JP2691777B2 - Bleaching starter and processing method of silver halide color photographic light-sensitive material using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a bleaching starter and a method for processing a silver halide color light-sensitive material using the same.

<Prior Art> A silver halide color light-sensitive material (hereinafter referred to as a color light-sensitive material) is subjected to processes such as color development, desilvering, washing with water and stabilization after exposure.

A color developing solution is used for color development, a bleaching solution, a bleach-fixing solution and a fixing solution are used for desilvering, tap water or ion-exchanged water is used for washing, and a stabilizing solution is used for stabilizing. The temperature of each processing solution is usually adjusted to 30 to 40 ° C., and the color photographic material is immersed in these processing solutions for processing.

Among such processing steps, the basics are a color development step and a desilvering step.

In the color developing step, the exposed silver halide is reduced by a color developing agent to generate silver, and the oxidized color developing agent reacts with a color forming agent (coupler) to give a dye image.

In the desilvering step subsequent to the color development step, silver produced in the color development step is oxidized by the action of a bleaching agent as an oxidizing agent, and then dissolved by a fixing agent as a complex ion forming agent of silver ions. Thus, only a dye image is formed.

The desilvering process described above includes a method in which the bleaching step and the fixing step are performed in the same bath, a method in which they are performed in different baths, a method in which the bleach-fixing step and the bleach-fixing step are performed in different baths, and the like. In this case, each bath may be a multi-bath.

And, in addition to the above basic steps,
Various auxiliary steps are performed for the purpose of maintaining physical quality or improving storage stability. Such a process is performed using, for example, a hardening bath, a stop bath, a stabilizing bath, a washing bath, or the like.

The steps as described above are usually carried out using an automatic processor.

Generally, when performing continuous processing with an automatic processor, the "replenishment method" is used to replenish the auxiliary liquid according to the processing amount of the color photosensitive material to keep the performance of the processing liquid constant, and the processing amount of the color photosensitive material is a predetermined amount. There is a "batch method" in which a part or all of the used processing liquid is replaced with a new liquid when the temperature reaches the above level.

Of these two methods, the replenishment method is often adopted because of the simplicity of the processing work.

In this replenishment method, at the start of continuous processing or when performing continuous processing by replacing the processing solution with a new solution, that is, at the start of processing, the replenisher itself (replenisher) is stored in the processing tank of the automatic developing machine. In some cases, the replenisher itself does not provide the desired photographic performance. In such a case, a replenisher having a composition slightly different from that of the replenisher is prepared, and the replenisher is used as a start-up processing solution ( (Mother liquor).

As the processing solution for the start, a case where a dedicated processing agent kit is used as it is, and a solution prepared by adding a processing agent for correction called a “starter” to a replenisher and further adding water as needed, are used. May be used.

In particular, a small in-store processing service system called a minilab often employs the latter method using a “starter”.

Under such circumstances, the bleaching solution used in the desilvering process also employs the above-mentioned method of using a starter, and this bleaching starter is usually a compound (alkaline) which shows basicity (alkaliness) when made into an aqueous solution. Agent).

Generally, a bleaching solution is designed so that a bleaching replenishing solution having a low pH and an alkaline color developing solution which a color light-sensitive material brings from a prebath are mixed, and a pH which is preferable for photographic performance is obtained from a starter.

Conventionally, ammonia water, potassium hydroxide, sodium hydroxide, and the like have been used as the alkaline agent.

<Problems to be Solved by the Invention> However, the conventional alkaline agents as described above have problems in handling and photographic performance.

For example, when ammonia water is used, there is a problem in that the effective concentration of ammonia acting as an alkaline agent is reduced because the odor is severe and the water easily evaporates.

Also, with kalimuu and sodium hydroxide, since these compounds are strong alkalis, it is dangerous if they adhere to the skin, etc. Furthermore, since carbon dioxide in the air is absorbed, the effective concentration is also the same as with ammonia. There is a problem of decrease. Further, when an aminopolycarboxylic acid iron (III) complex salt which is currently widely used as a bleaching agent is used, iron hydroxide precipitates easily.

In addition to or due to such problems, when using the above alkaline agent, particularly potassium hydroxide or sodium hydroxide, the bleaching speed is reduced and the desilvering performance is impaired. Results.

Such a decrease in desilvering performance is particularly remarkable when rapid processing is attempted, and rapid processing cannot be performed.

A first object of the present invention is to provide a bleaching starter which has no problem in terms of handling properties such as odor and safety in processing with a processing solution having bleaching ability. A second object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material which can be rapidly processed using the bleaching starter described above and has sufficient desilvering performance even in the rapid processing. is there.

<Means for Solving the Problems> In order to achieve the above object, the present invention has the following configurations (1) and (2).

(1) A bleach starter, which is mixed with a replenisher having the same composition as a replenisher used for subsequent processing in order to prepare a processing solution having a bleaching ability for starting a silver halide color photographic light-sensitive material, The replenisher does not substantially contain the compound represented by the following general formula (I), and contains the compound represented by the following general formula (I) as an alkaline agent at a concentration of 1 mol / mol or more up to the solubility limit. A bleaching starter characterized by that.

General formula (I) に お い て In the above general formula (I), R ₁ , R ₂ , R ₃ and R ₄ are
Each represents a hydrogen atom, an alkyl group or an alkenyl group. } (2) In a processing method in which an imagewise exposed silver halide color photographic light-sensitive material is subjected to color development processing and then treated with a processing solution having a bleaching ability, a starting processing solution is used as the processing solution having a bleaching ability, The treatment is carried out while replenishing the replenisher, and a bleaching starter and a solution having the same composition as the replenisher are mixed to prepare the starting treatment solution. A silver halide color photograph containing a compound represented by the formula (I) at a concentration of 1 mol / mol or more up to a solubility limit, and the replenisher does not contain a compound represented by the following general formula (I). Method of processing photosensitive material.

General formula (I) に お い て In the above general formula (I), R ₁ , R ₂ , R ₃ and R ₄ are
Each represents a hydrogen atom, an alkyl group or an alkenyl group. <Operation> According to the present invention, a bleach starter is used for treatment with a treatment solution having a bleaching ability. The bleach starter contains the compound represented by the general formula (I) as an alkaline agent. Therefore, quick processing is possible,
Even in such rapid processing, the desilvering performance is sufficient.

Further, the bleaching starter described above has no problem in terms of handleability such as odor and safety.

The present invention is particularly effective when applied to the step of bleaching immediately after color development.

This is when bleaching is performed immediately after color development.
Since the concentration of the color developing solution brought into the bleaching solution during continuous processing increases, there is a difference between the continuous processing and the start of processing.
This is because the alkali concentration in the bleaching starter must be high in order to balance the pH.

<Specific Configuration> Hereinafter, a specific configuration of the present invention will be described in detail.

In the processing method for a silver halide color photographic light-sensitive material (hereinafter, sometimes referred to as a light-sensitive material) of the present invention, the light-sensitive material after imagewise exposure is color-developed and then processed with a processing solution having a bleaching ability.

Examples of the processing solution having the bleaching ability include a bleaching solution and a bleach-fixing solution. Typical desilvering processing steps including processing with such a processing solution are as follows.

Bleach → Fix Bleach → Bleach Fix Bleach → Wash → Fix Inns → Bleach → Fix Bleach → Bleach Fix → Fix Water Wash → Bleach Fix Bleach Fix Fix → Bleach Fix In particular, among the above steps, step For example, JP-A-61-75352
Issue.

Further, the treatment baths such as the bleaching bath and the fixing bath applied to the above-mentioned steps may have one or more treatment tanks, but two or more treatment tanks (for example, 2 to 4).
(In this case, a counter-current system is preferable).

Among these, in particular, in the present invention, a step in which desilvering treatment is immediately performed with a processing solution having a bleaching ability after the color development processing is preferable, and the processing solution having a bleaching ability in this case is bleached. A liquid is preferable, and a remarkable effect is obtained in such a process.

Therefore, it is preferable to perform a bleaching process immediately after the color developing process. Hereinafter, such a bleaching process will be representatively described.

The bleaching treatment in the present invention is performed using a bleaching starter.

This bleach starter adjusts the start bleaching solution (mother liquor) stored in the processing tank when processing is started or when processing is replaced with a new solution and processing is restarted when continuous processing is performed by an automatic processor. It is used when doing.

That is, a bleaching starter is added to the bleaching replenisher, and if necessary, water is added to prepare a starting bleaching solution.
Thus, the bleach starter can be said to be a processing agent for correction.

Since the bleaching solution starter has a lower pH than the pH of the bleaching solution as described above for the bleaching replenisher, it is mainly used for the purpose of adjusting the bleaching solution for start to an appropriate pH, and contains an alkaline agent. To do.

The bleaching starter of the present invention is an aqueous solution containing a compound represented by the following general formula (I) as an alkaline agent.

General formula (I) In the above general formula (I), R ₁ , R ₂ , R ₃ and R ₄ are
Each represents a hydrogen atom, an alkyl group or an alkenyl group.

The alkyl group may have a substituent, and preferably has 1 to 5 carbon atoms, and particularly 1 to
It is preferably 2. Of these, unsubstituted ones are preferred, and examples include methyl and ethyl.

The alkenyl group may have a substituent and preferably has 2 to 5 carbon atoms, particularly 2 to
It is preferably 3.

Of these, unsubstituted ones are preferred, for example vinyl /
Allyl is mentioned.

When the alkyl group or alkenyl group has a substituent, examples of the substituent include a hydroxy group, an amino group and a nitro group.

Among the above, in the present invention, it is preferable that R ₁ to R ₄ is an unsubstituted hydrogen atom or an alkyl group having 1 to 2 carbon atoms, one of R ₁ to R ₄ when having an alkyl group One is preferably an alkyl group, and most preferably R _{1 to} R ₄ are all hydrogen atoms.

Hereinafter, specific examples of the compound represented by the general formula (I) will be given, but it should not be construed that the invention is limited thereto.

(1) Imidazole (2) 1-methylimidazole (3) 2-methylimidazole (4) 4-methylimidazole (5) 4-hydroxymethylimidazole (6) 1-ethylimidazole (7) 1-vinylimidazole (8) 4-Aminomethylimidazole (9) 2,4-Dimethylimidazole (10) 2,4,5-Trimethylimidazole (11) 2-Aminoethylimidazole (12) 2-Nitroethylimidazole Among the compounds exemplified above, (1), (2),
(3), (4) and (6) are particularly preferable, and (1) is most preferable.

In addition, these compounds have acid dissociation constants (pKa) of 6 to 10,
Particularly preferred is 6.5 to 8.5.

Compounds (imidazole compounds) represented by the general formula (I) are commercially available, and they can be used as they are in the present invention.

These compounds may be contained in the bleaching starter up to the solubility limit of 1 mol / mol or more, preferably 3 to 10 mol / mol, and the pH of the bleaching starter is 6 to 12, preferably 8 to 11. If the pH is too high, absorption of carbon dioxide increases, which is not preferable.

The bleaching starter of the present invention can have a pH that cannot be obtained with conventionally used potassium hydroxide, sodium hydroxide or aqueous ammonia, and can improve the reduction of the active ingredient due to carbon dioxide.

When preparing the starting bleaching solution, the pH of the bleaching replenisher used together with the bleaching starter described above is 0.2 to 0.2.
6, preferably about 2 to 4 and the starting bleaching solution
The pH will be 0.4 to 9.0, preferably 2.5 to 6.5.

When preparing the bleaching solution for start, the mixing volume ratio of the bleaching replenisher and the bleaching starter is 1/2 to 100/1, preferably 5/1.
~ 20/1 is recommended.

The compounds represented by the general formula (I) may be used alone or in combination of two or more. When they are used in combination, the total content may be the above.

Conventionally, aqueous ammonia, sodium hydroxide, potassium hydroxide, and the like have been used as alkaline agents for the bleaching starter, but these alkaline agents have problems in handling properties and desilvering performance.

In particular, when the replenishment method is employed, when the replenishment amount is low, or as in the present invention, the bleach replenisher has a low pH.
When it is, it is necessary to make the alkali added to the bleaching starter rich, and the above problem becomes particularly remarkable.

For example, ammonia water has a bad odor and is liable to evaporate, and its concentration is liable to change. Sodium hydroxide and potassium hydroxide are likely to absorb carbon dioxide in the air and change its concentration. When an aminopolycarboxylic acid iron (III) complex salt is used, iron hydroxide precipitates easily, and since it is a strong alkali, its safety is difficult.

In addition, there is a problem that the bleaching speed is lowered and the desilvering performance is inferior, especially due to the above-mentioned change in concentration, especially with sodium hydroxide and potassium hydroxide.

The above problems can be solved by using the compound represented by the general formula (I).

That is, even when the concentration is high, not only there is no problem in terms of handleability, but also a bleaching accelerating effect is obtained and the desilvering performance is excellent.

Then, such an effect is obtained only by using the compound represented by the general formula (I), and is not obtained by applying other compounds.

For example, British Patent No. 1,138,842 discloses a 2-mercaptoimidazole compound having an imidazole nucleus similar to the compound represented by the general formula (I). It cannot be an alkaline agent to be adjusted and does not exert the effect of the present invention.

The bleaching starter in the present invention may contain only the compound represented by the general formula (I). If necessary, an acid for fine adjustment of pH (for example, hydrochloric acid, sulfuric acid, acetic acid, nitric acid) or the compound of the present invention may be used. Other alkali agents (for example, potassium hydroxide, sodium hydroxide, aqueous ammonia) and the like may be contained within a range where the effect is obtained.

The concentration in that case is 1/2 or less, preferably 1/10 or less, of the total concentration of the compound represented by the general formula (I).

In the present invention, examples of the bleaching agent used for the bleaching replenisher and the starting bleaching solution prepared from the bleaching replenisher (hereinafter, bleaching solution) include iron (III), cobalt (III), chromium (VI), copper ( II) Compounds of polyvalent metals such as peracids,
Quinones, nitro compounds and the like are used. Typical bleaching agents include iron (III) salts such as ferric chloride; ferricyanide: dichromate; iron (III) or cobalt (I
II) organic complex salts, for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, aminopolycarboxylic acids such as glycoletherdiaminetetraacetic acid or citric acid, tartaric acid, Complex salts such as malic acid; persulfates; bromates; permanganates; nitrobenzenes can be used.

From the viewpoints of environmental protection, safety in handling, corrosiveness of metals, etc., it is preferable to use an aminopolycarboxylic acid iron (III) complex salt.

Specific examples of the iron (III) aminopolycarboxylic acid complex salt will be given below, but the invention is not limited thereto. In addition, the oxidation-reduction potential is described.

Compound No. Redox potential (mV vs. NHE, ph = 6) 1. N- (2-acetamido) iminodiacetic acid iron (III) complex salt 180 2. Methyliminodiacetic acid iron (III) complex salt 200 3. Iminodiacetic acid Iron (III) complex salt 210 4.1,4-Butylenediaminetetraacetate iron (III) complex salt 230 5. Diethylenethioetherdiaminetetraacetate iron (III) complex salt 230 6. Glycol etherdiaminetetraacetate iron (III) complex salt 240 7.1,3- Propylenediaminetetraacetic acid iron (III) complex salt 250 8. Ethylenediaminetetraacetic acid iron (III) complex salt 110 9. Diethylenetriaminepentaacetic acid iron (III) complex salt 80 10. Trans-1,2-cyclohexanediaminetetraacetic acid iron (III) complex salt 80 The redox potential of the bleach above is calculated by the Transactions of the Faraday Society (Tran
sactions of the Faraday Society), 55 (1959)
Year), defined by the oxidation-reduction potential obtained by the method described on pages 1312 to 1313.

In particular, in the present invention, in order to speed up the processing,
A bleaching agent having a redox potential of 150 mV, preferably 180 mV or higher, more preferably 200 mV or higher is used.

Of these, Compound No. 7 is particularly preferred.
1,3-propylenediaminetetraacetate iron (III) complex salt (hereinafter, referred to as
1,3-PDTA.Fe (III)).

The aminopolycarboxylate iron (III) complex salt is used as a salt of sodium, potassium, ammonium or the like, and an ammonium salt is preferred in terms of the fastest bleaching.

In the present invention, the bleaching agent may be used alone even if it is used alone.
More than one species may be used in combination.

In the present invention, in addition to a bleach having an oxidation-reduction potential of 150 mV or more, when a redox potential of less than 150 mV is used in combination, the oxidation-reduction potential is 15
0.5 mol or less of less than 150 mV per 1 mol of bleach
It is preferable that the content be about mol or less.

Particularly, when used in combination with an aminopolycarboxylic acid iron (III) complex salt having an oxidation-reduction potential of 150 mV or more, preferred examples thereof include a ferric complex salt of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and cyclohexanediaminetetraacetic acid. Can be.

The amount of the bleaching agent used in the bleaching solution is preferably 0.10 mol or more per bleaching solution, and more preferably 0.20 mol or more from the viewpoint of speeding up processing and reducing bleaching fog and stain. Particularly preferred is at least 0.25 mol. However, since the use of an excessively high concentration liquid adversely affects the bleaching reaction, the upper limit concentration is preferably about 0.7 mol.

When two or more kinds are used in combination, the total concentration may be within the above range.

The amount of the bleaching agent used in the bleaching replenisher is preferably at least 0.1 mol, more preferably at least 0.2 mol, particularly preferably at least 0.3 mol, per bleaching replenisher. Is the limit concentration at which the compound can be dissolved.

In the present invention, the oxidation-reduction potential 150 mV as described above
When the above-mentioned bleaching agent is used and the concentration of the bleaching agent in the bleaching solution is 0.2 mol / or more, particularly rapid bleaching treatment can be performed. Becomes noticeable.

When the aminopolycarboxylic acid iron (III) complex salt is used in the bleaching replenisher or the bleaching solution, it can be added in the form of a complex salt as described above. Iron salts (eg, ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, ferric acetate) in the presence of a complex salt in the bleaching solution Is also good.

In the case of this complex formation, the aminopolycarboxylic acid may be added in a slight excess over the amount required for complex formation with ferric ion, and when added excessively, it is usually 0.01
It is preferable to make it excessive in the range of -10%.

Bleaching solutions are generally used at pH 0.4-9. In order to speed up the treatment, the pH should be 2.5 to 6.5, preferably 2.5 to 4.0, particularly preferably 2.5 to 3.5, as described above.

As described above, the replenisher for bleaching is usually 0.2 to 6.0, and the above-mentioned pH can be adjusted by adding a bleaching starter.

In the present invention, a known acid can be used to adjust the pH of the bleach replenisher mainly used for preparing the bleaching solution to the above range.

As such an acid, an acid having a pKa of 2 to 5 is preferable. In the present invention, pKa represents the logarithm of the reciprocal of the acid decomposition constant, and shows the value obtained at an ionic strength of 0.1 mol / 25 ° C.

In the present invention, an acid having a pKa in the range of 2.0 to 5.0 is used.
It is preferable to use a bleaching solution containing at least 1.2 mol / mol in the desilvering step. 1.2 mol / acid of pKa 2.0-5.0 in the bleaching solution
By including the above, bleaching fog can be further eliminated, and the increase in stain in the uncolored portion after the treatment can be improved.

The acid of pKa2.0-5.0 may be any of inorganic acids such as phosphoric acid, acetic acid, malonic acid, and organic acids such as citric acid, but pKa2.0-showing the effect by the above improvement.
The 5.0 acid is an organic acid. Further, among the organic acids, an organic acid having a carboxyl group is particularly preferable.

The organic acid having a pKa of 2.0 to 5.0 may be a monobasic acid or a polybasic acid. In the case of a polybasic acid, if its pKa is in the range of 2.0 to 5.0, it can be used as a metal salt (for example, sodium or potassium salt) or an annium salt. Further, two or more organic acids having a pKa of 2.0 to 5.0 can be used in combination. However, aminopolycarboxylic acid and its Fe
Excludes complex salts.

Preferred specific examples of the pKa 2.0 to 5.0 organic acid used in the present invention include formic acid, acetic acid, monochloroacetic acid, monobromoacetic acid, glycolic acid, propionic acid, monochloropropionic acid, lactic acid, pyruvic acid, acrylic acid, butyric acid. , Isobutyric acid, pivalic acid, aminobutyric acid, valeric acid, isovaleric acid and other aliphatic monobasic acids; amino acid compounds such as asparagine, alanine, arginine, ethionine, glycine, glutamine, cysteine, serine, methionine and leucine Benzoic acid and mono-substituted benzoic acids such as chloro and hydroxy, aromatic monobasic acids such as nicotinic acid; oxalic acid, malonic acid, succinic acid, tartaric acid, malic acid, maleic acid, fumaric acid, oxaloacetic acid, glutaric acid Aliphatic dibasic acids such as acid and adipic acid; aspartic acid, glutamic acid, glutaric acid, cysteic acid , Amino acid-based dibasic acids such as ascorbic acid; can enumerate various organic acids such as polybasic acids such as citric acid; phthalic acid, aromatic dibasic acids such as terephthalic acid.

In the present invention, among these, a monobasic acid having a carboxyl group is preferred, and acetic acid and glycolic acid are particularly preferred.

In the present invention, the total amount of these acids used is 1.2 mol or more per bleach solution. Preferably 1.2
~ 2.5 mol /. More preferably, it is 1.5 to 2.0 mol /.

The pH of the bleach replenisher used primarily to prepare the bleach
When adjusting to the above range, the acid and the alkali agent (for example, aqueous ammonia, KOH, and NaOH) may be used in combination within a range where the effects of the present invention are exhibited. Among them, aqueous ammonia is preferable.

Various bleaching accelerators can be added to the bleaching solution (that is, the bleaching replenisher) or the prebath thereof in the present invention.

Examples of such a bleaching accelerator include, for example, U.S. Pat.No. 3,893,858, German Patent No. 1,290,812, U.S. Patent No. 1,138,842, JP-A-53-95630, Research Disclosure No. 17129. (1878
Compounds having a mercapto group or a disulfide group described in JP-A No. 50-140129, thiourea derivatives described in US Pat. No. 3,706,561, JP-A-58-140129. The iodide described in 16235, the polyethylene oxides described in German Patent 2,748,430, and the polyamide compound described in Japanese Patent Publication No. 45-8836 can be used. Particularly preferred are mercapto compounds as described in US Pat. No. 1,138,842.

In the bleaching solution of the present invention, in addition to the bleaching agent and the above compounds, a rehalogenating agent such as a bromide such as potassium bromide, sodium bromide, ammonium bromide or chloride such as potassium chloride, sodium chloride or ammonium chloride Can be included. The concentration of the rehalogenating agent is 0.1 to 5 mol per 1 as a bleaching solution, preferably
0.5 to 3 mol.

Further, it is preferable to use ammonium nitrate as the metal corrosion inhibitor.

When the replenishing method is adopted for the present invention, the replenishing amount of the bleaching solution is 200 ml or less, preferably 140 to 1 per 1 m ² of the light-sensitive material.
0 ml.

The bleaching time is 120 seconds or less, preferably 60 seconds or less, and more preferably 50 seconds or less. The present invention is effective in such a shortened processing time.

In addition, during the treatment, iron aminopolycarbonylate (II
It is preferable to subject the bleaching solution containing the complex salt I) to aeration to oxidize the resulting iron (II) aminopolycarboxylate complex salt.

In the preferred desilvering step of the present invention, the fixing solution and the bleach-fixing solution used for processing the photographic material after the bleaching treatment with the above-mentioned bleaching solution contain a fixing agent.

As fixing agents, sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, thiosulfates such as potassium thiosulfate, sodium thiocyanate,
Thiocyanates (rodane salts) such as ammonium thiocyanate and potassium thiocyanate, thiourea, thioether and the like can be used.

Among them, it is preferable to use ammonium thiosulfate. The amount of the fixing agent is 0.1% per fixing solution or bleach-fixing solution.
It is 3 to 3 mol, preferably 0.5 to 2 mol.

From the viewpoint of promoting fixing, it is also preferable to use the above ammonium thiocyanate (rhodanammonium), thiourea, and thioether (for example, 3,6-dithia-1,8-octanediol) in combination. Is generally about 0.01 to 0.1 mol per fixing solution or bleach-fixing solution. However, in some cases, the use of 1 to 3 mol can greatly enhance the fixing promoting effect.

Further, as a fixing agent in the fixing solution or the bleach-fixing solution,
For speeding up the treatment, it is particularly preferable to use a thiosulfate and a thiocyanate in combination, and particularly preferable to use an ammonium thiosulfate and an ammonium thiocyanate in combination.

In this case, the thiosulfate may be used at 0.3 to 3 mol / and the thiocyanate may be used at 1 to 3 mol /, preferably 1 to 2.5 mol /.

Other compounds that can be used in combination with thiosulfates (particularly ammonium thiosulfate) include thiourea and thioethers (eg 3,6-dithia-1,8-octanediol). it can.

The amount of these compounds to be used in combination is generally about 0.01 to 0.1 mol per 1 fixer or bleach-fixer, but may be 1 to 3 mol depending on the case.

Fixing solutions or bleach-fixing solutions include sulfites as preservatives (eg sodium sulfite, potassium sulfite, ammonium sulfite) and hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds (eg sodium acetate bisulfite). Can be included. Further, various optical brighteners and defoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol can be contained, and especially as a preservative, Japanese Patent Application No. 60-283881. It is preferable to use the described sulfinic acid compounds.

The bleach-fixing solution may contain the above-mentioned known bleaching agent. Preferably, it is a ferric aminopolycarboxylic acid complex salt.

In the bleach-fix solution, the amount of the bleaching agent per bleach-fix solution is from 0.01 to 0.5 mol, preferably from 0.015 to 0.3 mol, particularly preferably from 0.02 to 0.2 mol.

In the present invention, the bleach-fix solution at the start of processing (mother liquor)
Is prepared by dissolving the compound used in the above-mentioned bleach-fixing solution in water, but may be prepared by mixing separately prepared bleaching solution and fixing solution in appropriate amounts. The fixing solution has a pH of 5 to 5.
9 is preferable, and 7-8 is more preferable. The pH of the bleach-fixing solution is preferably 6 to 8.5, more preferably 6.5 to
8.0 is preferred.

When the replenishment method is adopted, the replenisher of the fixing solution or the bleach-fixing solution is preferably from 50 to 3000 ml per 1 m ² of the photographic material, more preferably from 100 to 1000 ml.

Further, it is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

Further, the total processing time of the fixing processing or the bleach-fixing processing performed after the bleaching processing in the desilvering processing which is preferable in the present invention is preferably 0.5 to 2 minutes, particularly preferably 1 to 1.5 minutes.

The present invention is effective when applied to such a device having a short processing time.

The shorter the total processing time of the desilvering step of the present invention is, the more the effect of the present invention can be obtained. The preferred time is 1-4 minutes,
More preferably, it is 1 minute 30 seconds to 3 minutes. The treatment temperature is 25 to 50 ° C, preferably 35 to 45 ° C.

In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented.

In the above description, the bleaching step immediately after the color development processing, which is the preferred desilvering step in the present invention, has been described. However, the bleach-fixing step immediately after the color development processing (for example, the desilvering step) may also be used. And the above-mentioned starter can be used.

In such a case, as in the case of the bleaching solution, a start bleach-fixing solution (mother liquor) is prepared using a bleach-fixing solution starter and a bleach-fixing replenisher.

The starter of the bleach-fixer essentially has the same composition as that of the bleach-starter, and has the general formula (I)
The concentration and pH of the compound (alkali agent) represented by are used in the same range.

When the start bleach-fix solution is prepared, the pH of the bleach-fix replenisher used together with the above-described bleach-fix solution starter is 2 to 6.5, preferably about 3 to 6, and the pH of the start bleach-fix solution. Is 3 to 7, preferably 4 to 6.5.

When preparing the bleach-fixing solution for start, the mixing volume ratio of the bleach-fixing replenisher and the starter of the bleach-fixing solution is 1 / 2-100 /
1, preferably 5/1 to 50/1.

Further, the composition of the bleach-fix replenisher is basically the same as that of the above-mentioned bleach-fix solution, and it is possible to use a compound in which the amount of the compound contained is generally about 4 to 100% larger than that of the above-mentioned bleach-fix solution. Good.

Further, such a method using a starter of a bleach-fix solution can be applied to a bleach-fix process performed after a bleach process and a bleach-fix solution in other general bleach-fix processes.

Specifically, the starter of the above-mentioned bleach-fixing solution can be used in the same manner.

Further, the bleaching starter described above can be applied not only to the bleaching process in the above-described preferable desilvering process but also to the overall bleaching process.

From the above, the starter of the bleach-fix solution is no different from the bleach starter, and in the present invention, the starter of the bleach-fix solution can be generically referred to as the bleach starter.

In the desilvering step of the present invention, it is preferable that stirring is strengthened as much as possible in order to more effectively exert the effects of the present invention.

As a concrete method for strengthening stirring, Japanese Patent Application No. 62-183460,
No. 62-183461, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material, a method of improving the stirring effect by using the rotating means of JP-A No. 62-183461, and further, providing in the solution. Examples include a method of moving the light-sensitive material while bringing the wiper blade into contact with the emulsion surface to make the emulsion surface turbulent, thereby improving the stirring effect, and a method of increasing the circulation flow rate of the entire processing solution. Such an agitation improving means is effective for any of a bleaching solution, a bleach-fixing solution and a fixing solution. It is considered that the improved stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed.

Further, the means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the bleaching accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator.

The present invention is applied to an automatic developing machine, is usually carried out by continuous processing, the automatic developing machine used in the present invention,
It is preferable to have a photosensitive material conveying means described in JP-A-60-191257, JP-A-60-191258 and JP-A-60-191259. As described in Japanese Patent Application Laid-Open No. 60-191257, such a transport means can significantly reduce the carry-in of the processing solution from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing solution from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The effect of the present invention is remarkable when the total processing time (however, except for the drying time) is short, and is specifically exhibited when the total processing time is 8 minutes or less, and further when the total processing time is 7 minutes or less. The difference from the conventional processing method becomes remarkable. Therefore, in the present invention, the total processing time is preferably 8 minutes or less, particularly preferably 7 minutes or less.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is a p-phenylenediamine derivative, representative examples of which are shown below, but are not limited thereto.

D-1 N, N-diethyl-p-phenenediamine D-2 2-amino-5-diethylaminotoluene D-3 2-amino-5- (N-ethyl-N-laurariamino) toluene D-4 4- [ N-Ethyl-N- (β-hydroxyethyl) amino] aniline D-5 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-6 4-amino-3-methyl -N-ethyl-N-
[Β- (methanesulfonamido) ethyl] aniline D-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p-phenylenediamine D-9 4-amino- 3-methyl-N-ethyl-N-methoxyethylaniline D-10 4-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above p-phenylenediamine derivatives, particularly preferred is Exemplified Compound D-5.

Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates. The amount of the aromatic primary amine color developing agent used is preferably from about 0.1 to about 2 per color developing solution.
0 g, more preferably a concentration of about 0.5 to about 10 g.

Further, as a preservative, a sulfite such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, or a carbonyl sulfite adduct is added to the color developer as needed. be able to.

The preferred amount of the preservative is 0.5 to 0.5 per color developing solution.
1010 g, more preferably 1-5 g.

Further, as the compound for directly preserving the aromatic primary amine color developing agent, various hydroxylamines, hydroxamic acids described in Japanese Patent Application No.
Hydrazines and hydrazides described in No. 170756, ibid.
Phenols described in 188742 and 61-203253;
It is preferable to add α-hydroxyketones and α-aminoketones described in 61-188741 and / or various sugars described in 61-180616.

Further, in combination with the above compound, Japanese Patent Application No. Sho 61-147832,
Nos. 61-166674, 61-165621, 61-164515,
61-170789 and 61-168159, and the like monoamines, 61-173595, 61-164515, 61-186560.
No. 61-165621, No. 61-1697, etc.
Polyamines described in No. 89 and No. 61-188619, No. 61-
Nitroxy radicals described in 197760, alcohols described in 61-186561 and 61-197419, 61-1989
It is preferable to use oximes described in No. 87 and tertiary amines described in No. 61-265419.

As other preservatives, Japanese Patent Application No. 57-44148 and 57
No. 53749, salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3582, polyethyleneimines described in JP-A-56-94349, U.S. Pat. An aromatic polyhydroxy compound described in No. 3,746,544 may be contained as necessary.

 Particularly, addition of an aromatic polyhydroxy compound is preferred.

The color developing solution used in the present invention is preferably pH 9-1.
2, more preferably 9 to 11.0, and the color developing solution may further contain a compound of a known developing component.

In order to maintain the above pH, it is preferable to use various buffers.

Specific examples of the buffer, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, trillium phosphate, disodium phosphate, dipotassium phosphate, sodium phonate, potassium borate, Sodium tetraborate (borax), potassium tetraborate, o-
Sodium hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples thereof include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the invention is not limited to these compounds.

The amount of the buffer added to the color developing solution is preferably 0.1 mol / or more, and particularly preferably 0.1 to 0.4 mol /.

In addition, various chelating agents can be used in the color developing solution as an agent for preventing precipitation of calcium or magnesium, or for improving the stability of the color developing solution.

The chelating agent is preferably an organic acid compound, and examples thereof include aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids. Specific examples are shown below, but the present invention is not limited thereto.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid,
1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphone Acid, N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid.

These chelating agents may be used in combination of two or more as necessary.

These chelating agents may be added in an amount sufficient to block metal ions in the color developing solution.
0.1 to 10 g per unit.

An optional development accelerator can be added to the color developing solution as needed. However, it is preferable that the color developing solution of the present invention does not substantially contain benzyl alcohol from the viewpoints of pollution, liquid preparation and prevention of color contamination. Here, “substantially” means 2 ml or less per developer,
Preferably, it means that it is not contained at all.

Other development accelerators include JP-B-37-16088,
Nos. 37-5987, 38-7826, 44-12380, 45-9
No. 019, thioether compounds described in U.S. Pat.No. 3,818,247 and the like, p-phenylenediamine compounds described in JP-A-52-49829 and JP-A-50-15554, JP-A-50-1377
No. 26, JP-B-44-30074, JP-A-56-156826, 52
-43429 and the like quaternary ammonium salts, U.S. Pat.Nos. 2,494,903, 3,128,182, 4,230,796,
No. 3,253,919, JP-B-41-11431, U.S. Pat.
2,546, No. 2,596,926, No. 3,582,346, etc., amine compounds, JP-B-37-16088, 42-25201
No. 3,128,183, JP-B-41-11431, 42
-23883, U.S. Pat. No. 3,532,501, and other polyalkylene oxides, 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as necessary.

In the present invention, an optional antifoggant can be further added, if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of the organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-
Nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole,
A typical example is a nitrogen-containing heterocyclic compound such as hydroxyazaindolizine and adenine.

The color developer used in the present invention may contain a fluorescent whitening agent. As the fluorescent whitening agent, a 4,4'-diamino-2,2'-disulfostilbene compound is preferable. The addition amount is 0 to 5 g / preferably 0.1 g to 4 g /.

Further, various surfactants such as alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added as necessary.

The processing temperature in the color developing solution in the present invention is 20 to 50 ° C,
Preferably it is 30-45 degreeC. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes 20 seconds. When the replenishment method is adopted, the replenishment amount is preferably smaller, but is preferably 100 to 1500 ml, preferably 100 to 800 ml per 1 m ^{2 of} the light-sensitive material. More preferably, the volume is 100 to 400 ml.

Also, the color developing bath is decomposed into two or more baths if necessary,
The color developing replenisher may be replenished from the first bath or the last bath to shorten the developing time and reduce the replenishing amount.

The processing method of the present invention can also be used for color reversal processing. The black-and-white developing solution used at this time is a so-called black-and-white first developing solution which is generally used for reversal processing of a color photosensitive material. Various well-known additives used in a black-and-white developing solution used in a processing solution for a black-and-white silver halide light-sensitive material are added to a black-and-white primary color reversal photosensitive material.
It can be contained in a developer.

Typical additives include a developing agent such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, a preservative such as sulfite, and an accelerator composed of an alkali such as sodium hydroxide, sodium carbonate or potassium carbonate. , Inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole and methylbenzthiazole, hard water softeners such as polyphosphates, and development inhibitors consisting of trace amounts of iodides and mercapto compounds. You can

The processing method of the present invention comprises the above-described processing steps such as color development, bleaching, bleach-fixing and fixing. Here, after the bleach-fixing or fixing step, processing steps such as washing and stabilization are generally performed, but after processing with a processing solution having a fixing ability, substantial water washing is not performed. A simple treatment method for performing a stabilization treatment can also be used.

The washing water used in the washing step may contain known additives as required.

For example, inorganic phosphoric acid, aminopolycarboxylic acids, water softeners such as organic phosphoric acid, bactericides for preventing the growth of various bacteria and algae, antifungal agents (for example, isothiazolone, organochlorine fungicides, benzotriazole, etc.), It is possible to use a surfactant or the like for preventing drying load and unevenness. Or LEWest, “Water Quality Criteria”, P
hot. Sci. and Eng., vol. 9, No. 6, p. 344-359 (1965) and the like can also be used.

As a stabilizing solution used in the stabilizing step, a processing solution for stabilizing a dye image is used. For example, a liquid having a buffer capacity of pH 3 to 6, a liquid containing an aldehyde (for example, formalin), or the like can be used. In the stabilizing solution, if necessary, an ammonium compound, Bi, Al, etc., a metal compound, an optical brightening agent, a chelating agent (for example, 1-hydroxyethylidene-1,1-diphosphonic acid), a bactericide, an antifungal agent, Hardeners, surfactants, alkanolamines and the like can be used.

In the washing step and the stabilizing step, a multi-stage countercurrent method is preferable, and the number of stages is preferably two to four. The replenishing amount is 1 to 50 times, preferably 2 to 30 times, more preferably 2 to 15 times the amount brought in from the previous bath per unit area.

Water used in these washing or stabilizing steps is not limited to tap water, and may be C
a, It is preferable to use water deionized to an Mg concentration of 5 mg / or less, or water sterilized by halogen, an ultraviolet germicidal lamp, or the like.

In each processing step of the above color photosensitive material, when continuous processing is performed by an automatic developing machine, concentration of the processing liquid may occur due to evaporation, particularly when the processing amount is small or when the opening area of the processing liquid is large. Will be noticeable. In order to correct such concentration of the processing solution, it is preferable to replenish an appropriate amount of water or a correction solution.

Further, the amount of waste liquid can be reduced by using a method in which the overflow liquid of the washing process or the stabilizing process is caused to flow into a bath having a fixing ability as a pre-bath.

The light-sensitive material of the present invention may be provided with at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer of a silver halide emulsion layer on a support. There is no particular limitation on the number and order of the emulsion layers and the non-light-sensitive layers.

A typical example is a silver halide color photographic light-sensitive material having a light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light and red light. In a multilayer silver halide color photographic material, the arrangement of the unit photosensitive layers is generally supported. The red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer are provided in this order from the body side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different color-sensitive layers are sandwiched between the same color-sensitive layers.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

For the intermediate layer, JP-A-61-43748, JP-A-59-113438,
Nos. 59-113440, 61-20037 and 61-20038, which may contain couplers, DIR compounds, etc., as described in the specification, and a color mixing inhibitor and an ultraviolet absorber as commonly used. And a stain inhibitor.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470 or British Patent No. 923,045.
No. 2 of the high-speed emulsion layer and the low-speed emulsion layer
A layer configuration can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers.

In addition, JP-A-57-112751, 62-200350, and 62-
As described in Nos. 206541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support, low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL) / order, or BH / B
They can be installed in the order of L / GL / GH / RH / RL or BH / BL / GH / GL / RL / RH.

Also, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL / RL is selected from the side farthest from the support.
Can be arranged in this order. JP-A-56-25738
As described in JP-A-62-63936, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

Also, as described in JP-B-49-15495, the upper layer is the most sensitive silver halide emulsion layer, the middle layer is the lower sensitive silver halide emulsion layer, and the lower layer is more than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low sensitivity is arranged and three layers having different sensitivities are sequentially reduced in sensitivity toward a support. Even when such a three-layer structure having different photosensitivity is used,
As described in JP-A No. 59-202464, middle-speed emulsion layer / high-speed emulsion layer / low-speed emulsion layer may be arranged in this order from the side distant from the support in the same color-sensitive layer.

As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

Any of these layer arrangements can be used in the color light-sensitive material of the present invention, but in the present invention, the dried film thickness of all the constituent layers except the support and the undercoat layer and the back layer of the color light-sensitive material is 20.0 μm or less. It is preferable to achieve the object of the present invention. More preferably 18.0μ
It is as follows.

The definition of these film thicknesses is based on the color developing agent incorporated into these layers of the color light-sensitive material during and after the processing, and the amount of the remaining color developing agent greatly affects the bleaching fog and stain generated during image storage after processing. By influencing. In particular, the occurrence of bleaching fog and stain is considered to be caused by the green-sensitive color-sensitive layer, and the increase in magenta color is larger than that in other cyan and yellow colors.

In addition, it is desirable that the lower limit value in the film thickness regulation is reduced within the range that does not significantly impair the performance of the photosensitive material from the above regulation. The lower limit value of the total dry film thickness of the support of the photosensitive material and the constituent layers excluding the undercoat layer of the support is 12.0 μ, and the structure provided between the photosensitive layer closest to the support and the undercoat layer of the support. The lower limit of the total dry film thickness of the layer is 1.0μ.

Further, the reduction of the film thickness may be applied to any of the photosensitive layer and the non-photosensitive layer.

The film thickness of the multilayer color light-sensitive material in the present invention is measured by the following method.

The photosensitive material to be measured is stored at 25 ° C. and 50% RH for 7 days after the preparation of the photosensitive material. First, the total thickness of the photosensitive material was measured, and then the thickness of the coating layer on the support was removed and the thickness was measured again. Thickness. This thickness is measured, for example, using a contact-type thick-electric conversion element.
ritus Electric Co. Ltd., K-402B Stand.). The removal of the coating layer on the support can be performed using an aqueous solution of sodium hypochlorite.

Then, using a scanning electron microscope, take a photograph of a cross section of the photosensitive material (magnification of 3,000 or more is preferable)
Then, the total thickness on the support and the thickness of each layer can be measured, and the thickness of each layer can be calculated by comparing with the measured value of the total thickness (absolute value of the measured thickness) by the film thickness measuring instrument.

Swelling ratio of photosensitive material in the present invention [(equilibrium swollen film thickness in H ₂ O at 25 ° C.−25 ° C., dry film thickness at 55% RH / 25 ° C., 5
The total dry film thickness at 5% RH) × 100] is preferably 50 to 200%, more preferably 70 to 150%.

If the swelling ratio deviates from the above value, the remaining amount of the color developing agent increases, and adversely affects photographic performance, image quality such as desilvering properties, and film properties such as film strength.

Further, the swelling rate of the light-sensitive material in the present invention is 90% of the maximum swelling film thickness reached when processed in a color developing solution (38 ° C., 3 minutes and 15 seconds), and the swelling rate is 1/2 of this. When the time required to reach the film thickness is defined as the swelling rate T 1/2, T 1/2 is preferably 15 seconds or less. More preferably, T 1/2 is 9 seconds or less.

The preferred silver halide contained in the photographic emulsion layer of the color light-sensitive material used in the present invention is silver iodobromide, silver iodochloride or silver iodochlorobromide containing about 30 mol% or less of silver iodide.

Particularly preferred is silver iodobromide containing up to about 2 to about 25 mol% iodide.

The silver halide grains of a photographic emulsion include those having regular crystals such as cubic, octahedral, and tetrahedral, those having irregular crystal forms such as spheres and plates, and those having twin planes. It may have a crystal defect or a composite form thereof.

The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion that can be used in the present invention is described in, for example, Research Disclosure (RD) No. 17643 (1978).
December, p. 22-23, "I. Emulsion preparati
on and types) ”and No. 18716 (November 1979), 64
Page 8, Physics and Chemistry of Photography by Grafkid, published by Paul Montell (P. Glafkides, Chimie et Physique Photograp)
hique Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographi
c Emulsion Chemistry (Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., VLZelikman et al, Marking and Coating Photogr.
aphic Emulsion, Focal Press, 1964).

Monodisperse emulsions described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are written by Gatoff, Photographic Science and Engineering,
14, 248-257 (1970); U.S. Patent No. 4,434,226
No. 4,414,310, No. 4,430,048, No. 4,439,52
It can be easily prepared by the method described in No. 0 and British Patent No. 2,112,157.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a phase structure. Further, silver halides having different compositions may be joined by an epitaxial junction, or may be joined to a compound other than silver halide such as, for example, rhodane silver or lead oxide.

 Also, a mixture of particles of various crystal forms may be used.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used.

Additives used in such a process are described in Research Disclosure Nos. 17643 and 18716, and the relevant portions are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

Various color couplers can be used in the present invention, and specific examples are described in the above-mentioned patents described in RD No. 17643, VII-CG.

As a yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,401,7
No. 52, No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent Nos. 1,425,020 and 1,476,760, U.S. Pat.No. 3,973,96
No. 8, No. 4,314,023, No. 4,511,649, European Patent No. 2
Those described in No. 49,473A are preferred.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferred, and U.S. Pat.
No. 0,619, No. 4,351,897, European Patent No. 73,636, U.S. Pat.No. 3,061,432, No. 3,725,064, RD No. 24220 (1
June 984), JP-A-60-33552, RD No. 24230 (1984)
June), JP-A-60-43659, JP-A-61-72238, JP-A-60-43659.
35730, 55-118034, 60-185951, U.S. Pat.Nos. 4,500,630, 4,540,654, 4,556,630, W
Those described in 0 (PCT) 88/04795 and the like are particularly preferable.

Examples of the cyan coupler include phenol-based and naphthol-based couplers, and U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, and 4,296,200.
No. 2,369,929, No. 2,801,171, No. 2,772,162
No. 2,895,826, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, No. 249,453
A, U.S. Pat.Nos. 3,446,622, 4,333,999,
No. 4,753,871, No. 4,451,559, No. 4,427,767, No. 4,690,889, No. 4,254,212, No. 4,296,199,
Preferred are those described in JP-A-61-42658.

Colored couplers for correcting unwanted absorption of color-forming dyes are described in RD No. 17643, Section VII-G, U.S. Pat.
No., JP-B-57-39413, U.S. Pat.No. 4,004,929,
No. 4,138,258 and British Patent No. 1,146,368 are preferred. Further, a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.No. 4,774,181 and a dye that can form a dye by reacting with a developing agent described in U.S. Pat.No.4,777,120 It is also preferable to use a coupler having a precursor group as a leaving group.

As a coupler in which the coloring dye has an appropriate diffusivity,
Preferred are those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570, and West German Patent (Published) No. 3,234,533.

Typical examples of polymerized dye-forming couplers include U.S. Patent Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 4,409,320, No. 4,576,910, UK Patent No. 2,
No. 102,173, etc.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are described in RD No. 17643, VII above.
-F, JP-A-57-151944 and JP-A-57-151944.
Those described in 154234, 60-184248, 63-37346, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include UK Patent Nos. 2,097,140 and 2,1
No. 31,188, JP-A Nos. 59-157638 and 59-170840 are preferred.

In addition, as couplers that can be used in the light-sensitive material of the present invention, competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472 and 4,338,393,
No. 4,310,618 and the like, multi-equivalent couplers described in
No. 185950, No. 62-24252, etc., DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, recoloring after separation as described in EP 173,302A. Dye-releasing coupler, RD No. 11449, 2
4241, bleach accelerator releasing couplers described in JP-A-61-201247, etc., ligand releasing couplers described in U.S. Pat.No. 4,553,477, etc., couplers releasing leuco dyes described in JP-A-63-75747, U.S.A. Couplers that release a fluorescent dye described in Japanese Patent No. 4,774,181 are exemplified.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods.

Examples of high-boiling solvents used in the oil-in-water dispersion method are described in U.S. Patent No. 2,322,027, and specific examples of high-boiling organic solvents having a boiling point at normal pressure of 175 ° C or higher used in the oil-in-water dispersion method Examples include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,
4-di-t-amylphenyl) phthalate, bis (2,4-
Di-t-amylphenyl) isophthalate, bis (1,1
-Diethylpropyl) phthalate), esters of phosphoric or phosphonic acids (triphenyl phosphate,
Tricresyl phosphate, 2-ethylhexyl phenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphonate, etc., benzoic acid esters ( 2-
Ethylhexyl benzoate, dodecyl benzoate,
2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecaneamide, N, N-
Diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, Dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-
Dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene,
Diisopropylnaphthalene). As the auxiliary solvent, the boiling point is about 30 ° C. or more, preferably 50 ° C.
An organic solvent having a temperature of not less than ° C and not more than about 160 ° C can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in U.S. Pat. No. 4,199,363 and West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

Further, these couplers are hydrophilic by impregnating them with a loadable tarex polymer (for example, US Pat. No. 4,203,716) in the presence or absence of the above high boiling point organic solvent or by dissolving in a water-insoluble and organic solvent-soluble polymer. It can be emulsified and dispersed in a water-soluble colloid solution.

Preferably, International Publication No.W088 / 00723, twelfth
Homopolymers or copolymers described on pages 30 to 30 are used. In particular, use of an acrylamide-based polymer is preferred for stabilizing a color image.

The present invention can be applied to various color photosensitive materials. In particular, it is preferably applied to a color negative film for general use or movies, and a color reversal film for slides or televisions.

Suitable supports that can be used in the present invention include, for example, those described above.
RD No. 17643, page 28 and No. 18716, page 647, right column, 64
It is described in the left column on page 8.

<Example> Hereinafter, the present invention will be described specifically with reference to examples.

Example 1 A multilayer color light-sensitive material was prepared by applying multiple layers of the following composition on a subbed cellulose triacetate film support.

(Composition of photosensitive layer) The number for each component indicates the coating amount in g / m ² . However, for silver halide and colloidal silver, the coating amount is expressed in units of g / m ^{2 in} terms of silver, and for the sensitizing dye, the coating amount is expressed in units per mol of silver halide in the same layer.

(Photosensitive material) First layer (antihalation layer; film thickness 1.2μ) Black colloidal silver Silver coating amount 0.18 Gelatin 1.50 Second layer: (intermediate layer; film thickness 1.7μ) 2,5-di-t-pentadecylhydroquinone 0.18 EX-1 0.07 EX-3 0.02 EX12 0.002 U-1 0.06 U-2 0.08 U-3 0.10 HBS-1 0.10 HBS-2 0.02 Gelatin 1.40 Third layer (first red-sensitive emulsion layer; film thickness 1.5 μ) Emulsion A silver 0.25 emulsion B silver 0.25 sensitizing dye I 6.9 × 10 ^-5 sensitizing dye II 1.8 × 10 ^-5 sensitizing dye III 3.1 × 10 ^-4 EX-2 0.335 EX-10 0.020 HBS-1 0.060 gelatin 1.20 4th Layer (second red-sensitive emulsion layer; film thickness 2.0 μ) Emulsion G Silver 1.0 Sensitizing dye I 5.1 × 10 ⁻⁵ Sensitizing dye II 1.4 × 10 ⁻⁵ Sensitizing dye III 2.3 × 10 ⁻⁴ EX-2 0.400 EX -3 0.050 EX-10 0.015 HBS-1 0.060 Gelatin 1.55 Fifth layer (third red-sensitive emulsion layer; film thickness 2.4 μ) Emulsion D Silver 1.60 Sensitizing dye I 5.4 × 10 ⁻⁵ Sensitizing dye II 1.4 × 10 ^{− 5} Sensitizing dye III 2.4 × 10 ^-4 EX-3 0.010 EX-4 0. 080 EX-2 0.097 HBS-1 0.22 HBS-2 0.10 Gelatin 1.85 6th layer (intermediate layer; film thickness 1.0 μ) EX-5 0.040 HBS-1 0.020 Gelatin 1.15 7th layer (1st green emulsion layer; film thickness) 1.5 μ) Emulsion A Silver 0.15 Emulsion B Silver 0.15 Sensitizing dye V 3.0 × 10 ^-5 Sensitizing dye VI 1.0 × 10 ^-4 Sensitizing dye VII 3.8 × 10 ^-4 EX-6 0.100 EX-14 0.250 EX-1 0.021 EX-7 0.030 EX-8 0.025 HBS-1 0.300 HBS-3 0.010 Gelatin 0.90 Eighth layer (second green emulsion layer; film thickness 1.0 μ) Emulsion C Silver 0.45 Sensitizing dye V 2.1 × 10 ⁻⁵ Sensitizing dye VI 7.0 × 10 ^-5 Sensitizing dye VII 2.6 × 10 ^-4 EX-6 0.060 EX-14 0.053 EX-8 0.018 EX-7 0.026 HBS-1 0.160 HBS-3 0.008 Gelatin 0.70 9th layer (3rd green sensitive emulsion) Layer; film thickness 2.2 μ) Emulsion C Silver 1.2 Sensitizing dye V 3.5 × 10 ^-5 Sensitizing dye VI 8.0 × 10 ^-5 Sensitizing dye VII 3.0 × 10 ^-4 EX-13 0.015 EX-11 0.100 EX-1 0.025 HBS-1 0.25 HBS-2 0.10 Gelatin 1.75 10th layer (yellow filter layer; film thickness 1.0μ) Yellow colloidal silver Silver 0.05 EX-5 0.08 HBS-1 0.03 Gelatin 1.10 11th layer (1st blue emulsion layer; film thickness 2.0 μ) Emulsion A Silver 0.08 Emulsion B Silver 0.07 Emulsion F Silver 0.07 Sensitizing dye VIII 3.5 × 10 ^-4 EX-9 0.721 EX-8 0.042 HBS-1 0.28 Gelatin 1.25 12th layer (2nd blue emulsion layer; film thickness 1.1 μ) Emulsion G Silver 0.45 Sensitizing dye VIII 2.1 × 10 ⁻⁴ EX-9 0.154 EX -10 0.007 HBS-1 0.05 Gelatin 0.95 13th layer (3rd blue sensitive emulsion layer; film thickness 1.2μ) Emulsion H Silver 0.77 Sensitizing dye VIII 2.2 × 10 ^-4 EX-9 0.20 HBS-1 0.07 Gelatin 0.90 14th Layer (first protective layer; thickness 1.5 μ) Emulsion I Silver 0.5 U-4 0.11 U-5 0.17 HBS-1 0.05 Gelatin 1.30 Fifteenth layer (second protective layer; thickness 2.0 μ) Polymethyl acrylate particles (diameter About 1.5 μm) 0.54 S-1 0.20 Gelatin 1.25 In addition to the above components, a gelatin hardening agent H-1 and a surfactant were added to each layer.

HBS-1 Tricresyl phosphate HBS-2 Di-n-butyl phthalate The dried film thickness of all the constituent layers of the prepared photographic material except the support and the undercoat layer of the support was 23.3 μm. This light-sensitive material was cut and processed into a width of 35 mm, given uniform exposure at a color temperature of 4800 ° K 10 CMS, and processed according to the following processing steps. Processing process Time Temperature Color development 2 minutes 30 seconds 38 ℃ Bleach 40 seconds 38 ℃ Fixing (1) 40 seconds 38 ℃ Fixing (2) 40 seconds 38 ℃ Washing (1) 30 seconds 38 ℃ Washing (2) 30 seconds 38 ℃ Stabilization 30 seconds 38 ℃ Drying 1 minute 55 ℃ Below is the formulation of the treatment liquid. The bleaching solution was prepared from a bleaching replenisher and a bleaching starter.

(Color developer) Unit (g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 2-Methyl- 4- [N-Ethyl-N- (β-hydroxyethyl) amino] aniline sulphate 4.5 Add water to 1.0 pH 10.05 (bleaching solution) 700 ml of the bleaching replenisher of the following formulation, 50 ml of the following bleaching starter and 250 ml of water. Was added and stirred to prepare a solution. The pH was adjusted to 3.0 respectively.

Bleach replenisher Unit (g) 1,3-Propylenediaminetetraacetic acid Ferric ammonium monohydrate 210 1,3-Propylenediaminetetraacetic acid 4.0 Ammonium bromide 150 Ammonium nitrate 42 Hydroxyacetic acid 95 Acetic acid (98%) 55 Water In addition, 1 pH [adjusted with ammonia water (27%)] 2.5 Bleach starter A bleaching starter was prepared by using distilled water so that the following compounds (alkali agents) had the following concentrations. Also shows the pH of each solution.

Bleach Starter A Ammonia water (27%) 194g / (pH12.0) B Sodium hydroxide 122g / (pH14 or more) C Potassium hydroxide 172g / (pH14 or more) D Imidazole 209g / (pH10.2) E 2-Methylimidazole 251g / (pH10.8) F 4-methylimidazole 251g / (pH10.8) (fixer) unit (g) ethylenediaminetetraacetic acid disodium salt 5.0 ammonium sulfite 12.0 ammonium thiosulfate aqueous solution (700g /) 290.0 ml ammonia water (27 %) 6.0 ml by adding water to 1.0 pH 6.8 (wash water) Tap water is used as H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type strongly basic anion exchange resin (Amberlite). IRA-400) was passed through a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / or less, followed by sodium diisocyanurate dichloride 20 mg / and sodium sulfate. 150 mg thorium
/ Was added.

 The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizer) Unit (g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water 1.0 pH 5.8 ~ 8.0 As above The treatments are treatments AF (Table 1), depending on the bleach starters AF used.

The bleaching starters A to F were examined for odor.

The residual silver amount (μg / cm ² ) in the unexposed portion of the light-sensitive material processed by each of the processings A to F was measured by the fluorescent X-ray method to examine the desilvering failure.

 Table 1 shows the results.

Table 1 shows that the processing method (processing D, E, F) of the present invention to which the bleaching starters D, E, F are applied is excellent in desilvering performance.

On the other hand, in the treatment A using the aqueous ammonia, it is found that not only the desilvering performance is inferior but also the odor of the bleaching starter A is severe. Further, it has been found that the bleaching starter A is liable to evaporate and change the density easily, which is considered to be one of the causes of the poor desilvering performance.

Further, it can be seen that the treatments B and C using sodium hydroxide and potassium hydroxide are inferior in desilvering performance. The bleaching starters B and C in these treatments have no problem in terms of odor, but have a problem in safety because they are strong alkalis. Further, it absorbs carbon dioxide in the air and easily causes a change in concentration similarly to ammonia, but this is also considered to be one cause of poor desilvering performance.

Further, as described above, it was also confirmed that when the aminopolycarboxylic acid iron (III) complex salt is used as the bleaching agent, iron hydroxide precipitates easily.

On the other hand, in the processings DF of the present invention, no adverse effects caused in the processings A to C are observed.

Example 2 Fuji Photo Film Co., Ltd. color printing paper Fujicolor Super HG (117 mm wide) was imagewise exposed, and was replenished using a Fujicolor paper processor PP600 in the following processing steps until the color developing tank capacity was doubled. , Continuous processing (running test). Step Temperature Time Replenishment rate ^* Tank capacity color developing 38 ° C. 1 min 40 sec 290 ml 17 blix 38 ° C. 60 seconds - 9 washing 30 to 34 ° C. 20 seconds - 4 washing 30 to 34 ° C. 20 seconds - 4 washing 30 34 ℃ 20 seconds 364 ml 4 Dry 70 to 80 ℃ 50 seconds * per 1 m ^{2 of} light-sensitive material (wash tank → 3 tank counter-current method) The composition of each processing solution is as follows.

Bleach-fixing solution Replenishing solution Water 400 ml Ammonium thiosulfate (70%) 300 ml Sodium sulfite 10 g Ethylenediaminetetraacetic acid iron (III) ammonium 120 g Ethylenediaminetetraacetic acid disodium 10 g Water is added to 1000 ml pH (25 ° C) 6.30 Washing water (starting solution, replenishment) Same as the washing solution) Same as washing water in Example 1 In the above continuous treatment, 750 ml of the above bleach replenishing solution and 42 ml of the bleach starter of Example 1 were respectively added as a starting solution of the bleach-fixing solution and mixed to obtain a total of 1. The same results as in Example 1 were obtained when the treatment was performed using each of the above.

<Effects of the Invention> According to the present invention, in a process using a processing solution having a bleaching ability, particularly in a step of performing a bleaching process immediately after a color developing process, a rapid process can be performed by using a bleaching starter. .

Even in such a rapid processing, the desilvering performance is excellent, and no desilvering failure occurs. Further, the bleaching starter of the present invention has no adverse effect on handling properties such as odor and safety.

Claims (2)

(57) [Claims] 1. A bleaching starter for mixing a processing solution having a bleaching ability for starting a silver halide color photographic light-sensitive material with a solution having the same composition as a replenishing solution used for subsequent processing. The replenisher does not substantially contain the compound represented by the following general formula (I), and contains the compound represented by the following general formula (I) as an alkaline agent at a concentration of 1 mol / mol or more up to the solubility limit. Bleach starter characterized by containing. General formula (I) に お い て In the above general formula (I), R ₁ , R ₂ , R ₃ and R ₄ are
Each represents a hydrogen atom, an alkyl group or an alkenyl group. ｝ 2. A processing method in which an imagewise exposed silver halide color photographic light-sensitive material is subjected to color development processing and then processed with a processing solution having a bleaching ability, wherein a starting processing solution is used as the processing solution having a bleaching ability. , A treatment is performed while replenishing the replenisher with it, and a bleaching starter and a solution having the same composition as the replenisher are mixed to prepare the treatment liquid for start, and the bleaching starter has the following composition as an alkaline agent. A halogen containing the compound represented by the general formula (I) at a concentration of 1 mol / mol or more up to the solubility limit, and the replenisher does not substantially contain the compound represented by the following general formula (I). Processing method of silver halide color photographic light-sensitive material. General formula (I) に お い て In the above general formula (I), R ₁ , R ₂ , R ₃ and R ₄ are
Each represents a hydrogen atom, an alkyl group or an alkenyl group. ｝