JPS62178959A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To stabilize a dye image by processing the titled material within 120 seconds at 30 deg.C by using a developing soln. contg. >=0.05mol compd. having <0.4log p and >=10.3pka and having >=10.3pH. CONSTITUTION:The silver halide color photographic material consisting substan tially of a silver chlorobromide emulsion is processed within 120sec at >=30 deg.C by using the color developing soln. which is a highly alkaline developing agent contg. the compd. of <=0.4log p and >=10.3pka and having >=10.3pH and contains at least one of p-phenylene diamine color developing agents bound with an alkyl sulfone amide alkyl group on the arom. nucleus or amino nitrogen at least at >=1.5X10<-2>mol. The stable dye image is thereby obtd. even if the mate rial is subjected to the quick and continuous processing.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a color development processing method for a silver halide color photographic light-sensitive material (hereinafter referred to as a light-sensitive material), and more specifically, a color development processing method that performs color development processing in an extremely short time. A water-free stabilization process that provides stable dye density and images with poor storage stability in the dark, and can be processed without washing with water and with a stabilizing solution with a small amount of replenishment. Regarding the method.

[Prior art] Processing of color photosensitive materials basically involves color development, desilvering,
It consists of three steps: washing with water, and desilvering consists of either a bleaching and fixing step or a bleach-fixing step in which bleaching and fixing are performed in the same bath. Recently, instead of the water-washing process, a waterless washing process called stability ratio process has been proposed, and the process consisting of three steps of color development, bleach-fixing, and stabilization process has been widely used.

During color development, the exposed silver halide is reduced to silver, and at the same time, the oxidized aromatic primary amine developing agent reacts with the coupler to form indoaniline, indophenol, and azomethine dyes. It is well known to form color photographic images.

In these color photographic systems, a non-diffusible coupler is generally contained in the photographic emulsion layer and development is carried out using a color developing agent in a color developing solution. Methods of causing reactions in photographic materials are also known.

Further, the coupler contained in the light-sensitive material is generally made non-diffusible by being dispersed in a water-insoluble high-boiling organic solvent and then added thereto.

This method introduces an alkyl side chain of polymeric poison into the coupler as a ballast group, which improves color reproducibility and improves color reproducibility rather than non-diffusivity.
It is considered to be advantageous in terms of preservation of color purity images and is extremely commonly practiced.

The color developing solution for processing such light-sensitive materials contains an aromatic primary amine color developing agent and a poorly soluble organic solvent (lo
It is also well known that a solvent with a g p of 0.5 or more is contained. The most widely known organic solvent of this type is a poorly soluble alcohol, which is used to accelerate the reaction between a color developing agent and an image-forming coupler, ie, to increase the efficiency of the coupling reaction. This type of alcohol is often referred to as a ``development accelerator'' or ``development booster.'' See U.S. Pat.
．． Benzyl alcohol is particularly advantageous for this purpose, as seen in US Pat. No. 814,606.

Color development is promoted by supplying a large amount of color developing agent in a short time into the oil sphere in which the coupler is dispersed, and by distributing a relatively large amount of color developing agent into the swollen gelatin film than in the bulk of the developer. The use of poorly soluble alcohols, such as benzyl alcohol, which is thought to cause a high concentration of color developing agent in the oil and gelatin in the photosensitive material during processing, results in a high residual concentration after development. This disadvantage has been the main cause of deterioration in the storage stability of dye images.

Furthermore, this problem has become more apparent and emphasized due to the recent rapid processing, which has shortened the total processing time.Another major cause is that a large amount of washing water is supplied, and the photosensitive materials are not cleaned properly. The washing process was removed from photographic processing, and a stabilization process, in which a small amount of replenishment was provided, began to replace the washing process. These waterless washing stabilization treatments are described in JP-A-58-14834, JP-A-58-105145, JP-A-58-134634, and JP-A-5.
8-18631, as well as Japanese Patent Application Nos. 58-2709 and 59-89288.

In all of these methods, the color developing agent adsorbed on the gelatin film in the light-sensitive material and the color developing agent dispersed in the coupler dispersion oil cannot be sufficiently washed away and the residual density cannot be reduced, making it difficult to preserve the dye image. There is a problem that stability deteriorates significantly.

As a further problem, poorly soluble solvents such as benzyl alcohol with a log p greater than 0.4 have long caused problems due to the poor solubility of these compounds in water. For example, when preparing a developer, benzyl alcohol generally tends to dissolve slowly, requiring thorough forced stirring and heating of the dissolved water.

If even a portion of the benzyl alcohol remains undissolved, the color developing agent will be distributed and dissolved at a high concentration in this portion, resulting in oxidation and generation of 1 tar after several days, resulting in a serious malfunction.

One solution to incorporating benzyl alcohol into the color developer is to add a solvent other than water with a log p of less than 0.4, such as ethylene glyfur, diethylene glycol, polyethylene imine, triethanolamine, etc. Methods of solubilization are known.

This method is described in US Pat. No. 3,574,619. Furthermore, a disadvantage of solvents such as benzyl alcohol is that they deteriorate the solubility of the color developing agent in the solution, so the concentration of the color developing agent in the color developing solution cannot be sufficiently increased, and development is not promoted as much as expected, resulting in a slow progress. The problem is that it has become a mediocre thing.

A particularly important problem is that concentrated low-replenishment processing, which is advantageous in terms of labor-saving and requires only a small amount of replenishment, is limited by the color developing agent that can be dissolved in the replenisher when using a developer containing benzyl alcohol. The problem is that it cannot be enriched beyond a certain amount.

In contrast to such a coupling reaction promotion method using benzyl alcohol, another method for increasing the rate of dye image formation is to incorporate a single color developing agent into the color photosensitive material and process it at a higher pH than a normal developer. A method is also known in which the concentration of a color developing agent in a gelatin coating is increased and the silver development reaction rate is increased by increasing the pH.

Therefore, even color photographic materials that do not contain ordinary color developing agents can be expected to be developed more quickly by processing them with a color developer having a high pH.

However, even if the pH of the developing solution containing a highly soluble solvent such as benzyl alcohol is increased using a compound with an appropriate pka value as a buffer, and the development process is carried out at pH 11, for example, the pH of the developing solution containing a highly soluble solvent such as benzyl alcohol cannot be increased. In addition to the inability to achieve thickening, the color development reaction is not only not accelerated as expected, but also the dye density may even decrease in certain sensitive materials compared to the case of low pH. It was something. Furthermore, if continuous processing is continued using this processing solution, the maximum dye density obtained will gradually decrease, and the effect of accelerating development will be substantially lost. Another drawback is that the γ of the lobe increases and the resulting image becomes sharper.

, -Kihisa σ)IJIl, Tm Gomashihi σ)Ei r, = -n〒 -← fP A-Ko l, -Ya・Nishi 40 M+ With the decentralization of science, small-volume processing laboratories are emerging. In addition to the simplification of the above-mentioned work, there is a growing need to reduce the amount of replenisher and waste liquid used for color developing solutions as well as stabilization processing from an economic and pollution standpoint. It is not possible to meet these needs with a developer containing a high concentration and low replenishment.

In addition, in such small-volume processing laboratories, the interval between replenishment of replenisher is inevitably relatively long, which causes evaporation and concentration of the developer or prolongs the stagnation time, raising concerns about the storage stability of the developer. However, the disadvantages of high pH developers mentioned above should be particularly taken into consideration.

[Object of the present invention]

Therefore, an object of the present invention is, firstly, to provide a method for processing color photographic materials that is quick and allows stable dye images to be obtained even during continuous processing, and secondly, to eliminate the washing process and to The third objective is to provide a processing method that conserves resources and allows the processing of photographic materials to be produced safely without any harmful processing chemicals remaining and that is excellent in color photographs.
The fourth objective is to provide a color photographic processing method that allows easy dissolution and easy preparation of a processing solution.The fourth objective is to provide a processing method that allows the developer to be concentrated and replenished at low levels. However, even if the treatment is continued for a long time, tar,
The object of the present invention is to provide a stable processing method that does not generate sludge or the like.

Other objects of the invention will become apparent from the description below.

[Means for resolving the same paragraph]

As a result of various studies to achieve the above-mentioned object of the present invention, the present inventors have found that a silver halide color photographic material consisting essentially of a silver chlorobromide emulsion has a log p of 0.4 or more and has poor solubility. pH 10, which contains a compound that does not substantially contain a solvent, has a logp of 0.4 or less, and has a pka of 1000 or more;
It is a highly alkaline developer of 3 or more, and it is a p
- This can be achieved by processing within 120 seconds at (9)°C or above using a color developing solution containing at least one phenylenediamine color developing agent of at least 1.5X tO = mol or more. This is what I found.

The present invention can be obtained only by a combination of a specific developing agent, a specific developer solvent, a specific developer pH 1, a compound having a specific pka, and a specific silver halide emulsion, and when conventional benzyl alcohol is used. In order to carry out color development efficiently and to perform rapid processing, it is necessary to increase the penetration of the developing agent into the width of the oil containing the dispersed coupler, and to increase the infiltration of the developing agent into the width of the oil containing the dispersed coupler, and to use silver such as thioether and ocyanate, which are physical development accelerators. The solution is to add a solubilizer as a development accelerator, and in cases where the coupling reaction was thought to be rate-limiting, a compound with a high pka value may be added.
It was surprising that the color development reaction could be carried out quickly and stably even during long-term continuous processing simply by maintaining I() at a high level.

The present inventors found that although general primary amine color developing agents have good acidity and solubility, the color developing agent of the present invention has a specific p) of 1 or more, and conversely, the higher the pH, the more soluble the color developing agent is. We discovered the specificity of increasing the
Although the developer of the present invention has a pka of 10.3,
By using the following compounds, the development reaction is further accelerated, and the Dma observed during long-term continuous processing is
It was equally surprising that the various problems of a decrease in x and an increase in γ, that is, a high contrast image or generation of tar, were also solved. In other words, extremely efficient development acceleration can be obtained, and the amount of developing agent can be reduced compared to the case where a compound with a pka of 10.3 or more is not added. However, the residual group in the color photographic material can of course be further reduced compared to when benzyl alcohol is used, and even by stabilizing treatment with less replenishment, the negative effect on image storage stability can be reduced. At the same time, it also became possible to reduce the amount of concentrated replenishment.

The details of these effects are unknown, but when a compound with a specific pka value is added at a specific pH, the rate of OH- permeation into the gelatin film is much faster than when no compound is added. However, if a negative solubility solvent such as benzyl alcohol is added to this, the permeation rate will be impaired again, and considering that the higher the pH mentioned above, the better the solubility of the developing agent of the present invention is. Taken together, it can be understood that when benzyl alcohol is included, the effect of the buffer is small at high pH.

Furthermore, if it does not substantially contain benzyl alcohol, p
The pH buffering properties of compounds with a ka of 10.3 or higher not only increase the OH- concentration in the gelatin film, but also relatively increase the concentration of the developing agent that permeates into the gelatin film. It is presumed that this effect was greater than that of increasing the pH of the gelatin film, or simply increasing the OH concentration in the gelatin film using a Ca buffer.

On the other hand, regarding the effect of preventing tar generation, tar generated by oxidation of the color developing agent dissolves in a highly alkaline solution, so the above-mentioned pI (although the buffering effect may be considered, log p < 0.4 Since the following compounds which are extremely easily soluble in water are used, it is presumed that there is an advantage of not forming oxidation centers such as crystal nuclei, but the details are unknown.

Among compounds with a pka of 10.3 or more, those with a log of 0.4 or more are undesirable because they are insoluble or cause precipitation during long-term storage.

In addition, if a free base such as amphoteric gold is used, log
Even if p is less than 0.4, storage stability may be poor, but
This case can be easily solved by using a suitable complexing agent.

In this specification, "substantially silver chlorobromide emulsion" means that it may contain a trace amount of silver iodide in addition to silver chlorobromide,
For example, 0.3 mol% or less, more preferably 0.1 mol%
This means that it may contain the following silver iodide. However, silver chlorobromide emulsions containing no silver iodide are most preferred in the present invention.

It is sufficient that at least one of the light-sensitive emulsion layers of the silver halide color photographic light-sensitive material processed according to the present invention consists essentially of a silver chlorobromide emulsion; Preferably, it consists of a silver emulsion. The silver chlorobromide has a silver bromide content of preferably 90 mol% or less, preferably 70 mol% or more and 40 mol% or more, because the smaller the silver bromide mol%, the more sufficient dye formation can be obtained even in a short color development time. gives the most favorable result. Furthermore, the smaller the coating silver, the more preferable it is because sufficient pigment formation can be achieved in a short time; 10/ni"
It is particularly preferably 0.8E/mJ or less, and more preferably 0.8E/mJ or less.
7. ! The maximum effect can be obtained when the thickness is 7/m17 layers. The color development process is carried out at 30°C or higher and 120 seconds or less, preferably 33°C or higher and 120 seconds or less, particularly preferably 33°C or higher and 90 seconds or less, and most preferably 33°C or higher and 90 seconds or less. Therefore, when the treatment is carried out at 30'C or more and for 150 seconds or more, the storage stability of the dye deteriorates. In particular, processing time is more important than temperature; if the processing time exceeds 150 seconds, the fading resistance of the red dye will be markedly reduced, which is not preferred.

The processing temperature is raised to complete the development in a short time rather than the storage stability of the dye, and it is preferable to set it at 30°C or higher and 50°C or lower because it allows for a shorter processing time. In terms of stability, it is better not to be too high, and it is desirable to process at a temperature of 33°C or higher and 45°C or lower.

In the present invention, lo is not preferable to be added to the developer.
The solvent having a g p of 0.4 or more is an aliphatic alcohol, an aliphatic glycol ether, an alicyclic alcohol, or an aromatic alcohol, and among these, those having 5 to 20 carbon atoms.

A specific example is benzyl alcohol log pl, 1
00-Hydroxybenzyl alcohol log p 0
．． 73 cyclohexanol log p
1.232-Pendylokineethanol log
p 0.41 Anisyl alcohol l
og 0.70 above Phenylethyl Alcohol Ing p 1.
36p-tolylcarbinol log p
1.36 Phenol 〃p-Hydroxybenzyl alcohol 〃Benzylamine
〃Diethylene glycol motubutyl ether lo
g p 0.41 Solvents with a log p of less than 0.4 are mainly solvents with carbon atoms of 0 to 4, such as aliphatic alcohols and organic acids, and solvents with carbon atoms of 5 or more when highly polar functional groups are present. De l
og p Q may be less than 4, and specific examples include, although not particularly limited to, acetic acid ethanol acetone propionate propatool ethylene glycol diethylene glycol triethylene glycol triethanolamine jetanolamine.

In the present invention, a particularly preferred p-phenylenediamine color developing agent is an alkylsulfonamide alkyl moiety bonded to the aromatic nucleus or amine nitrogen: CH, 5o2NHC2H, C2H.

N)I2 NH2 N.H.

NH2 etc. can be mentioned.

These color developers are hydrochloride, sulfate, phosphate, p-)
It is used in the form of luene sulfate.

The color developing solution of the present invention is used at a pH of 10.3 or higher, preferably 10.50 or higher, particularly preferably 10.7.
It is 5 or more, and the upper limit is related to the capricity of the photographic emulsion, but in general, the higher the value, the more preferable it is.

In the present invention, since the solubility of the color developing agent in water is extremely high, the amount of the color developing agent used is at least 1.5 ml per 1 e of processing solution.
Preference is given to using X 10- mol, more preferably 1.5 to 15 X 1O-2 mol of lI! used in enclosures.

In addition, for this reason, the replenishment fluid replenishment π is 180 m#/m
Rich and low replenishment from more than 150 to less than πZ/rn' is now possible.

These alkyl sulfonamide alkyl-substituted -
p-phenylenediamine derivatives are published in Journal of American Chemical Society, Vol. 73, 3100.
(1951).

The color developing solution of the present invention has a bromide ion concentration of 5 x 10-3.
It is preferable that the amount is molar or more, but in the present invention, the higher the bromide, the lower the replenishment amount, so it is preferable. In conventional development methods, bromide suppresses the development reaction and is considered to be preferably as low as possible; however, in the combination of the color photographic light-sensitive material and developer of the present invention, the color photographic material of the present invention has a blue-sensitive emulsion layer,
In a multilayer color photographic material having three or more layers including each of a green-sensitive emulsion layer and a red-sensitive emulsion layer, the film thickness is 1 when dry.
The effects of the present invention can be maximized when the thickness is 3 μm or less, preferably 12 μm or less, particularly preferably 10 1 +m or less.

In the processing method of the photographic light-sensitive material of the present invention, it is possible to use a color developing solution containing the color developing agent according to the present invention. In addition, various other methods including bath treatment,
For example, various processing methods can be used, such as a spray set in which the processing liquid is atomized, a web method using contact with a carrier impregnated with the processing liquid, or a developing method using a viscous solution. Preferably, the process consists essentially of three steps: color development, deep fixation, and stabilization treatment.

The color developer used in the present invention further contains various commonly added components, such as alkaline agents such as sodium hydroxide and sodium carbonate, alkali metal sulfites,
Alkali metal bisulfite, alkali metal thiocyanate, alkali fully halogenated compound, polystyrene sulfonic acid, water softener, ethylene glycol, diethylene glycol, triethanolamine, thickening agent, development accelerator, etc. can also be optionally contained. .

Examples of additives other than the above added to the color developing solution include bromides such as potassium bromide and ammonium bromide;
Compounds for quick processing liquids such as alkali iodide, nitrobenzimidazole, mercaptobenzimidazole, 5-methylhensitriazole, 1-phenyl-5-mercaptotetrazole, as well as anti-stain agents, anti-sludge agents, and preservatives. , interlayer effect promoter, chelating agent, etc.

As the chelating agent in the developer, aminopolycarboxylic acid salts and organic phosphonates are mainly used.

The log p according to the present invention is a value determined from the partition coefficient p of n-octatool/water. The p value is determined by the following formula. The logarithm of the p value obtained in this way is the solute concentration in the n-octatool phase p = the solute concentration in the aqueous phase Iogp value, and this value has traditionally been widely used as a measure of lipid solubility in agricultural medicine. This is the value that has been used. lo
g The p value is determined by the chemical review
Review ) J Magazine 1971 Vol. 71 No. 6 55
Log Poc in the table described on pages 5 to 613
You can also know by It can also be determined, for example, by the calculation method described in ``Ecochemistry'', Vol. 6, pages 3 to 11, but it is preferable to use actual measured values, and particularly preferably values measured using an n-octatool. It is preferable to use

In order to more effectively achieve the present invention, the pH of the water washing alternative stabilizer in the present invention is preferably 5.5 to 10.
The pH is preferably in the range of 0, preferably in the range of 6.3 to 9.5, and particularly preferably in the range of 7.0 to 9.0. As the pH adjusting agent that can be contained in the water washing alternative stabilizer of the present invention, any commonly known alkaline agents or acid agents can be used.

The present invention is most effective when there are few places to replenish the stabilizing solution for water washing to the stabilizing bath. Preferably, the effect of the present invention is particularly remarkable in the range Ur4 of 2 to 20 times.

The treatment temperature for the stabilization treatment is preferably in the range of 15°C to 60°C, preferably 20°C to 45°C. In addition, from the viewpoint of rapid processing, it is preferable that the processing time be as short as possible, but it is usually 20 seconds or more.
The treatment time is 10 minutes, most preferably 1 to 3 minutes, and in the case of multiple tank stabilization treatment, it is preferable that the first stage tank be treated for a short time and the second stage tank be treated for a long time. Especially 20% of the anterior tank
It is desirable to process sequentially with 50% more processing time.

After the stabilization treatment according to the present invention, there is no need for any water rinsing treatment, but rinsing by rinsing with a small amount of water within an extremely short period of time, surface cleaning, etc. can be optionally performed as necessary.

When the method for supplying the washing substitute stabilizing solution in the stabilization treatment step according to the present invention is a multi-tank countercurrent method, it is preferable to supply it to the rear bath and overflow from the front bath. Of course, it can also be treated in a single tank. The above compounds can be added as a concentrated liquid to the stabilization tank, or the above compounds and other additives can be added to the washing alternative stabilizing solution supplied to the stabilizing tank, and this can be added to the washing alternative stabilizing solution. There are various methods of addition, such as using a supply solution for a liquid, and any method of addition may be used.

Conventionally, photosensitive materials were processed with a bleach-fix solution after color development.
Next, in the treatment method of processing with a washing substitute stabilizing solution, if the specific gravity of the washing substitute stabilizing solution at 24°C in the final tank of the washing substitute stabilization treatment becomes 1.002 or more as a result of continuous processing, contamination of the unexposed area will occur. Although there is a tendency for the color to turn dark, according to the present invention, the occurrence of staining under such conditions is also significantly improved.

In the present invention, processing with a bleach-fix solution and subsequent treatment with a water wash substitute stabilizing solution without substantial washing with water,
In other words, this indicates that the bleach-fix bath is followed by direct washing with a substitute stabilizing solution, and this treatment process is completely different from the conventional process of washing with water after the bleach-fixing bath and then processing with a stabilizing solution. It's different.

As described above, in the present invention, the treatment with a stabilizing solution refers to a treatment for stabilizing the area where the stabilizing treatment is performed immediately after the treatment with the bleach-fixing solution and substantially no washing treatment is performed. The processing liquid used for processing is called a washing alternative stabilizer, and the processing tank is called a stabilization tank.

In the present invention, when the number of stabilizing tanks is 1 to 5, the effect of the present invention is large, and the number of stabilizing tanks is particularly preferably 1 to 3, and it is preferable that the number of stabilizing tanks is 9 or less.

Bleaching agents that can be used in the bleach-fix solution used in the present invention are metal complex salts of organic acids. The complex salt is an aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid.
It is coordinated with metal ions such as copper. The most preferred organic acids used to form such metal complex salts of organic acids include polycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific examples of these include the following.

(13 egg diamine tetraacetic acid [2J diethylenetriaminepentaacetic acid (3)
Ethylenediamine-N-(β-oxyethyl)-N,
N', N'-) diacetic acid [・month] Propylenediaminetetraacetic acid (5) Nitrilotriacetic acid [6J Cyclohexanediaminetetraacetic acid (73 iminodiacetic acid (S)) Dihydroxyethylglycinecitric acid (or tartaric 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) Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt (15) Ethylenediaminetetraacetic acid tetrasodium salt (16) Diethylenetriaminepentaacetic acid pentasodium salt (17) Ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid sodium salt (18) Propylenediaminetetraacetic acid sodium salt (19) di)liloacetic acid sodium salt (20) Cyclohexanediaminetetraacetic acid Sodium salts These bleaches are used at 5-450 g/l, more preferably 20-250, i17/l. The bleach-fixing solution contains a silver halide fixing agent in addition to the above bleaching agent, and if necessary, a sulfite salt as a preservative. In addition, a bleach-fixing solution consisting of an ethylenediaminetetraacetic acid iron(I) complex salt bleach and a small amount of a halide such as ammonium bromide other than the silver halide fixing agent mentioned above, or conversely, a halide such as ammonium bromide may be used. A bleach-fix solution containing a large amount of iron (1) ethylenediaminetetraacetate, or a special bleach-fix solution containing a combination of an ethylenediaminetetraacetate iron (1) complex salt bleach and a large amount of a halide such as ammonium bromide, etc., may also be used. I can do it. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can.

The silver halide fixing agent contained in the bleach-fixing solution is a compound that reacts with silver halide to form a water-soluble complex salt, such as potassium thiosulfate, sodium thiosulfate, and thiosulfate, which are used in ordinary fixing processes. Typical examples include thiosulfates such as ammonium osulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, 1,000 urea, and thioether. These fixatives are used with a soluble range of 59/e or higher, but generally between 70.9 and 250 g/l.
Use with.

The bleach-fix solution contains boric acid, borax, sodium hydroxide,
Various pH adjusting agents such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination of two or more.

Furthermore, various fluorescent whitening agents, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, and bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and nitrates, and organic solvents such as methanol, dimethyl sulfoxide, and dimethyl sulfoxide. etc. can be contained as appropriate.

The bleach-fix solution used in the present invention includes JP-A No. 46-280, JP-B No. 45-8506, JP-B No. 46-556, Belgian Patent No. 770,910, JP-B No. 45-8836,
Various bleach accelerators described in JP-A-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added.

The pH of the bleach-fix solution is used at 4.0 or higher, but generally it is used at pH 5.0 or higher and pH 9.5 or lower, preferably at pH 6.0 or higher and p) 18.5 or lower, and more preferably, it is used at a pH of 6.0 or higher and p) 18.5 or lower. Treatment is performed with pI-1 of 6.5 or more and 8.5 or less. The processing temperature is 80° C. or lower, which is 3° C. or more, preferably 5° C. or more lower than the temperature of the processing solution in the color developing tank, but preferably 55° C. or lower to prevent evaporation.

The photographic constituent layer of the silver halide color photographic light-sensitive material of the present invention may contain a water-soluble dye or a dye (AI dye) that can be decolorized with a color developing solution. Examples of the AI dye include oxonol dye, hemioxonol dye, Dyes, merocyanine dyes and azo dyes are included. Among them, oxonol dyes, hemioxonol dyes, merocyanine dyes, and the like are useful.

Examples of AI dyes that can be used include British Patent No. 584.60.
No. 9, No. 1,277.429, Japanese Unexamined Patent Publication No. 48-8513
No. 0, No. 49-99620, No. 49-114420, No. 49-129537, No. 52-108115,
No. 59-25845, No. 59-111640, No. 5
No. 9-111641, U.S. Patent No. 2,274,782,
No. 2,533,472, No. 2,956,879, No. 3,125,448, No. 3,148,187, No. 3
, No. 177.078, No. 3.247, 127, No. 3,
260.601, 3゜540.887, 3.5
No. 75,704, No. 3゜653, No. 105, No. 3,7
No. 18,472, No. 4゜071.312, No. 4,07
Examples include those described in No. 0,352.

These AI dyes are generally used at a concentration of 2 per mole silver in the emulsion layer.
It is preferable to use ×lO- to 5 X to-' moles, more preferably I X lo-2 to I X 10-'
Use moles.

The crystals of the silver halide grains may be normal crystals, twin crystals, or other crystals, and any ratio of (i, o, o) planes to (1,1,1) planes can be used. Furthermore, even if the crystal structure of these silver halide grains is uniform from the inside to the outside, it has a layered structure (core-shell type) in which the inside and outside are different.
It may also be one that has been Further, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain. In addition, tabular silver halide grains (JP-A-58-113934, Japanese Patent Application No. 59-1982)
-170070) can also be used.

In the present invention, silver halide grains that are substantially monodisperse are particularly preferably used, and core-shell emulsions are preferred, since rapid processing and stabilization of image dyes can be improved. This may be obtained by any preparation method such as an acid method, a neutral method, or an ammonia method.

Alternatively, for example, a method may be used in which seed particles are produced by an acidic method and then grown by an ammonia method, which has a faster growth rate, to grow to a predetermined size. When growing silver halide grains, control I)f(, pAg, etc. in the reaction vessel,
For example, it is preferable to simultaneously implant and mix silver ions and halide ions in amounts commensurate with the growth rate of silver halide grains, as described in JP-A-54-48521.

Preferably, the silver halide grains according to the present invention are prepared as described above. A composition containing silver halide grains is referred to herein as a silver halide emulsion.

These silver halide emulsions contain activated gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, cis-sensitizers; selenium sensitizers; reduction sensitizers such as stannous salts. , thiourea dioxide, polyamines, etc.; noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride, etc.; or, for example, ruthenium, palladium, Sensitizers are water-soluble salts such as platinum, rhodium, and iridium, specifically ammonium chlorovaladate, potassium chlorooleate, and sodium chlorovaladate (these types can be used as sensitizers or sensitizers depending on the amount). (acts as a fog suppressant, etc.) alone or in appropriate combinations (for example, a combination of a gold sensitizer and a sulfur sensitizer, a combination of a gold sensitizer and a selenium sensitizer, etc.). It may be felt.

The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and during or after the chemical ripening, a nitrogen-containing heterogeneous emulsion having at least one kind of hydroxytetrazaindene and mercavite group is added. It may contain at least one kind of ring compound.

The halogenation used in the present invention is limited to 5xlO=~3xl with respect to 1 mole of silver halide in order to impart photosensitivity to each desired wavelength range.
Optical sensitization may be achieved by adding 0 to 3 moles.

Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more. Examples of the sensitizing dyes advantageously used in the present invention include the following.

That is, as sensitizing dyes used in blue-sensitive silver halide emulsions, for example, West German Patent No. 929,080 and U.S. Pat.
, No. 231,658, No. 2,493,748, No. 2
, 503, No. 776, No. 2,519,001, No. 2.912,329, No. 3,656,959, No. 3
゜672.897, 3,694,217, 4
,025.

No. 349, No. 4,046,572, British Patent No. 1,24
2゜588, Special Publication No. 44-14030, 52-2
Examples include those described in No. 4844 and the like.

Further, as sensitizing dyes used in green-sensitive silver halide emulsions, for example, U.S. Pat.
No. 72,908, No. 2,739,149, No. 294
Representative examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 5.763, British Patent No. 505,979, and the like. Further, as sensitizing dyes used in red-sensitive silver halide emulsions, for example, U.S. Pat.
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes such as those described in No. 2,270,378, No. 2,442,710, No. 2,454.629, No. 2,776.280, etc. It can be mentioned as something similar.

Furthermore, U.S. Pat. No. 2,213. '195 No. 2,49
No. 3゜748, No. 2,519,001, West German Patent No. 92
Cyanine dyes such as those described in No. 9゜080, etc.
A merocyanine dye or a composite cyanine dye is used in a green-sensitive silver halide emulsion or a red-sensitive silver halide emulsion.These sensitizing dyes may be used alone or in combination.

The photographic material of the present invention may be optically sensitized in a desired wavelength range by a spectral sensitization method using cyanine or merocyanine dyes alone or in combination, if necessary.

A typical example of a particularly preferred spectral sensitization method is, for example, Japanese Patent Publication No. 43-493 concerning a combination juice of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 6, No. 43-22884, No. 45-18433,
No. 47-37443, No. 48-28293, No. 49
No.-6209, No. 53-12375, JP-A-52-2
No. 3931, No. 52-51932, No. 54-8011
No. 8, No. 58-153926, No. 59-116646
No. 59-11fi647.

Further, regarding the combination of carbocyanine and other cyanine or merocyanine that causes benzimidazole cough, for example, Japanese Patent Publication No. 45-2583148-384.
No. 06, No. 48-38407, No. 54-34535, No. 55-1569, No. 50-33220, No. 50-38526, No. 51-107127, No. 5
No. 1-115820, No. 51-135528, No. 52
-104916, No. 52-104917, and the like.

Furthermore, regarding combinations of benzoxazolocarbocyanine (oxapot carbocyanine) and other carbocyanines, for example, Japanese Patent Publication No. 32753/1986;
No. 6-11627, JP-A-57-1483, and regarding merocyanine, for example, JP-B No. 48-384.
No. 08, No. 48-41204, No. 50-40662, No. 56-25728, No. 58-10753, No. 58-91445, No. 59-116645, No. 50-33828, etc. It will be done.

In addition, regarding the combination of 1,000 acarpocyanine and other carbocyanins, for example, Japanese Patent Publication No. 43-4932
No. 43-4933, No. 45-26470, No. 4
No. 6-18107, No. 47-8741, - JP-A-59
In addition, the method described in Japanese Patent Publication No. 49-6207 using zeromethine or dimethine merocyanine, monomethine or trimethine cyanine and styryl dye can be advantageously used.

In order to add these sensitized dyes to the silver halide emulsion according to the present invention, in advance, a dye solution is prepared using, for example, methyl alcohol, ethyl alcohol, acetone, dimethyl formamide, or the fluorinated dye solution described in Japanese Patent Publication No. 50-40659. It is used by dissolving it in a hydrophilic organic solvent such as alcohol.

The addition may be made at any time such as at the start of chemical ripening of the silver halide emulsion, during ripening, or at the end of ripening, and in some cases, it may be added at a step immediately before coating the emulsion.

Each of the silver halide emulsion layers according to the present invention can contain a coupler, that is, a compound capable of reacting with a grayed product of a color developing agent to form a dye.

As the above-mentioned couplers that can be used in the present invention, various yellow couplers, magenta couplers and cyan couplers can be used without particular limitation. These couplers may be 2-equivalent type couplers or 4-equivalent type couplers, and in combination with these couplers, it is also possible to use diffusible dye-releasing type couplers. .

The yellow couplers include open-chain ketomethylene compounds, active point -〇-aryl substituted couplers called so-called two-equivalent type couplers, active point -〇-acyl substituted couplers, active point substituted couplers with hydantoin compounds, and active point substituted couplers with urazole compounds. Couplers and active point succinimide compound substituted couplers, active point fluorine substituted couplers, active point chlorine or bromine substituted couplers, active point -0-sulfonyl substituted couplers, etc. can be used as the movable yellow coupler. Specific examples of yellow couplers that can be used include U.S. Pat. No. 2,875,057, U.S. Pat.

No. 194, No. 3,551,155, No. 3,582,3
No. 22, No. 3,725,072, No. 3,891,445
No., West German Patent No. 1,547,868, West German Application Publication No. 2,
No. 219゜917, No. 2,261,361, No. 2,
414,006, British Patent No. 1,425,020,
JP 51-10783, JP 47-26133, JP 48-73147, JP 51-102636, JP 50-6341, JP 50-123342, JP 50-
No. 130442, No. 51-21827, No. 50-87
No. 650, No. 52-82424, No. 52-11521
Examples include those described in No. 9, No. 58-95346, and the like.

Examples of magenta couplers used in the present invention include pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, and indacylon compounds. These magenta couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of magenta couplers include U.S. Pat. Nos. 2,600,788 and 2,983.
, No. 608, No. 3,062,653, No. 3,127,
No. 269, No. 3,311,476, No. 3,419,3
No. 91, No. 3,519,429, No. 3,558,3
No. 19, No. 3゜582.322, No. 3,615.50
No. 6, 3, 834.

No. 908, No. 3,891,445, West German Patent No. 1,81
No. 0゜464, West German patent application (OLS) 2,40
No. 8,665, No. 2,417,945, No. 2,418
, No. 959, No. 2,424,467, Special Publication No. 1973-
No. 6031, JP-A-51-20826, JP-A No. 52-58
No. 922, No. 49-129538, No. 49-7402
No. 7, No. 50-159336, No. 52-42121, No. 49-74028, No. 50-60233, No. 5
No. 1-26541, No. 53-55122, Patent Application No. 1982
-110943 etc. can be mentioned.

Further, useful cyan couplers used in the present invention include, for example, phenol couplers, naphthol couplers, and the like. These cyan couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of cyan couplers include U.S. Pat. Nos. 2,369,929 and 2.
, 434°272, 2,474,293, 2,
No. 521,908, No. 2,895.826, No. 3,0
No. 34,892, No. 3,311,476, No. 3,45
No. 8,315, No. 3.476.563, No. 3,58
No. 3,971, No. 3591.383, No. 3, 76
7, No. 411, No. 3,772゜002, No. 3,93
No. 3,494, 1I, 004. 2'1, West German Patent Application (OLS) No. 2,414,830, OLS No. 2,454
, No. 329, JP-A-48-59838, JP-A No. 51-26
No. 034, No. 48-5055, No. 51-146827
No. 52-69624, No. 52-'10932,
Examples include those described in Japanese Patent Publication No. 58-95346, Japanese Patent Publication No. 11572-1972, and the like.

Couplers such as non-diffusible DIR compounds, colored magenta or cyan couplers, polymer couplers, and diffusible DIR compounds may be used in combination in the silver halide emulsion layer of the present invention and other photographic constituent layers.

Regarding non-diffusible DIR compounds, colored magenta or cyan couplers, the applicant's patent application No. 59-193
611, and regarding polymer couplers,
Reference may be made to the description in Japanese Patent Application No. 172151/1989 filed by the present applicant.

The above-mentioned coupler that can be used in the present invention can be added to the photographic constituent layer of the present invention by a conventional method, and the amount of the above-mentioned coupler added is not limited, but I
o-3 to 5 mol is preferable, more preferably lX10-
˜5×10−.

The silver halide color photographic material of the present invention may contain various other photographic additives. For example, antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, fluorescent whitening agents, color image fading inhibitors, antistatic agents, hardeners, and surfactants described in Research Disclosure No. 17643. Agents, plasticizers, wetting agents, etc. can be used.

In the silver halide color photographic light-sensitive material of the present invention, the hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and hydrophilic colloids used to prepare the emulsion. Any of synthetic hydrophilic polymers such as cellulose derivatives such as ethethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, 11- or copolymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide are included.

Examples of the support for the silver halide color photographic light-sensitive material of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, and a reflective layer. Or a transparent support used in combination with a reflector, such as a glass plate, a polyester film such as cellulose acetate, cellulose/trade, or polyethylene terephthalate, a polyamide film, a polycarbonate film, a polystyrene film, and other ordinary transparent supports. It's okay.

These supports are appropriately selected depending on the intended use of the photosensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used to coat the silver halide emulsion J and other photographic constituent layers used in the present invention. Also, US Patent 2,7
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 61,791 and No. 2,941°898.

In the present invention, the coating position of each emulsion layer can be determined arbitrarily. For example, in the case of a photosensitive material for full-color photographic paper, a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer are arranged in order from the support side. is preferred. Each of these photosensitive silver halide emulsion layers may consist of two or more layers. The effects of the present invention are most effective when all of these photosensitive emulsion layers are substantially composed of silver chlorobromide emulsion.

In the photosensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and a filter layer,
Various layers such as an anti-curl layer, a protective layer, and an antihalation layer can be used in appropriate combinations as constituent layers.

In these polishing processes, hydrophilic colloids that can be used in the emulsion layer as described above can be used as a binder, and they can also be contained in the emulsion layer J as described above. Various photographic additives can be included.

Examples are shown below, but it goes without saying that the present invention is not limited to these Examples.

The log p according to the present invention is less than 0.4 and pka 1
Examples of the compound having a molecular weight of 0.3 or more include the following.

(B-t) Sodium aluminate NaAr0゜(B-
2) Sodium silicate Na2O"n5iO□ (low 0
．． Inorganic bases such as 5-1).

(B-3) Phosphate (B-4) Borate saccharide pka C2 (dioses) (B-5) Glycolaldehyde C3 (triose) (B-6) Glyceraldehyde (B-7) Dihydroxy Acetone C4 (tetrose) (B-8) Erythrose (B-
9)) Rheos (B-1o) Erythrulose C, (pentose) ~12-14 (B-1
1) Arabinose (B-12) Xylose (B-13) Ribose (B-14) Lyxose 1'B-15) Xylulose (n-+6) Ribulose c, (methylpentoses) (B-17) Rhamnose (B- 18) Fucose C, (hexoses) ~12-141-19
) Glucose 12.2, 13.85 (B
-20) Mannose (B-21) Galactose 12.3, 14.
1 (B-22) Talos, -su (B-23) Idose (B-24) Gulose (B-25) Aldrose (B-26) Fucose (B-27) Fructose 12.1, 13.
8N3-28) Sorbose (B-29) Tagatose (B-30) Psicose C1 (Heptose) (B-31) Heptulose disaccharide pka (B-32) ) Levalose (B-33) Saccharose 12.6, 13.
5 (B-34) Maltose 12, 13.
3 (B-34) Hepta-robiose (I3-35) Genthiobinase (n-36) Lactose 12.1, 13.
5 trisaccharides (pka)
(B-37) Raffinose (B-38) Methyletose (B-41) 4-acetyl-β-mercaptoisoleucine 10.30 (B-42)
2-acytyl-1-naphthol 13,.10 (B-43) Alizarin-3-sulfonic acid ratio 01 (
+3-1Il+ ) α-amino-1-butyric acid [
α56(n-lI5) α-amino-lobylic acid
to, 80(B-′+6) 1-aminocyclohebutanecarboxylic acid 10.1I6(
B-・17) 2-amino-45-dimethylphenol
10.・10 (B-48:)
5-Amino-N-7enylsulfonic acid
10.95 (B-49) 4-aminophenol 10.30 (13-50) '2-aminopyridine-1-oxide 16.74 (n-51) 5-amino-N-valeic acid 10.77 (
13-52) Ascorbic acid 11.8
2(B-53) Benzyl-α-dioxime 12.
0(B-54) Benzyl-mercaptan 10.
70 (B-55) Betaine 12
．． 16(B-56) t-butyl hydroxide 1
2.80 (B-57) Caffeine
LO14 (B-58) Karmajito
lλ34 (+3-59) Chrome Azuror S
Ll, 47(-n -60) Hooniin
11.0 (B-61) Cycloacetyl hydrazide 11.17 (B-62) cis-cis-
Cyclohexanone-1,3,5-) Reamin 10.4 (B-63)
1.3-diamino-2-aminomethylpropane
10.38 (B-64) f Hydroascorbin m 10.3 (+3-65) α, γ
-Diaminobutyric acid 10.4 (B-66) 5.5
-Diethylbarbiteric acid 13,31 (B-67) Diethyl biguand 11.6
8(13-68) N,N-diethylglycine 1
0. ．． 17 (B-09) 2.3-dihydroxybenzoic acid 11.76 (n-70) 2.5-dihydroxybenzoic acid to, 50 (+3-71) 2.4-dihydroxybenzoic acid to, 13 (B-72) 3.4-dihydroxybenzoic acid 11.74 (B-73) 2.3-dime-lucatopropane-1-ol'-ol (', a A L
, ) Bo, 5s (13-74) Dimethyl biguanide 11.52 (B-75) Dimethylglyoxime 10.60 (B-76)
2.4-dimethyl-8-hydroxyquinoline
10.60 (B-77) 2.3-dimethylphenol to, 50 (B-78) 2.4-dimethylphenol 10.58 (B-79) 3.4
-dimethylphenol 10.32 (13-80)
Dithiooxide 10.89 (B-131)
Eriofrom Black T 11.55 (13-
32) Ethane-1,2-dithiol 10.54 (
B-83) Ethyl acetoacetate 10.68
(B-84) Ethylene-N,N-diacid i'ii
11.05 (B-85) Ethyl biguanide
11. -47 (+3-86) Ethylenediamine 4th m +0.05 ('B-87) Ethyl hydroxyperoxide -11,80 (n-88) Ethyl mercaptan 10.5
0(B-89) 3-ethylpentane-dione 2.4
11.34 (B-90) 2000 rubirolidine 10.4
3(B-91) Gelcoasfulpic acid 11.
58 (B-92) Glucose 1
2.43 (B-93) Glutamide
1]・43(B-94) Glycerol
14.15 (B-95) Glycol
14.22 (B-96) Guanylethylurea 11. t.

(B-97) o-hydroxybenzoic acid 12.38(
B-98) N-(2-hydroxyethyl)piguaado 11.53(B-99) 2-
Hydroxypyridine 11.62 (n-1oo)
4-Hydroxypyridine 11.09 (B-lot
) indole 4 10-32 (B -1
02) Leucine to, 53C
B-103) Mercaptoacetic acid 10
．． 55<B-104) Mercaptoacetic acid citric acid
to,'14(B-105) 2-methyl-2
-butanethiol 11.35 ('[3-106) 2.2'-methylene-bis(4
,6-dichlorophenol) to, G5('B
-107) Methyl ethyl ketoxime 12.4
5(B-108) Methyl mercaptan 1
0.70 (B -109) 3-methylpe>'zn-2,4-dione 10.87 (B
-110) Methylbiperazine 11.02
(B-111) 2-methyl-2-propanethyl
IF, 2
(B-112) Murekito 10.5
0CB-113) Nicotinic acid 1
1.0(B-114) L-proline
10.64 (B -115) 2-propanethiol 1.0.86 (13-116) Bilocatefur 12.08 (B -117) Pyrogallol 12.153 (B -118
) Resorcinol 12-32 (13
-119) β-resorcinic acid 〉13(
B-120) Salicylaldoxime 12.
11CB-121) Salicylic acid
12. :38CB-122) Spartine
11.76 (B -123) 5-sulfosalicylic acid 12.00 (B -124) Tetraol 2 10.48CB -125)
Thioglycolic acid to, 55 (B-126
) Hydroquinone 11.62 (B
-127) Tyrone 12-6
(B-128) 2.2', 2''-Tria
Mi no trie 1000 ruan
10.37 (nt29) 2,4. ．． 6-
) Limethylphenol 10.88 (B-130) Xanthine 11
．． 68 EXAMPLES Specific examples of the present invention will be described below using Examples, but the embodiments of the present invention are not limited thereto.

(Example 1) Silver halide color photographic light-sensitive material samples/iG 1 to 4 were prepared by sequentially coating the following layers on a paper support laminated with polyethylene from the support side.

Layer 1. -・---1,2,9/m" gelatin, 0
．． Blue-sensitive silver halide gelatin emulsion (silver halide composition and average grain size are shown in Tables 1 and 2), 0.50 El/m 0.80 g/m' dissolved in dioctyl phthalate
A blue-sensitive silver halide emulsion containing a yellow coupler ('Y-1).

fif42--- ・------0,70,! i'/
m' gelatin, 107179/rd anti-irradiation dye (AI-1), 5 m7/d (AI-2)
The middle layer consists of

Layer 3...1.25.9/m' gelatin, Q, 28 g/m' green-sensitive silver halide gelatin emulsion (silver halide composition and average grain size are shown in Table 1) and shown in Table 2.) A green-sensitive silver halide emulsion layer containing a magenta coupler (M-1) of 0.62 F/rr dissolved in 0.309 F/m' of dioctyl phthalate.

Layer 4...1.2. ! ? /rr? middle layer consisting of gelatin.

Polishing 5...1.4F/m' gelatin,
0.269/m'' red ga silver halide gelatin emulsion (silver halide composition and average grain size are shown in Tables 1 and 2). Red-sensitive silver halide emulsion layer containing a cyan coupler (C-1) of 45 E/m'.

Layer 6 Protective layer containing 0.50 g/m' of gelatin.

The silver halide in each of the blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer was one whose color had been increased by a general sensitizing dye.

(y-1) (M-1) Shido (C-1) (AI-1) (AI-2) As a hardening agent, 2,4-dichloro-o-5-hydroxy-8-) riazine Sodium was added into layers 2.4 and 6.

The photosensitive material sample prepared as described above was exposed through an optical web and processed in the following steps.

Processing steps (38°C) Color development 40 seconds Bleach-fixing 50 seconds Stability 50 seconds Drying 60 seconds 60-80°C The composition of each processing solution is as follows.

[Color developer]

Pure water 800 mt Benzyl alcohol (log p 1.1) Hydroxyamine sulfate 2.0,! i' Potassium bromide
0.69 Sodium Chloride
1.0g potassium sulfite 2
．． 0g triethanolamine (log p 0.27)
2.0 g color developing agent CD-30,023%/l-hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution') 1.5 m and magnesium chloride 0.3 g buffer
0.3 cost Kaycol I-P
K-Conc (PK-7) (fluorescent brightener, manufactured by Shin Nisso Kako Co., Ltd.) Add 2 me pure water to bring the pH to 11 with 20% potassium hydroxide or 10% dilute sulfuric acid. Adjustments were made to the values shown in the table or Table 2.

The following buffers were used in the color developing solution.

potassium carbonate buffer Add KOH to 0.3 mol of potassium carbonate to adjust pH.

Add HCr to 0.3 mol of dimethylglycine sodium dimethylglycine buffer to make an adjustment.

Add sodium hydroxide to 3 moles of phosphate buffer (phosphate buffer) to adjust the pH.

Boric acid buffer: 0.07 mol of sodium chloride is added to 0.3 mol of boric acid, and borax is added to adjust the pH.

glucose buffer Add NaOH to 0.3 mol of glucose to adjust pH.

[Bleach-fixing solution] Pure water 500 ml: Ethylenediamine 4-diamine ai<a Ammonium salt fi5,9 Ammonium thiosulfate (70% water iJ&) 85g Sodium bisulfite 10g Sodium metabisulfite 2g Ethylene diamine tetraacetic acid-distrium Add pure water to 11! Adjust to p) ( = 7.0 with aqueous ammonia or dilute sulfuric acid.

[Stabilizing liquid]

5-chloro-2methyl-lt-isothiazoline-3,-
On 0.03 g ortho-phenylphenol 0.02,! 72-methyl-4
-Isothiazolin-3-one 0.03 91-Hydroxyethylidene-1,1 nibosonic acid 0.5g Magnesium nitrate 0.01+,! 7 Zinc sulfate 0.5g Ammonia water (2
8% aqueous solution) 2I 11 with water! The pH was adjusted to 7.8 using sulfuric acid and potassium hydroxide.

The sample was imagewise exposed and processed using the above processing solution according to the conditions in Tables 1 and 2.

The maximum blue density of the obtained sample was measured using an optical densitometer.

Table 1 shows the results when the sample is essentially silver chlorobromide,
Table 2 shows the results when silver iodide was contained in an amount of 5 mol %.

Table 1 (AgC1!:AgBr = 30 near 0)
In the table, 0 is log p Q, the ratio of solvent less than 4 to 0.4 or more, and less than 0.4 also includes water.

-ゝ Below] Bottom margin blank table 2 (AgC/:AgBr:AgI = 20
: 75 : 5) In the table, ni) is log p 0.4
The ratio of solvent less than 0.4 to solvent less than 0.4 if4 also includes water.

From Table 1, log for solvent 1 with logp less than 0.4
If 0.015 of benzyl alcohol with a pka of 1 is used, the maximum concentration will not increase sufficiently even if a buffer with a pka of 10.3 or more is used. In the absence of alcohol, the maximum concentration is sufficient. However, pka 10
．． Maximum concentration is not obtained with or without benzyl alcohol with buffers below 3.

As can be seen from the results in Table 2, in the case of silver halide photographic materials containing silver iodide, compared to the case of silver chlorobromide shown in Table 1, the formulation and conditions according to the method of the present invention have a sufficient maximum density. It can be seen that this results in unfavorable results.

(Example 2) When an experiment was conducted using CD-6 instead of CD=3 used in Example 1, the same results as in Tables 1 and 2 were obtained. However, when CD-3 and CD-6 were compared at the same molar concentration, CD-6 seemed to have a slightly lower color density. However, when CD-4 is used, the magenta color fades (80°C, 70°C).
It was found that 20-day storage at RH) was likely to occur.

(Example 3) For the purpose of investigating the influence on the development processing time, a comparison was made between the use of a phosphate buffer and the use of a potassium carbonate buffer.

At this time, benzyl alcohol was set to O, and r)H was set to 11. The results are shown in Table 3. The photosensitive material used was the silver chlorobromide emulsion of Example 1, and the fading rate (Example 4) was conducted in the same manner as in Example 3, with the pH changed to 10.1 and 10.5. , 1, the maximum density decreased significantly, but 10.5 showed almost no decrease, while the magenta fading rate obtained similar results in both cases.

The results of Examples 3 and 4 show that in the absence of benzyl alcohol, when a buffer with a pka of 10.3 or less is used, a longer treatment time is preferable in order to obtain the maximum concentration; When using a buffer of
It has become possible to shorten the development time and improve processing stability.

(Example 5) Using phosphate buffer, the main drug was CD-3, CD-4゜CD-
The maximum blue density was determined by varying the concentration of the six color developing agents and further varying the pH. The results are shown in Table 4. However, the processing time was the same as in Example 1, the amount of benzyl alcohol was 0, and the light-sensitive material was any one of CD-3, CD-4, and CD-6 to obtain the maximum density according to the results of Example 2. CD-3 and CD-6 are preferred from the viewpoint of image storage stability, and CD-3 is preferred from the viewpoint of maximum color density.

(Example 6) Instead of phosphate buffer, glucose buffer, boric acid, etc.
Even when a buffer having a ka of 10.3 or more was used, the same results as in Example 2, Example 3, Example 4, and Example 5 were obtained.

(Example 7) Using a phosphate buffer, the generation of tar during storage at room temperature and the presence or absence of a decrease in the maximum concentration due to storage of the solution were investigated. The experimental method was the same as in Example 1, and the benzyl alcohol concentrations shown in Table 5 were used in dishes. In Table 5, the values obtained were obtained by using the developer immediately after preparation on the same day, and by storing it at room temperature for 10 days before developing. The results are shown in Table 5.

7,...) Below, regarding the amount of tar generated in the margins, - indicates no tar generation, 10 indicates a small amount of tar generation, and ++ indicates a considerable amount of tar generation. From this result,
If you do not add a solvent with a benzyl alcohol'J logp of 0.4 or more, the storage stability of the liquid will be good, especially if the logp
p 0.00 for main volume l of solvent and water less than 0.4
It has been found that the results are particularly good when the tar content is 3 or less, and when there is no tar content, there is a surprising effect in that no tar is generated even when stored at room temperature for 40 days.

(Example 8) 1ogp is 0-582 (calculated value) and pka is 10.4
When an experiment was carried out in the same manner as in Example 7 using 0.0 2-amino-4,5-dimethylphenol, the same results as those for benzyl alcohol shown in Table 5 were obtained.

(Example 9) Continuous treatment was performed using the treatment liquid used in Example 1. However, the color developing solution did not contain benzyl alcohol, and the buffering agent shown in Table 6 was used. The color developing agent was 0.02 mar/l CD-3 and the pH was adjusted to 11.
And so. Each treatment solution of Example I was used as a tank solution, and the following replenisher was used.

The charging distance for the color development liquid is 2 m per loo side 2 of the photosensitive material.
Replenishment of lml bleaching solution is 1.5mA stabilizing solution for photosensitive material 10ocIn2A1;
T? The area was 25m1 per area.

[Color developer replenisher]

Pure water 800 mt Hydroxylamine sulfate 2.7g Potassium sulfite 2.7,! 9 color developing agent
0,031 mol 1-hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) i, s mt
Magnesium t-chloride 0.49 buffer
0.4 Myo Kaycall
-PK-Conc (Kikol-PK-:7ink) (fluorescent brightener manufactured by Nippon Sokako Co., Ltd.)
2 mt pure water was added to make the solution 11, and 20% potassium hydroxide or 10% dilute sulfuric acid was added to make the pA2, O.

[Bleach-fix replenisher]

Pure water 550 rmt Amine iron tetraacetate (1) Ammonium 87 g Ammonium acetate (70% water soluble, night) Sodium hydrogen sulfite 149 Sodium metabisulfite
2.7g crushed egg Diaminetetraacetic acid disodium salt g Add pure water and ll! Close and adjust the pH to 6.5 with aqueous ammonia or dilute sulfuric acid.

[Stable replenisher]

5-chloro-2-methyl-4-isothiazolin-3-one 0.04 g ortho-phenylphenol 0.0392-methyl-4-inthiazolin-3-one 0. O7l El-
Hydroxyethylidene-1,1-diphosphonic acid 0.79 Magnesium nitrate 0.05 g Zinc sulfate
0.79 ammonia water (28%
Aqueous solution) 2.7.9 The solution was made le with water and adjusted to pH 7.8 with fi acid and potassium hydroxide.

60 E size (92c, m2) while replenishing as above.
00 sheets were processed.

The results are shown in Table 6. Figures in ) indicate values for new solution.

The situation of rice tar generation is the same as in Table 5.

From the results in Table 6, pka 1 even when continuous processing is performed.
It has been found that using a buffer of 0.3 or more has the surprising effect of not reducing Dmax, not reducing γ2, and not generating tar.

(Example 10) In the same manner as in Example 9, the photosensitive material Nito 100c was prepared using a color developing solution.
When 6,000 8-size sheets were continuously processed by varying the amount of replenishment per m2, the same results as in Table 6 were obtained for replenishment I of 0.8 mt per 100 shoulders and 1 me.

In addition, when we processed 3,000 E-size sheets continuously, stopped the developing machine for 6 days, and processed 3,000 sheets again, we found that the K2C
In O3 buffer, Dmaxγ2 decreased and tarring increased. However, almost no change was observed in phosphate buffer.

(Example 12) When the magenta fading property of a light-sensitive material developed using a solution continuously processed in the same manner as in Example 9 by washing with water instead of the stabilizing solution was investigated in the same manner as in Example 3, the image quality was lower than that in Table 3. Preservability deteriorated by about 5%.

(Example +3) A photosensitive material consisting of the processing solution and silver chlorobromide emulsion used in Example 1 was used, and processing was carried out under the same conditions as in Example 1. However, in this case, laxative (B-1), '(B-11)
Oriku B-16), (B-19) Oriku
B-30), (B-33) and (B-,10) or B-130) were used, and the pH was adjusted to 10.0 and 10.5 under the condition that benzyl alcohol was O.
.

1] and 12. When the maximum blue density of the photosensitive material after processing was measured, it was found that p
Good maximum blue density was obtained with H10.5 or higher.

Patent applicant Konishiroku Photo Industry Co., Ltd. 5.hl? positive object

Claims (8)

[Claims] (1) In a method of color-developing a silver halide color photographic material consisting essentially of silver chlorobromide to obtain an image, the color-developing solution is a color-developing agent represented by the following general formula [1]. containing at least 1.5 x 10^-^2 mol of at least one of 0.003 or less, contains at least 0.05 mol or more of at least one compound having a log p of less than 0.4 and a pka of 10.3 or more, and has a pH of 10.3.
A method for processing a silver halide color photographic material, which is characterized in that the development is carried out at 30° C. and processed within 120 seconds. (2) When the color developer is water and a solvent other than water, the log p
The method for processing a silver halide color photographic light-sensitive material according to claim 1, characterized in that the method comprises a solvent having a log p of less than 0.4 and substantially does not contain a solvent having a log p of 0.4 or more. (3) Halogenation according to any one of claims 1 and 2, characterized in that the silver halide color photographic light-sensitive material is processed in three steps: color development, bleach-fixing, and stabilization treatment. Processing method for silver color photographic materials. (4) Any one of claims 1 to 3, characterized in that during continuous processing of silver halide color photographic light-sensitive materials, replenishment of the color developing solution is carried out at a rate of 150 ml/m^2 or less. A silver halide color photographic light-sensitive material as described above. (5) Any one of claims 1 to 4, characterized in that during continuous processing of silver halide color photographic light-sensitive materials, the amount of replenishing solution to the stabilizing solution is 500 ml/m^2 or less. A method for processing a silver halide color photographic light-sensitive material as described in . (6) The method for processing a silver halide color photographic material according to any one of claims 1 to 5, wherein the color developer has a pH of 10.5 or more. (7) The method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 to 6, wherein the color developer has a pH of 10.75 or more. (8) The method for processing a silver halide color photographic material according to any one of claims 1 to 7, wherein the color developer has a pH of 14 or less.