JPH02193148A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To diminish changes during processing even in the case of a small amt. of a developing agent replenished and to enhance distinguishing effect by making the amt. of the developing agent replenished <=2.5 times as large as the amt. of the agent consumed by development and by allowing a development retarding component to act from the middle of a color developing stage. CONSTITUTION:When a silver halide color photographic sensitive material is color-developed with an arom. prim. amine developing agent, the amt. of the developing agent replenished is made <=2.5 times as large as the amt. of the agent consumed by development and a development retarding component is allowed to act from the middle of the color developing stage. Though changes in sensitivity, color balance, contrast, etc., are increased during processing by increasing the concn. of a replenisher and reducing the amt., the changes are diminished by allowing the retarding component to act from the middle of development and stable development can be carried out. A superior image ensuring a high distinguishing effect is stably obtd. without deteriorating the photographic performance of the sensitive material even in the case of a small amt. of the developing agent replenished.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for processing a silver halide color photographic material, and particularly to a developing method that produces a small amount of waste liquid and has a high discrimination effect.

(Prior Art) In developing color and some black and white silver salt photosensitive materials, it has been reported in JP-A-59-1999 that the discrimination effect can be improved by adding an inhibitory component to the intermediate stage of the development process.
No. 135463. The discrimination effect is an effect in which there is a clear difference in the speed of development between the exposed area and the area that is not irradiated with light, resulting in a clear image, and is also called discrimination.

It is described in Japanese Patent Application No. 62-321481 that the discrimination effect achieved by the additional action of the suppressing portion is more effective in forward flow slit development.

On the other hand, as social demands for environmental protection are increasing these days, it is of great significance to reduce the load of waste liquid discharged during color development processing, and methods for reducing the amount of waste liquid are becoming popular. For example, treatment methods and machines are in use that eliminate the need for piping by completing the washing process with an extremely small amount of water.

Furthermore, thickening the developer without reducing the amount of replenisher has the meaning of directly reducing the waste liquid load (BOD, COD components, etc.) rather than the amount of waste liquid, and also leads to resource savings. Therefore, the current situation is to make the developer solution as concentrated as possible and to make it as low in replenishment as possible.

(Problems to be Solved by the Invention) There are two problems when thickening the developer replenisher and reducing the replenishment level. One is that accidents such as crystallization and precipitation of the concentrated liquid are likely to occur. Another problem is that the accumulated residual amount of reaction products generated during the processing of the light-sensitive material and eluates from the light-sensitive material increases, which affects photographic performance.

The main influencing component of the development reaction product is halide ion (B
r-, do) and leaving residues of 2-equivalent couplers (especially DIR
The main components that affect the eluate of light-sensitive materials are spectral sensitizers and emulsion stabilizers. Since most of these act as development inhibitors, especially in low-replenishment development, the development reaction takes place in an atmosphere of such inhibitory accumulations, resulting in decreased sensitivity and color during processing. A major defect is that there are large fluctuations in balance, contrast, etc.

This drawback makes it highly desirable to have a processing method or photosensitive material with a greater degree of reduction in the amount of replenishment.

Therefore, an object of the present invention is to solve the above-mentioned problems of high concentration and low replenishment, and to make it possible to stably obtain excellent images even with a small amount of replenishment without impairing the inherent photographic performance of the light-sensitive material. The goal is to find a development processing method that is possible.

The second object of the present invention is to eliminate the drawbacks associated with concentrated and low replenishment, and to reduce the load (BOD, C0D) associated with waste liquid treatment. A third objective is to reduce the amount of color developing agent required and to lower development costs by increasing the utilization efficiency of the color developing agent. Also, the fourth
The purpose of
By reducing the amount of waste liquid, the waste liquid generated can be kept within the volume of the supplied replenisher container, simplifying the waste liquid treatment operation, and as mentioned in the introduction, it is possible to avoid such concentrated replenishment. The aim is to maintain the discrimination effect at a stable and high level.

(Means for solving problems) Needless to say, the acceleration increases with the increase in speed.

Therefore, the traditional idea of replenishment is to use a large amount of replenisher so that such an effect does not occur, and generally the replenisher contains several times the amount of developing agent that is actually consumed during development. Contains. Conventional replenishers usually have a replenishment ratio [replenisher concentration/equilibrium concentration in the tank (referred to as mother liquor concentration)] of about 1.0 to 1.20.

However, this no longer meets the needs of the current market and society, and there is a need to overcome this problem.

In recent years, due to low replenishment, products with high concentration and low replenishment amount exceeding 1.2 and around 1.7 have appeared on the market.
Naturally, if the amount of replenishment is reduced, the accumulated concentration of these reaction products and eluates will increase, which will have a negative effect on the photographic performance of the light-sensitive material, and this will limit the ability to reduce the amount of replenishment. .

Therefore, even if reaction products and eluates accumulate, there is a replenishment method and a developing method that are not easily affected by the accumulation.
When carrying out color development of a silver halide color light-sensitive material using an aromatic primary amine type developing agent, the amount of replenishment of the developing agent is within 2.5 times the amount of developing agent consumed during development, and the color development step It has been found that the problem can be solved by a method for processing a silver halide color photographic material, which is characterized in that a development inhibiting component is added to the action of a new component in the middle of the process.

As mentioned above, variations in sensitivity, color balance, contrast, etc. during processing increase as the developer replenisher becomes more concentrated and replenished less.Surprisingly, however, at this time, inhibitory components are applied from the middle of development. Under these conditions, this fluctuation becomes smaller and stable development processing can be performed, resulting in lower replenishment and
In particular, we have found that it is possible to achieve reduced replenishment, which is the ultimate in low replenishment.

The reason why processing fluctuations associated with low replenishment or reduced replenishment can be reduced by acting midway is not known, but it is presumed that it is because the fluctuations that occur in the early stages of development are suppressed in the later stages.

The method of the present invention is effective in high-concentration, low-replenishment replenishment methods that have been practiced in recent years, such as low replenishment amounts with a replenishment ratio of about 1.4 to 1.7 degrees, or especially low replenishment amounts that exceed this. Demonstrate. If expressed in terms of replenishment magnification, 1.8 or higher is good. However, in the present invention, since a multi-tank system or an Il flow system is preferable, it is more appropriate to represent the ratio of the amount of developing agent replenished to the amount of developing agent consumed by development rather than the replenishment magnification. It has been found that in low replenishment processing in which this ratio is 2.5 or less, preferably 2.3 or less, that is, the effective utilization rate of the developing agent exceeds 40%, the effect of applying the inhibitory component from the middle is particularly large.

Additionally, the present invention allows for reduced supplementation.

The term "loss replenishment" refers to replenishing the amount lost due to carryover, etc., which is occluded or attached to the photographic material being processed and carried out of the developing tank, and is a particularly preferred embodiment of the present invention. In the case of supplementation at reduced doses, it may be difficult to determine the effective utilization rate or the ratio of supplemented main drug amount/consumed main drug amount by actual measurement.
If this ratio roughly corresponds to the equivalent ratio of the amount of replenishing main agent/the amount of developed silver salt, the concentration of the inhibitor has been increased, but if a solution containing a different type of inhibitor is used, etc. This is the way to do it. In a special case, it is also possible to use a second development that has the same effect as high inhibition by lowering the pH.

Furthermore, as described in Japanese Patent Application No. 62-321481, in downflow slit development, an inhibitor can be added through an injection port during development. The processing method called slit development is a development method that uses a narrow opening and a long and narrow processing tank to reduce air oxidation and has a small tank volume in relation to the processing amount.
No. 21481.

The time to apply the inhibitory component is when the development of the image area, that is, the exposed area, has already substantially progressed, but it is best to apply the inhibitory component to prevent fogging in the unexposed area, before it has started to grow. Details are described in JP-A-59-135463.

A wide variety of known inhibitors can be used in the present invention.

These include, for example, C, E, Mees and T
, H. James.

Therefore, this value can be used.

The meaning of applying a new inhibitory component during development is to increase the degree of inhibition in the developing environment at an appropriate time after the photographic material is immersed in a developer and development has begun.
Suppression components generally act on non-image-like or inverse images. Increasing the degree of inhibition includes adding or generating an inhibitor, as well as lowering the activity by lowering the pH of the developer. Further, among the inhibitory components, as described below, inhibitory components such as development reaction products and photosensitive material eluates are also included in the present invention if they are devised so that their effects are strengthened from the middle of development.

As a specific method for newly suppressing development from the middle of the development process, for example, several methods listed in JP-A-59-135463 can be used, but the most direct method is two-step development, That is, the development is divided into two stages, and the first development is carried out with a developer solution containing, for example, only KBr as an inhibitor, or even without KBr, or even if it contains other inhibitors, at a relatively low concentration.
The second developer is a developer with higher inhibition than the first developer and “Th
e Theory of Photographic
Processes I[IrdEd, (1966
It is described in textbooks such as Mac Millan Co.) P344-346. The main compounds are shown below.

1.1-phenyl-5-mercaptotetrazole derivative 1-phenyl-5-mercaptotetrazole 1-(4-
Hydroxyphenyl)-5-mercaptotetrazole 1-(4-aminophenyl)-5-mercaptotetrazole 1-(4-carboxyphenyl)-5-mercaptotetrazole 1-(4-chlorophenyl)-5-mercaptotetrazole 1-(4 -Methylphenyl)-5-mercaptotetrazole 1-(2,4-dihydroxyphenyl)-5-mercaptotetrazole 1-(4-sultubumoylphenyl)-5-mercaptotetrazole 1-(3-carboxyphenyl)-5-mercaptotetrazole 113 .5-dicarboxyphenyl)-5-mercaptotetrazole 1-(4-methoxyphenyl)-5-mercaptotetrazole 1-(2-methoxyphenyl)-5-mercaptotetrazole 1-(4-(2-hydroxyethoxy)phenyl 5-mercaptotetrazole 1-(2,4-dichlorophenyl)-5-mercaptotetrazole 1-(4-dimethylaminophenyl)-5-mercaptotetrazole 1-(4-nitrophenyl)-5-mercaptotetrazole 1,4-bis (5-mercapto-1-tetrazolyl)benzene 2.1-Aliphatic substituted 5-mercaptothi3, benzotriazoles 56-dimethylbenzotriazole 5-butylbenzotriazole 5-methylbenzotriazole 5-chlorobenzotriazole 5-bromo Benzotriazole 5.6-Dichlorobenzotriazole 4.6-Dichlorobenzotriazole 5-Nitrobenzotriazole 4-Nitro-6-chloro-benzotriazole 4.56-)Dichlorobenzotriazole 5-Carboxybenzotriazole Penzotriazole 5-Sulfo Benzotriazole Na salt 5-methoxycarbonylbenzotriazole 5-aminobenzotriazole 5-butoxybenzotriazole 5-ureidobenzotriazole 4, thiouracil derivatives torazoles 1-methyl-5-mercaptotetrazole 1-ethyl-
5-mercaptotetrazole 1-propyl-5-mercaptotetrazole 1-octyl-5-mercaptotetrazole l-dodecyl-5-mercaptotetrazole 1-
cyclohexyl-5-mercaptotetrazole 1-palmityl-5-mercaptotetrazo-J-1-carboxyethyl-5-mercaptotetrazole 1-(2,2-jethoxyethyl)-5-mercaptotetrazole 1-(2-aminoethyl) -5-mercaptotetrazole hydrochloride 1-(2-diethylaminoethyl) -5-mercaptotetrazole 2-(5-mercapto-1-tetrazolyl)ethyltrimethylammonium chloride thiouracil methylthiouracil ethylthiouracil probylthiouracil nonylthiouracylaminothio Uracil Hydroxythiouracil 5.2-Mercaptobenzimidazoles 2-Mercaptobenzimidazole 5-Carboxy-2-mercaptobenzimidazole 5-Amino-2-mercaptobenzimidazole 5-Nitro-2-mercaptobenzimidazole 5-chloro-2- Mercaptobenzimidazole 5-methoxy-2-mercaptobenzimidazole 2-mercaptonaphthoimidazole 2-mercapto-5-sulfobenzimidazole 1-(2-hydroxyethyl)-2-mercaptobenzimidazole 6, indazoles 5-nitroindazole 6- Nitroindazole 5-aminoindazole 6-aminoindazole indazole 7, benzimidazoles Benzimidazole 5-chlorobenzimidazole 5-nitrobenzimidazole 5-n-butylbenzimidazole 5-methylbenzimidazole 4-chlorobenzimidazole 5. For example, when KBr is used as an inhibitor for methylbenzimidazole, relatively good results are obtained at a concentration of about 50 mM, and there are considerable differences depending on the inhibitor.

In one embodiment of the present invention, when the inhibitor is incorporated into a photographic material after being released in a sustained manner, the inhibitor released in the photoresist film during development is released in eight cycles so that the concentration is as described above. Ru.

For example, in the case of compounds releasing 1-phenyl-5-mercaptotetrazole derivatives, 1-aliphatic substituted 5-mercaptotetrazoles, thiouracil derivatives or 2-mercaptobenzimidazoles, 0 per gram of silver in the silver halide emulsion layer. ．． Preferably it is from 1 to 20XIO-6 mol, especially from 0.25 to 2.5XIO-6 mol.

In the case of compounds that release relatively weak inhibitors, such as benztriazoles, indazoles, and benzimidazoles, 0.0. 5-100XIO-6 moles, especially 2.5-25X
Preferably it is 10-' moles.

9. In addition to adenine anine and its analogues, inorganic inhibitors such as Kl and KB'r can also be used.

The concentration of the inhibitor varies depending on the type of inhibitor, the photosensitive material used, and the type of developer, but the key is to find an appropriate concentration that effectively suppresses the formation of fog but does not have a large effect on the density of the image area. All you have to do is choose. This density is such that, if applied from the beginning of development, the suppression of the image area would be large and the discrimination between the image area and the unexposed area would be deteriorated.

Roughly speaking, for example, when an inhibitor is contained in a developer, the amount of non-mercapto type inhibitor is 0.0% per developer H2.
02mM to 10mM, 0.0 for mercapto-type inhibitors
Concentrations ranging from 0.02mM to 1mM are effective, especially 0.1mM to 1mM for the former and 0.00mM for the latter.
A range of 5mM to 0.1mM is suitable.

However, this concentration is only a guideline, and the precursor that can be used for the purpose of octopus is determined by the appropriate release timing of the inhibitor, as can be seen from the mechanism of action of the effect of the present invention, which has already been explained. is necessary. In other words, even if the release of the inhibitor occurs early when the development of the image area has not yet reached a suitable level, or conversely, the release of the inhibitor occurs at a later stage when the fog in the unexposed area increases, the present invention is still effective. effect cannot be obtained.

The inhibitor precursor applicable to the present invention is one that releases the inhibitor at an appropriate time depending on the combination of the photosensitive material and developer used. Examples of such inhibitors include the following compounds:

For example, Special Publication No. 55-9696, Special Publication No. 55-173
No. 69, Japanese Patent Publication No. 55-34927, Japanese Patent Publication No. 56-77
Precursors and their analogs described in No. 842 and the like. (Reverse Michael type) 1-phenyl-5-(2-cyanoethylthio)tetrazole 1-(3-hydroxyphenyl)-5-(2-cyano-
1-methylethylthio)tetrazole 1-(3,5-dicarboxyphenyl)-5(2-acetylethylthio)
Tetrazole 1-phenyl-5-(2-phenylsulfonethoxycarbonylthio)tetrazole 1-(2-phenylsulfonethoxycarbonyl)-5
-Methylbenzotriazole 1-phenyl-3-(1-phenyl-5-tetrazolylthio)succinimide 1-ethyl-3-(5-nitro-2-benzimidazolylthio)succinimide 2-phenylsulfonyl-1 -(1-phenyltetrazolylthio)styrene 1-(1,2-dibenzoylethyl)penztriazole In addition, in the present invention, the development inhibiting component is So-called development inhibitor releasing compounds (DIR compounds) which are released imagewise are not included.

is transferred from the first tank to the next tank, and then from the last tank to the next process. A processing method in which the replenisher is replenished in the first tank, the overflow is sequentially replenished in the next tank, and the overflow in the final tank is discharged outside the developing process system. Therefore, the buildup caused by development becomes very expensive in the subsequent tank.

In this processing method, in the case of reduced replenishment, which is the ultimate in low replenishment, the amount of replenishment in the first tank is equal to the amount of carryover contained in the photosensitive material and carried out to the next tank, so there is no overflow. .

(2) Forward-flow slit development process If the slit development described above is performed in a forward-flow manner, that is, in such a way that the photosensitive material sample and replenisher are added to the developing tank from the same side of the tank, development is performed with little accumulation in the early stages of development. As the development progresses, that is, from the middle of the development, the generated inhibitory components act on the photosensitive material.

In the method of adding a development inhibitor during development, there is a method of adding a non-mercaptoazole solution to the second or third tank in multi-tank development (for example, 2 or 3 tanks), or a method of adding a development inhibitor during development in forward flow slit development. A method of adding the non-mercaptoazole solution through the injection port is particularly preferred.

More preferred examples of such non-mercaptoazoles include hentriazole, 4-methylpenztriazole, 5-nitroindazole, 6-nitroindazole, 4-nitropenztriazole, 5-methylhenreimidazole, adenine, and the like.

On the other hand, special examples of inhibitory components that are allowed to act midway include development reaction products and photosensitive material elution inhibiting components as described above. In this case, it is necessary to select a development processing method that allows these to act from an intermediate stage of development.

Examples of this processing method include the following.

(1) Multi-stage forward-flow tank processing A plurality of developing tanks are used to produce a photosensitive material (sensitive material) In the present invention, in particular, the above-mentioned multi-stage forward-flow tank processing or down-flow slit development processing removes inhibitory components generated during development. Preferably, the processing method is assembled to act on the light-sensitive material.

This method does not require any additional intentional addition of an inhibitor, and is surprisingly effective in terms of stability of photographic performance, degree of reduction in replenishment amount, and identification effect.

The forward flow development is particularly advantageous when developed at high temperatures (eg above 40'C). Generally, a method in which a suppressing component is applied midway through is a disadvantageous method from the viewpoint of shortening the development processing time. However, in such a forward flow slit high temperature development system, this drawback is eliminated due to the speeding-up effect of high temperature processing, and surprisingly, the drawbacks of increased processing fluctuations and decreased discrimination effect due to high temperature processing are also eliminated.

In addition to downflow slits and high temperatures, it is particularly advantageous in the present invention to perform reduced replenishment.

Examples of the light-sensitive material used in the method of the present invention include color paper, color reversal paper, color negative film for photography, color reversal film, negative or positive film for motion pictures, and direct positive color light-sensitive materials.

As the silver halide emulsion for the light-sensitive material, any known silver halide emulsion can be used. For rapid processing, high silver chloride emulsions, especially those with a silver chloride content of 80 to 100 mole percent, are preferred. In the case of light-sensitive materials for color printing, silver chlorobromide emulsion (for rapid processing, silver chloride is preferably 90 mol% or more), and in the case of color light-sensitive materials for photography, silver iodobromide emulsion (silver iodobromide emulsion) The silver content is preferably 2 to 15 mol%). Silver halide grains are spherical, cubic, octahedral, rhombic dodecahedral, tetradecahedral, etc., and tabular (preferably aspect ratio 5 to 20) are used for high-sensitivity photosensitive materials.
) is preferred. These particles may be particles consisting of a uniform phase or may be particles consisting of a multilayer structure. Further, the particles may be surface latent image type particles or internal latent image type particles.

The particle size distribution may be polydisperse or monodisperse (preferably standard deviation/average particle size ≦15%) 2 Sensitivity enhancer Same as above 3 Spectral sensitizer
Pages 23-24 Page 648 Right column ~ 4 Supersensitizer
Page 649 right column 5 Brightener page 24 6 Anti-fogging agent pages 24-25 Page 649 right column and stabilizer 7 Coupler page 25 8 With @solvent page 25 9 Light absorber, fu page 25-26 page 649 right column ~Ilter dyes Page 650 left column 10 Ultraviolet absorbers 11 Stain inhibitors Page 25 right columns Page 650 left to right columns 12 Dye image stabilizers Page 25 13 Hardeners Page 26 Page 651 Left column 1
4 Binder page 26 Same as above 15
Plasticizers, lubricants Page 27 Page 650 Right column 16 Coating aids, Surface Pages 26-27 Same as above Activators, but the latter is preferred. These silver halide grains may be used alone, or may be used in combination depending on the purpose.

The photographic emulsion used in the present invention is described in Research Disclosure (RD) vol. 176 Item No. 1.
”16431 (1, I[, Ii[) term (1978 1
It can be prepared using the method described in (February).

The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are described in Research Disclosure Vol. 176, No. 17643 (December 1978) and Research Disclosure Vol. 187, No.

18716 (November 19'?9), and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the two Research Disclosures mentioned above, and their locations are shown in the table below.

17 Static Prevention Page 27 Same Agent Various color couplers can be used in the present invention, specific examples of which can be found in the Research Disclosure + -
(RD) No. 17643. ■It is described in the patent described in -C-C. As dye-forming couplers, couplers that give the three primary colors (i.e., yellow, magenta, and cyan) in subtractive color development are important.Specific examples of diffusion-resistant, 4-equivalent or 2-equivalent couplers are mentioned above.
In addition to the couplers described in the patents D17643, ■-C and D, the following can be preferably used in the present invention.

Typical examples of yellow couplers that can be used include known oxygen atom elimination type yellow couplers and nitrogen atom elimination type yellow couplers. α-pivaloylacetanilide couplers have excellent color fastness, particularly light fastness, while α-henzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include hydrophobic 5-pyrazolone and pyrazoloazole couplers that have a ballast group.

As the 5-pyrazolone coupler, a coupler in which the 3-position is substituted with an arylamino group or an acylamino group is preferable from the viewpoint of the hue and coloring density of the coloring dye.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant naphthonyl and phenol couplers, and representative examples include preferably oxygen atom-eliminating two-equivalent naphthol couplers. Couplers that can also form cyan dyes that are stable against humidity and temperature are
Typical examples of preferred examples include phenolic cyan couplers having an alkyl group of ethyl group or higher at the meta-position of the phenol nucleus, 2,5-diacylamino-substituted as described in U.S. Pat. No. 3,772,002. Phenolic couplers, couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position are useful.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline, .3 -Methyl-4-amino-N-β-hydroxyethylaniline, 3-methyl-4-amino-N
-ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-1-luenesulfonates Can be mentioned. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
phenolic couplers such as benzimidazoles, benzothiazoles or mercapto compounds,
These include the 5-amidnaphthol cyan coupler described in European Patent No. 161626A.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusivity of 4. Such a coupler is
Examples of magenta couplers are described in US Pat. No. 4.3.66.237, and examples of yellow, magenta or cyan couplers are described in European Patent No. 96,570.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3,451.82.
It is written in No. 0, etc.

Specific examples of polymerized magenta couplers are described in U.S. Pat.
, No. 367.282, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler that releases the development inhibitor is the aforementioned (7) RD17643.
．． It generally contains patented image suppressants or antifoggants as described in Items (1) to (F). Also, if necessary,
Hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanol aliquots, catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo[2°2.2]
octane), ethylene glycol,
organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, ■-phenyl-3-pyrazolidone; auxiliary developing agents, viscosity-imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, etc. Acetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1 diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N
Representative examples include 'N'-tetramethylenephosphonic acid, ethylene diamine di(0-hydroxyphenylacetic acid), and salts thereof.

At high temperatures, mercapto compounds with water-soluble groups (JP-A-51-27935), 5
-Mercapto-1,3,4-thiadiazole
1-102639), mercaptohydrotriazine (
Although it has been disclosed that 3-mercaptobenzoic acid (Japanese Unexamined Patent Publication No. 55-79436) and 3-mercaptobenzoic acid (German Publication No. 3226231) are particularly effective, compounds commonly used as anti-fogging agents cannot be used at high temperatures. Generally, it can be used effectively even in the case of development.

In addition, in order to adjust the balance between the development speed of the surface layer and the deep layer during high-temperature development, compounds with relatively high activity and strong selective action on the surface layer are added to the photosensitive material, pre-bath solution, or developer. It may be appropriate to include. For this purpose, the specific implementation of the development treatment described in British Patent No. 1 and above includes:
A special formulation may be designed for high-temperature development, or an existing process may be modified for high-temperature development by adjusting the time, temperature, use of antifoggants and development inhibitors, and the concentration of each component including the developing agent. It's okay.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. Examples of bleaching agents include iron (■), Kobal l-(I
Compounds of polyvalent metals such as [[), chromium (■), and copper (n), peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobal (In), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and cyclohexanediamine 4457664 3-mercapto-5- Amidotriazole derivatives, mercaptotriazoles disclosed in Japanese Patent Publication No. 46-19039, benzothiazoliums disclosed in U.S. Pat. No. 3,342,596, mercaptotetrazaindenes disclosed in U.S. Pat. No. 3,833,376, thiazolium salts and selenazolium as disclosed in Japanese Patent Publication No. 43332-1980. Salt, etc. are suitable.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. In this black and white developer, known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as -phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol are used alone or Can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. Furthermore, when reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

Aminopolycarboxylic acids such as acetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol ether diamine tetraacetic acid, etc. or complex salts of citric acid, tartaric acid, malic acid, etc.; persulfates; bromates; permanganates ;Nitrobenzenes and the like can be used. Among these, aminopolycarboxylic acid iron (I[[) complex salts and persulfates, including iron(III) ethylenediaminetetraacetate complex salts, are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron(1) complex salts are particularly useful in both bleach and bleach-fix solutions.

The pH of bleaching solutions or bleach-fixing solutions using these aminopolycarboxylic acid iron(III) complexes is usually 5.5 to 8, but in order to speed up the processing, the pH can be lowered. .

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnalof the 5ociety of Mo
tion Picture and Televisi
on Engineers Volume 64, P, 248~
253 (May 1955 issue).

In the stabilization process, Jikai [No. 57-8, 543, 5
All known methods described in Nos. B-14,834 and 60-220,345 can be used.

(Example) Examples of the present invention will be shown below.

Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color light-sensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is expressed in g/rrY units of silver for silver halide and colloidal silver, the amount expressed in g/rd unit for coupler additives and gelatin, and the amount expressed in g/rd unit of silver for silver halide and colloidal silver. The number of moles is expressed per mole of silver halide in the same layer.

1st layer (antihalation layer) Black colloidal silver...0,2 Gelatin...1.3ExM-8...0
．． 06 UV-1...0. l UV-2...0.2 Solv-1=...0. 0I Solv-2...0. 01 Second layer (intermediate layer) Fine grain silver bromide (average particle size 0.07μ)...0.10 Gelatin...1.5UV-1...
0.06 UV-2...0.03 ExC-2...0.02 EχF-1...0,004 Solv-1--0. l 5olv-2-0,09 Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (Ag 12 mol%, internal height A, g T type,
Equivalent sphere diameter 0.3μ, coefficient of variation of equivalent sphere diameter 29%, normal crystal, twinned mixed particles, diameter/thickness ratio 2.5) Gelatin ExS-I ExS-2 ExS-3 ExC-3 Exl:, -4 ExC-7 ExC-2 olv-I olv-3 Coated silver amount ・ ・ ・ ・ ・ 0.4 ・ ・ 0.6 ・ ・ ・ 1. 0XIO-' ・ ・ ・3. OXl, 0-' ・ ・ ・ lXl0-' ・ ・ ・0.06 ・ ・ ・0.06 ・ ・ ・0.04 ・ ・ ・0.03 ・ ・ ・0.03 ・ ・ ・0.012 4th layer (Second red-sensitive emulsion layer) Silver iodobromide emulsion (Agxs mol%, internal high Agl type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 25%, normal crystal, mixed twin grains, diameter/thickness Ratio 4) Coated silver amount...0.1 ExS-1... lXl0-' ExS-2... 3xlO-' ExS-3-lXl0-5 ExC-3...0. 24 ExC-4・--0, 24 ExC-7...0.04 ExC-2-...0. 04 Solv-1=0. 15 SO1v-3...0.02 5th layer (third red-sensitive emulsion layer) Silver iodobromide emulsion (Ag 110 mol%, internal high Agl type, equivalent sphere diameter 0.8 μ, coefficient of variation of equivalent sphere diameter 16 %, normal crystal,
Twinned mixed particles, diameter/thickness ratio 1.3) Coated silver amount...1.0 Gelatin...1.0ExS-1
... I X 10-'EχS-2... 3X
10-'ExS-3...-lXl0-' ExC-5--0,05 ExC-6...-0,l 5olv-1...0.01 Solv-2-=0. 05 6th layer (middle layer) Gelatin...1.0cpd-t
...0.03So Iv-1・
...0.05 7th layer (first green-sensitive emulsion layer) Silver iodobromide emulsion (Ag 12 mol%, internal high Agl type, equivalent sphere diameter 0.3 μ, coefficient of variation of equivalent sphere diameter 28%, normal crystal, Twin crystal mixed grains, diameter/thickness ratio 2.5) Coated silver amount......0.30 ExS-4-5X10-' So 1v-1...-0,2 9th layer (3rd glaucoma) Emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, internal high Agl type, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 80%, normal crystal, mixed twin grains, diameter/thickness ratio 1.2) Coated silver amount ...0.85 ...1.0 ...3.5X10-'...1.4X10-' ...0.01 ...0.03 ...0 .20 ...0.02 ...0.02 ...0.20 ...0.05 Gelatin ExS-7 ExS-8 xM-11 xM-12 xM-13 xM-8 xY-15 olv- 1 olv-2 10th layer (yellow filter layer) Gelatin...1.2 Yellow colloidal silver...0.08ExS-6...
・0.3X10-'ExS-5・ ・ ・ 2X
10-' Gelatin...1. OE
xM-9= -0,2 ExY-14...0.03 ExM-8...0.03 Solv-1...0. 5 8th layer (second green emulsion layer) Silver iodobromide emulsion (Ag 14 mol%, internal high Agl type, equivalent sphere diameter 0.6μ, coefficient of variation of equivalent sphere diameter 38%, normal crystal, twin mixed grains , diameter/thickness ratio 4) Coated silver amount...0.4 ExS-4= 5X10-' ExS-5... 2X10-'ExS-6--・0.3X10-' ExM-9・・・0.25 ExM-8・−・0.03 ExM-10・−・0.015 ExY-14−・・0. 01 Cpd-2・・・0. l 5olv-1... 0.3 11th layer (first blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag 14 mol%, high Agl type, equivalent sphere diameter 0.5 μ, coefficient of variation of equivalent sphere diameter 15% , octahedral particles) Coated silver amount...0.4 Gelatin...1,0ExS-9
=・2X10-'ExY-16...0. 9 ExY-14...0. 07 Solv-4-0,2 12th layer (second blue-sensitive emulsion layer) Silver iodobromide emulsion (Agllo mol%, internal high Agl type, equivalent sphere diameter 1.3μ, coefficient of variation of equivalent sphere diameter 25%, normal crystal,
Twinned mixed particles, diameter/thickness ratio 4.5) Coated silver amount...0.5 Gelatin...0.6ExS-9
・・・ IXLO-' ExY-16・ ・ ・0.25 Solv-1・ ・・0.07 13th layer (first protective layer) Gelatin ・・0.8UV-1・
・・0. l UV-2...0.2 Solv-1...0. 01 Solv-2-0,01 14th layer (second protective layer) Fine grain silver bromide (average particle size 0.07μ)...0.5 Gelatin...0.45 polymethyl methacrylate particles (diameter 1.5μ)...01 H-1...0゜cp d-3...0゜Cpd-4...O0 In addition to the above ingredients, each layer contains a surfactant as a coating aid. Added. Sample 10 was prepared as above.
It was set to 1.

ExY xF Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below.

UV-2 Solv-1 Tricresyl phosphate 5olv-2 Dibutyl phthalate 5olv-37 Bis(2-ethylhexyl) talate Ex
Y x Y CH.

CH.

C(CH3)3 xM xC xM mol, sail, approximately 20°xY pd pd xS ■ xS xS-3 xS-4 xS xS-9 CH2=CH-so2-CH2-CONH-cHzCH
2=CH-3Oz-CH2-CONH-cHzxS-5 xS-6 EχS-7 pd-3 p d-4 The sample prepared in the above manner was designated as 101, and the slit developing machine shown below (see Figure 1) was used. ) was used to perform the below-described treatments (A) and (B).

As shown in the cross-sectional view of FIG. 1, the developer tank 2 includes a lid 8 with a developer tank comb-shaped upper lid 6 suspended above the upper opening of the developer housing 4. As shown in FIG. A handle 10 is provided at the center of the upper surface of M8. The upper lid 6 has a plurality of upper lid members 12 made of vinyl chloride each having a rectangular cross section arranged substantially vertically, and a photosensitive material feed reel 16 is arranged at the joining portion of the upper and lower ends of these upper lid members 12 .

A heat conductive wall material 14 that forms a processing path 15 in combination with the upper lid material 12 is arranged inside the developing housing 4 .

Therefore, the upper cover material 12 and the heat conductive wall material 14 form a continuous wave-shaped processing path 15, and photosensitive material feeding reels 16 are arranged at the upper and lower bends of the processing path 15, respectively. In FIG. 1, two photosensitive material feed reels 16 are provided at the top and three photosensitive material feed reels 16 are provided at the bottom, but in the simplest device, only one photosensitive material feed reel 16 is provided at the bottom. , one processing path 15 is provided on each side. Furthermore, a photosensitive material feeding reel may be provided in the intermediate portion of the processing path 15 if desired.

An overflow hole 22 is provided at the slit-shaped outlet of the processing path 15, and the level of the developer in the processing path 15 is never higher than the overflow hole 22. In addition, processing path 1
A photosensitive material supply reel 2 is provided above the inlet and outlet portions of 5.
4 and a photosensitive material take-out reel 26 are arranged.

The refill port is located at 27, 28, and 29 in Figure 1,
It can be used depending on how it is used. Further, inside the developing housing 4, there is a hot water channel 1 for heating the liquid in the processing channel 15.
7 is provided, and hot water is circulated by a pump 11. A panel heater 19 is connected to the panel heater to heat the hot water in the hot water channel 17, and a temperature sensor 18 is connected to the panel heater for temperature control. Furthermore, a heat retaining wall material 13 is provided to prevent the temperature of the hot water in the hot water channel from decreasing.

In the above configuration, a developer is put into the processing path 15,
Hot water is poured into the hot water channel 17 to keep the developer at a constant temperature. The photosensitive material S is then supplied to the processing path 15 via the photosensitive material supply reel 24, developed while being conveyed by a plurality of photosensitive material feed reels 16, and taken out by the photosensitive material take-out reel 26.

In addition, the pump 11 has a discharge amount of 1! Since a powerful l/min pump was used, the amount of liquid contained in the hot water channel (52 minutes) was exchanged once every 20 seconds, and the water temperature in the hot water channel was approximately 38-3B, 5°C.
was maintained.

In processing (A) and CB), processing was carried out under the conditions shown below in the developer tank shown in FIG.
．． 29 is not used in Processes A and B). These results are shown in Table 1.

The effective utilization rate of the main drug and the mode of action of the inhibitory component in steady-state treatment were as follows.

Then, KBr was 3.35g/I during treatment! ,,Kl is about 1
48mg/ffi is released.

Processing method Color development 3 minutes 15 seconds Bleach 1 minute 00 seconds Bleach-fixing 3 minutes 15 seconds Processing A 38°C45mj2 38°C20rr1 38°C30mj2 Processing B 0m 1 0mff1 0mj2 In Processing A, one of the inhibitors is used in the development process. KBr increases by 0.75g#2, but Kl hardly increases. It is thought that it is adsorbed to the photosensitive material.

Process B is a low replenishment process of the present invention, and in this example water washing (2
) 1 minute 00 seconds 35°C30rnI! , 30rne cheaper
Constant 40 seconds 38°C20mff1 20mj
! Drying 1 minute 15 seconds 55°C The amount of replenishment is per 1 meter length of 35+nm width, and the amount of bleach-fix solution brought into the washing process in the above process is 2 ml per 1 meter length of photosensitive material with a width of 35 m/m. Ta.

Next, the composition of the treatment liquid will be described.

(color developer) diethylenetriamine pentaacetic acid 1-hydroxyethyl ten-1,1-diho Sulfonic acid sodium sulfite potassium carbonate potassium bromide potassium iodide hydroxylamine sulfur acid salt 4-(N-ethyl-N β-hydroxye thylamino)-2 Methylaniline sulfate add water pH adjustment Mother liquor (g) 1.0 3.0 4.0 30.0 1.4 1.5■ 2.4 4.5 1.0f 10.05 Replenisher (g) Processing A Processing B 1.1 1.1 3.2 3.2 4.4 37.0 O17 2,8 5,5 9,0 1,0! 1. Or! .

10.10 10.40 Ammonium thiosulfate water? 9 240.0m j
2 liquid (70%) Ammonia water (27%) 6.0m I
V.

Add water 1.0! pH7
, 2 (Water wash solution) common to mother liquor and replenisher Processes A and B common tap water to H-type strongly acidic cation exchange resin (Amberlite IR-120B, manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite J, manufactured by Rohm and Haas). Water was passed through a mixed bed column packed with R-400) to bring the concentration of calcium and magnesium ions to 3 mg/l! , followed by the addition of 20 mg/4 sodium isocyanurate dichloride and 150 mg/j2 sodium sulfate.

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

(Stable liquid) Common to mother liquor and replenisher (unit: g) Common to treatments A and B Formalin (37%) 2.0 mj
2 Polyoxyethylene-P -0,3 Monononylphenyl ether (bleaching solution) Common to mother liquor and replenisher (unit: g) Treatments A and B common Ethylenediamine tetranoic acid 120.0 Diammonium trihydrate Ethylenediamine tetrahydrochloride Diacetate 10.0 Sodium chloride Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleach accelerator
0.005M ammonia water (2
7%) Add 15.0ml water
1.0ρpH
6.3 (Bleach-fix solution) Common to mother liquor and replenisher (unit: g) Treatments A and B common Ethylenediaminetetraacetic acid 50.0 Diiron ammonium dihydrate Ethylenediaminetetraacetic acid disodium salt Sodium sulfite 5,0 12,0 By adding ethylenediaminetetraacetic acid-sodium brine T) H 0, 05 1, 02 5, 0 to 8.0 As a result, the same photographic properties as Process B could be obtained. That is, even in high-temperature and rapid processing, the method of the present invention can improve the identification effect.

Example 3 The following points in Process B of Example 1 were changed.

l) Processing temperature: 5o"c ii) Add 5-methylbenztriazole to 9mg/l at 30 seconds in the middle of the slit tank iii) Processing time: 110 seconds The photographic properties obtained are the same as those in Process B. The difference was the same, and the distinguishability was improved despite the high temperature and rapid formation of the layer.

Example 4 Fuji Color Paper Type A was developed using a three-tank processing apparatus. The developer and bleach-fix solution used at this time and the processing steps are shown below.

The following three treatments were performed.

Processing (1) Using only the first tank, add the indicated replenisher 3 times.
55mff1/rrf was supplemented.

Results Photographic Properties 2 The method according to the present invention in which the inhibitory component acts midway with low replenishment is such that Dmin is 0. 02 to 0.04, and the graininess also improved.

In terms of processing load of waste liquid, the development replenishment amount is 1.3n/n (0°2'l!
/n(, the amount of waste liquid decreased from 1.26!/bo to 0.
2! I was able to reduce it to M2/Bo.

The COD load also decreases in proportion to this amount ratio.

The amount of economical herbal medicine used is 5.5g #2X1.3j2/bo to 9g
/j2xO,291,/bo decreased.

Example 2 The same procedure as in Example 1 was carried out except for the following changes in Process B of Example 1.

i) Raise the treatment temperature to 46°C.

ii) The processing time is 2 minutes and 10 seconds.

Treatment (2) Only the first tank was used and replenishment was performed at a reduced volume (60 mI!, /rr?).

Treatment (3) Transferred to No. 1-2-3 tank at equal time intervals. Replenishment was done by replenishing the first tank in reduced quantities.

Processing process Developer solution 50°C bleach-fix solution Wash with water 30 seconds 30 seconds 30 seconds (bleach-fix solution) EDTA, iron (1), ammonium 30 g EDTA
・4Ammonium 3g48% ammonium thiosulfate aqueous solution 80m4Sodium sulfite
Add 3g water to total amount
Let's say 1.

Results: Compared to the standard process of process (1), process (2) is not practical because the development is significantly delayed and the contrast is low.

When processing (3) is performed, fog is low, sensitivity and gradation are sufficient, and discrimination is improved.

In the present invention, the occurrence of fog is suppressed and the color density of the image area is not affected, resulting in improved discrimination and an increase in relative sensitivity at the point of fog +0.2. .

(Effect of the invention) The present invention has achieved the following effects.

1. Even with low replenishment amount (replenishment active ingredient/consumed active ingredient <2.5), processing fluctuation is small. 2. Discrimination effect is large. 3. Waste liquid treatment load (BOD, COD) due to low VA replenishment range.
(both in terms of load and waste volume).

4. Effective use of developer is important. thus saving resources 5. Cost reduction 6. Downsizing of processing machines due to reduction in replenishment

[Brief explanation of the drawing]

FIG. 1 shows a sectional view of a developer tank that can be used in the present invention. 2: Developer tank, 4: Developer housing, 6-Developer tank comb-shaped upper lid, 8: Lid, 10: Handle, 11: Pump,
12: Top cover material, 13: Heat retaining wall material, 14: Heat conductive wall material, 15: Processing path, 16: Feed reel, 1
7: Hot water channel, 18: Temperature sensor, 19; Panel heater 22 = Overflow hole, 24: Supply reel, 26: Takeout reel, 27, 28, 29: Refill port, Attorney (8107) Kiyotaka Sasaki (and 3 others) Name) Procedural amendment dated 2z/q/1999

Claims (1)

[Claims] When carrying out color development of a silver halide color light-sensitive material using an aromatic primary amine type developing agent, the amount of replenishment of the developing agent is within 2.5 times the amount of developing agent consumed during development, and the color development step A method for processing a silver halide color photographic light-sensitive material, characterized in that a development inhibiting component is newly applied during the process.