose)     (B-6) Glycerin aldehyde     (B-7) Dihydroxyacetone C_Four  (Tetrose)     (B-8) Erythrose     (B-9) Threose     (B-10) Erythrulose C_Five  (Pentose) ~ 12 ~ 14     (B-11) Arabinose     (B-12) Xylose     (B-13) Ribose     (B-14) Lyxose     (B-15) Xylulose     (B-16) Ribulose C₆  (Methyl pentoses)     (B-17) Rhamnose     (B-18) Fucose C₆  (Hexoses) ~ 12 ~ 14     (B-19) Glucose 12.2, 13.85                                            pKa     (B-20) Mannose     (B-21) Galactose 12.3, 14.1     (B-22) Tallow     (B-23) Idose     (B-24) Growth     (B-25) Altrose     (B-26) Allose     (B-27) Fructose 12.1, 13.8     (B-28) Sorbose     (B-29) Tagatose     (B-30) Push Course C₇  (Heptose) pKa     (B-31) Heptulose Disaccharide     (B-32) Trehalose     (B-33) Saccharose 12.6, 13.5     (B-34) Maltose 12, 13.3     (B-34) Cellobiose     (B-35) Gentiobiners                                            pKa     (B-36) Lactose 12.1, 13.5 Trisaccharide     (B-37) Raffinose     (B-38) Methyletose     (B-39) Gentianose     (B-40) 2-acetylcyclohexanone 14.1     (B-41) 4-acetyl-β-mercaptoisolo
Isin 10.30     (B-42) 2-acetyl 1-naphthol 13.40     (B-43) Alizarin-3-sulfonic acid 11.01     (B-44) α-amino-i-butyric acid 10.56     (B-45) γ-amino-n-butyric acid 10.80     (B-46) 1-aminocycloheptanecarboxylic acid                                              10.46                                            pKa     (B-47) 2-amino-4,5-dimethylphenol
Le 10.40     (B-48) 5-amino-N-phenylsulfonic acid                                              10.95     (B-49) 4-aminophenol 10.30     (B-50) 2-aminopyridine-1-oxide                                              16.74     (B-51) 5-amino-N-valeic acid 10.77     (B-52) Ascorbic acid 11.82     (B-53) benzyl-α-dioxime 12.0     (B-54) Benzyl-mercaptan 10.70     (B-55) Betaine 12.16     (B-56) t-butyl hydroxide 12.80     (B-57) Caffeine 10.4     (B-58) Karmajito 12.34                                            pKa     (B-59) Chromazurol S 11.47     (B-60) Corniin 11.0     (B-61) cycloacetylhydrazide 11.17     (B-62) cis-cis-cyclohexanone-1,3,
5-triamine 10.4     (B-63) 1,3-diamino-2-aminomethylp
Lopan 10.38     (B-64) dehydroascorbic acid 10.3     (B-65) α, γ-diaminobutyric acid 10.4     (B-66) 5,31-diethylparbituric acid 13.31     (B-67) Diethyl pigand 11.68     (B-68) N, N-diethylglycine 10.47                                            pKa     (B-69) 2,3-dihydroxybenzoic acid 11.76     (B-70) 2,5-dihydroxybenzoic acid 10.50     (B-71) 2,4-dihydroxybenzoic acid> 10.3     (B-72) 3,4-dihydroxybenzoic acid 11.74     (B-73) 2,3-dimercaptopropane-1-o
(BAL) 10.58     (B-74) dimethyl biguanide 11.52     (B-75) dimethylglyoxime 10.60     (B-76) 2,4-dimethyl-8-hydroxyquino
Phosphorus 10.60     (B-77) 2,3-dimethylphenol 10.50     (B-78) 2,4-dimethylphenol 10.58                                            pKa     (B-79) 3,4-dimethylphenol 10.32     (B-80) dithiooxamide 10.89     (B-81) Eriochrome Black T 11.55     (B-82) Ethane-1,2-dithiol 10.54     (B-83) Ethyl acetoacetate 10.68     (B-84) Ethylene-N, N-diacetic acid 11.05     (B-85) Ethyl biguanide 11.47     (B-86) Ethylenediaminetetraacetic acid 10.95     (B-87) Ethyl hydroxy peroxide 11.80     (B-88) Ethyl mercaptan 10.50     (B-89) 3-ethylpentane-dione 2,411.34                                            pKa     (B-90) Ethylpyrrolidine 10.43     (B-91) Glycoscorbic acid 11.58     (B-92) Glucose 12.43     (B-93) Glutamide 11.43     (B-94) Glycerol 14.15     (B-95) Glycol 14.22     (B-96) Guanylethyl urea 11.10     (B-97) o-hydroxybenzoic acid 12.38     (B-98) N- (2-hydroxyethyl) bigua
Nido 11.53     (B-99) 2-hydroxypyridine 11.62     (B-100) 4-hydroxypyridine 11.09     (B-101) Indole 4 10.32     (B-102) Leucine 10.53     (B-103) Mercaptoacetic acid 10.55     (B-104) Mercaptosuccinic acid 10.94     (B-105) 2-methyl-2-butanethiol                                              11.35     (B-106) 2,2'-methylene-bis (4,6-jig
Lolophenol) 10.65     (B-107) Methyl ethyl ketoxime 12.45     (B-108) Methyl mercaptan 10.70     (B-109) 3-methylpentane-2,4-dione                                              10.87     (B-110) Methylpiperazine 11.02     (B-111) 2-methyl-2-propanethiol                                              11.2     (B-112) Murekid 10.50     (B-113) Nicotinic acid 11.0     (B-114) L-proline 10.69     (B-115) 2-Propanethiol 10.86     (B-116) Pyrocatechol 12.08     (B-117) Pyrogallol 12.63     (B-118) Resorcinol 12.32     (B-119) β-resorcinic acid> 10.3     (B-120) Salicylaldoxime 12.11     (B-121) salicylic acid 12.38     (B-122) Spartine 11.76     (B-123) 5-sulfosalicylic acid 12.00     (B-124) Tetralol-2 10.48     (B-125) Thioglycolic acid 10.55     (B-126) Toluhydroquinone 11.62     (B-127) Tyrone 12.6     (B-128) 2,2'-2 "-triaminotriethyl
Ann 10.37     (B-129) 2,4,6-trimethylphenol 10.88     (B-130) Xanthin 11.68 Example   Hereinafter, specific examples of the present invention will be described using examples.
However, embodiments of the present invention are not limited thereby. (Example 1)   On a paper support laminated with polyethylene,
Each layer is applied sequentially from the support side, and silver halide color
True photosensitive material samples Nos. 1 to 28 were prepared. Layer 1: 1.2 g / m^TwoGelatin, 0.32g / m^Two(Silver equivalent, hereinafter the same
Silver halide gelatin emulsion (silver halide)
The composition and average particle size are shown in Tables 1 and 2. ), 0.50
g / m^Two0.80 g / m dissolved in dioctyl phthalate^TwoNo
Blue-sensitive silver halide containing low coupler (Y-1)
Emulsion layer. Layer 2: 0.70 g / m^TwoGelatin, 10mg / m^TwoIrradiation
Anti-dye (AI-1), 5mg / m^TwoOf (AI-2)
Interlayer. Layer 3: 1.25 g / m^TwoGelatin, 0.28g / m^TwoGreen Sensitive Halogen
Silver halide gelatin emulsion (Silver halide composition and average grain size are
The results are shown in Table 1 and Table 2. ), 0.30g / m^TwoThe dioctyl lid
0.62g / m dissolved in rate^TwoMagenta coupler (M-
A green-sensitive silver halide emulsion layer containing 1). Layer 4: 1.2 g / m^TwoIntermediate layer made of gelatin. Layer 5: 1.4g / m^TwoGelatin, 0.26g / m^TwoRed-sensitive halogen
Silver halide gelatin emulsion (Silver halide composition and average grain size are
See Table 1 and Table 2. ), 0.20g / m^TwoThe dioctyl lid
0.45 g / m dissolved in rate^TwoCyan coupler (C-1)
And a red-sensitive silver halide emulsion layer. Layer 6: 0.50 g / m^TwoProtective layer containing gelatin.   The blue-sensitive silver halide emulsion layer and the green-sensitive silver halide
Halogen of each emulsion layer and red-sensitive silver halide emulsion layer
Use silver halide whose color has been increased by a general sensitizing dye.
Was.   In addition, 2,4-dichloro-6-hydroxy is used as a hardening agent.
Add sodium S-triazine in layers 2, 4 and 6
did.   An optical wedge is used for the photosensitive material sample prepared as described above.
And then processed in the following step.   Processing process (38 ° C)     Color development 40 seconds     Bleaching and fixing 50 seconds     Stable 50 seconds     Drying 60 seconds 60-80 ° C   The composition of each processing solution is as follows. [Color developing solution]     800ml pure water     Benzyl alcohol (log P1.1)
Was     Hydroxyamine sulfate 2.0 g     Potassium bromide 0.6 g     Sodium chloride 1.0 g     Potassium sulfite 2.0 g     Triethanolamine (log P0.27) 2.0     The color developing agent Kodak CD-3 (Ip2) of the present invention (Ip2)
0.023 mol)     1-hydroxyethylidene-1,1-diphosphonic acid (6
0% aqueous solution) 1.5ml     Magnesium chloride 0.3 g     0.3 mol buffer     Kaycoll-PK-Conc
(Fluorescent whitening agent, manufactured by SINCO Chemical Co.) 2ml   Add pure water to 1 to make 20% potassium hydroxide or 10% diluted
The pH was adjusted with sulfuric acid to the values shown in Table 1 or Table 2.   The buffers used in the color developer are listed below.
Used. Potassium carbonate buffer   Adjust pH by adding KOH to 0.3 mol of potassium carbonate Dimethyl glycine buffer   Add HCl to 0.3 mol of sodium dimethylglycine to adjust pH
Adjustment Phosphate buffer   Sodium hydroxide to 0.3 mol of disodium phosphate hydroxide
PH adjustment Borate buffer   Add 0.07 mol of sodium chloride to 0.3 mol of boric acid and add
Add sand and adjust pH Glucose buffer   Adjust pH by adding NaOH to 0.3 mol of glucose [Bleaching fixer]     Pure water 550ml     Iron (III) ammonium ethylenediaminetetraacetate                                               65 g     Ammonium thiosulfate (70% aqueous solution) 85 g     Sodium bisulfite 10 g     Sodium metabisulfite 2 g     Ethylenediaminetetraacetic acid-2-sodium 6 g   Add pure water to make 1 to pH with ammonia water or diluted sulfuric acid.
Adjust to = 7.0. Stabilizing liquid     5-chloro-2-methyl-4-isothiazoline-3-
ON 0.03g     Orthophenylphenol 0.01g     2-methyl-4-isothiazolin-3-one 0.03 g     1-hydroxyethylidene-1-diphosphonic acid                                              0.5 g     Magnesium nitrate 0.04g     0.5 g zinc sulfate     Ammonia water (28% aqueous solution) 2 g   Adjust to 1 with water and adjust to pH 7.8 with sulfuric acid and potassium hydroxide.
Was.   Exposure is performed imagewise using the sample,
It was adjusted and processed according to the conditions in Tables 1 and 2.   Measure the maximum blue density of the obtained sample with an optical densitometer.
Was.   Table 1 shows the results when the sample is substantially silver chlorobromide.
Table 2 shows the results when silver iodide was contained at 5 mol%.
did.   From Table 1, log P is 1.1 for solvent 1 with log P less than 0.4.
When benzyl alcohol of 0.015 is also used, the pKa is
Even with buffers above 10.3, the maximum concentration is still sufficiently high.
No, but use a buffer with a pKa of 10.3 or higher
If there is no call, the maximum concentration is sufficient.
You. However, if a buffer with a pKa of 10.3 or less is used,
No maximum concentration can be obtained with or without zyl alcohol
No.   As can be seen from the results in Table 2, the halogenation containing silver iodide
In the case of silver halide photographic material, the silver chlorobromide field shown in Table 1 is used.
Compared with the case where the formulation conditions according to the method of the present invention are sufficient,
It can be seen that the maximum concentration is not obtained and the result is unfavorable
You. (Example 2)   Compound of the Invention Instead of CD-3 Used in Example 1
(II-1) Kodak CD-6 manufactured by Eastman Kodak Company
The results were similar to those in Tables 1 and 2
I got However, comparing CD-3 and CD-6 at the same molar concentration
As a result, the color density was somewhat lower for CD-6. Only
When using CD-4, magenta dye fading (at 80 ° C and 70RH)
Storage for 20 days). (Example 3)   To investigate the effect on development processing time, use a phosphate buffer
Compared with the case using potassium carbonate buffer.
Compared. At this time, the benzyl alcohol was set to 0, and the pH was set to 11.
did. The results are shown in Table 3. The photosensitive material is the salt of Example 1.
Using a bromide emulsion with a fading rate of 80 ° C and 70RH for 20 days
Asked between. (Example 4)   The pH was changed to 10.1 and 10.5 as in Example 3.
The experiment showed that the maximum concentration was not significant at pH 10.1.
Although it decreased sharply, it hardly decreased at 10.5,
Similar results were obtained for the magenta fade rate at any pH.
From the results of Example 3 and Example 4, benzyl alcohol was
If no buffer is used with a pKa of 10.3 or less,
To obtain a large concentration, longer processing time is preferable, but pK
Using a buffer with a of 10.3 or more shortens the development time.
And increase the processing stability.
became. (Example 5)   The main drug is CD-3 using a phosphate buffer, and the present invention (II-11)
Compound Kodak-CD-4, CD-, manufactured by Eastman Kodak Company
6 Blue color by changing the color developing agent concentration and further changing the pH
The maximum concentration was determined. The results are shown in Table 4. However
The treatment conditions were the same as in Example I, with benzyl alcohol being 0
The photosensitive material used was the silver chlorobromide emulsion of Example I.
Was used.   From this result, to obtain the maximum concentration, CD-3, CD4, and CD-6
Either one may be used, but CD-3,
CD-6 is preferred, and CD-3 is preferred because of the maximum color density.
No. (Example 6)   Glucose buffer, boric acid, etc. instead of phosphate buffer
Even with a buffer having a pKa of 10.3 or more, Example 2, Example 3,
The same results as in Examples 4 and 5 were obtained. (Example 7)   Tar generation during storage at room temperature using phosphate buffer
Conditions and whether the maximum concentration has decreased with storage of the solution
Was. The experiment was carried out in the same manner as in Example 1, except that benzyl was used.
The concentration shown in Table 5 was used as the alcohol concentration. In Table 5
The one used immediately after preparing the developer is the same day, the one after storage is
It is a value obtained by developing after storage at room temperature for 10 days. The result is
Table 5 shows the results.  As for the amount of tar generation, there is no-, a small amount of +, ++
Each shows a situation where considerable occurrences occur.   From this result, log P of benzyl alcohol etc. is 0.4 or more
If the solvent is not added, the preservability of the liquid will be good, especially
gP 0.003 or less per volume of solvent and water less than 0.4
It is especially good when the temperature is low
Surprising effect that tar does not occur even if it exists
It became clear. (Example 8)   2-amino with a log P of 0.582 (calculated) and a pKa of 10.40
As in Example 7, using -4,5-dimethylphenol
In the experiment, benzyl alcohol in Table 5
Similar results were obtained. (Example 9)   Continuous processing was performed using the processing liquid used in Example 1.
However, benzyl alcohol is not required in the color developer.
The buffers shown in Table 6 were used. Color developing agent
Was adjusted to pH 11 using 0.02 mol / CD-3. Example 1
Use each treatment solution as a tank solution and use the replenisher shown below.
Was. Replenishment amount of color developing solution is 100cm for photosensitive material^Two2ml per
The replenishment amount of the bleach-fixing solution is 100cm for photosensitive material^Two1.5ml per stable
The replenishment amount is 100 cm of photosensitive material.^TwoThe volume was 25 ml per bottle. (Color development replenisher)     800ml pure water     Hydroxyamine sulfate 2.7 g     2.7 g potassium sulfite     0.031 mol of color developing agent     1-hydroxyethylidene-1,1-diphosphonic acid (6
0% aqueous solution) 1.5ml     Magnesium chloride 0.4 g     0.4 mol buffer     Kaycall-PK-Conc     (Fluorescent brightener, manufactured by Shin Nisso Chemical Co., Ltd.) 2 ml   Add pure water to 1 and add 20% potassium hydroxide or 10%
The pH was adjusted to 12.0 with dilute sulfuric acid. (Bleach-fix replenisher)     Pure water 550ml     Ammonium iron (III) ethylenediaminetetraacetate                                               87 g     Ammonium thiosulfate (70% aqueous solution) 113 g     Sodium bisulfite 14 g     2.7 g sodium metabisulfite     8 g of disodium ethylenediaminetetraacetate   Add pure water to 1 and adjust the pH with ammonia or dilute sulfuric acid.
Adjust to 6.5, (Stable replenisher)     5-chloro-2-methyl-4-isothiazoline-3
−0.04 g     Orthophenylphenol 0.03 g     0.04 g of 2-methyl-4-isothiazolin-3-one     1-hydroxyethylidene-1,1-diphosphonic acid                                            0.7 g     Magnesium nitrate 0.05 g     0.7 g of zinc sulfate     Aqueous ammonia (28% aqueous solution) 2.7 g   Adjusted to 1 with water and adjusted to pH = 7.8 with sulfuric acid and potassium hydroxide
did.   E size (92cm^Two) 6000 sheets processing
did. The results are shown in Table 6. Values in parentheses are values for new solution
Indicated.   According to the results in Table 6, pKa was 1 even when continuous processing was performed.
When a buffer of 0.3 or more is used, the decrease in Dmax is small and r_Two
Surprising that no drops and no tar is generated
It turned out to be effective. (Example 10)   In the same manner as in Example 9, the light-sensitive material of the color developing solution was 100 cm.^TwoAh
6,000 sheets of E size were continuously processed by changing the replenishment amount
Ro, 100cm^Two0.8ml per 1ml and 1ml replenishment amount as same as Table 6
Was obtained.   In addition, 3,000 sheets of continuous processing were performed in E size, and a developing machine was used for 6 days.
After stopping and processing 3,000 sheets again, K_TwoCO_ThreeBuffer
Then Dmax, r_TwoDecrease, tarling increases
Was. However, little change was observed in the phosphate buffer.
won. (Example 12)   A liquid that has been continuously treated in the same manner as in Example 9 by washing with water instead of the stable liquid.
Implements magenta fading of photosensitive material developed using
When examined in the same manner as in Example 3, the image storability was about
It was about 5% worse. (Example 13)   Consisting of the processing solution used in Example I and silver chlorobromide emulsion
Processing was performed using the photosensitive material under the same conditions as in Example I.
Was. However, here, the buffer (B-1) and (B-11)
Chairs (B-16), (B-19) to (B-30), (B-
33) and (B-40) to (B-130)
PH and 10.0,10.
Changed to 5,11 and 12. Maximum blue color of processed photosensitive material
When the concentration was measured, phosphorus was used as the buffer of Example I.
As with acids, boric acid and glucose, pH
Was 10.5 or more, and a good maximum blue density was obtained.

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Claims (1)

(57) [Claims] A silver halide color photographic light-sensitive material having a silver halide emulsion layer substantially consisting of a silver chlorobromide emulsion was mixed with a color developing agent represented by the following formula (I) or (II) at 1.5 × 10 5
^-2 mol / l or more, and a solvent having a logP of 0.4 or more with respect to the volume of water and a solvent having a logP other than water of less than 0.4 (where P represents a partition coefficient for n-octanol and water). PKa with a volume ratio of 0.003 or less and logP less than 0.4
Contains a compound of 10.3 or more, 0.05 mol or more, pH ≧ 10.3
A method for processing a silver halide color photographic light-sensitive material, wherein the processing is performed at 30 ° C. or higher for 120 seconds or less using the color developing solution described above. General formula (I) [Wherein R _1, R ₂ represents a hydrogen atom, a halogen atom or a C ₁ ~ ₅ straight or branched alkyl group or alkyl group substituted with an alkyl sulfonamide group of C ₁ ~ _5. R ₃ is -R ₃₁ -NHSO ₂ -R ₃₂ , R ₃₁ is a lower alkylene group,
_R32 represents a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, or a t-butyl group. General formula (II) [Wherein R ′ ₁ and R ′ ₂ are a hydrogen atom, a halogen atom or C _{1-
5 represents} a linear or branched alkyl group. R _'3 represents a hydrogen atom, an alkyl group of C ₁ ~ _5, an alkyl group of C ₁ ~ ₅ having a hydroxyl group, n is an integer. ]