JP2001166440A - Color developing composition for silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color developing composition for a silver halide color photographic sensitive material which shortens color developing time, gives good color balance and is excellent in color reproducibility and a developing method and to particularly provide a thick liquid processing agent composition which is hardly oxidized by air and does not cause deposition, the climbing of crystals on the wall surface of a developing tank, tar contamination and the coloring of a vessel. SOLUTION: The color developing composition contains a compound of the formula R1-SO3M (where R1 is a 4-10C alkyl; and M is a cation) and at least one compound selected from a polyethylene glycol having a number average molecular weight of <=2,000, ureas and polyvinylpyrrolidones. In the developing method, color development is carried out with a replenisher solution for color development or a developing solution obtained by diluting the developer composition within 2.5 min or at >=40 deg.C processing temperature.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color developing composition used for processing a silver halide color photographic material and a developing method using the same. The present invention relates to a color developing composition and a developing method capable of obtaining an excellent color balance and effectively preventing crystal crawling of the color developing tank and tar stains.

[0002]

2. Description of the Related Art In recent years, with the spread of small in-store processing service systems called mini-labs, silver halide photographic materials (hereinafter referred to as photographic materials for simplicity, There is a strong demand for reducing the time required for development processing.

[0003] As a means for speeding up the color development process, a method of increasing the pH and processing temperature of a developer has been attempted.
The photographic performance during continuous processing greatly fluctuated, and the stability of the developing solution was also deteriorated, which was not suitable for practical use. Also,
Examination of speeding up processing by activating a color developing solution such as increasing the concentration of a color developing agent described in JP-A-4-67038 or increasing the temperature as described in JP-A-4-81848. Has been repeated.

[0004]

However, in the color development processing step, the color developing agent and the alkaline agent are
The permeation, reaction, and consumption from the upper layer of the light-sensitive material delay consumption of the active ingredients of the main drug and the alkaline agent to the lowermost layer. In particular, when rapid processing is performed, the main agent is not sufficiently supplied to the lowermost layer. Therefore, improvement of the developability of the lowermost layer is the greatest problem in realizing rapid processing. The development of the layer close to the support (lower layer) shortens the color development time, so the supply of the developing agent is rate-limiting, and is slower than the development of the layer farther from the support (upper layer), resulting in color balance Is greatly disturbed, and the color reproducibility is remarkably deteriorated.

Therefore, as described above, by increasing the concentration of the main agent of the color developing solution and increasing the temperature of the processing solution, the activity of the color developing solution is increased, thereby improving the developability of the lowermost layer. In order to obtain a sufficient color density of the lowermost layer, the supply of the color developing agent and the alkaline agent to the upper layer becomes excessive, and the density becomes lower than the standard density obtained by the current processing. The density is too high, and especially in the case of a photosensitive material for photographing, it causes a large obstacle such as difficulty in printing during printing. Thus, rapid processing cannot be realized only by increasing the concentration of the main agent of the color developing solution and increasing the temperature of the processing solution.

On the other hand, as the color development processing of the silver halide color photographic light-sensitive material is continued in the color developing tank, a color developing solution component precipitates and a crystal crawls up from the wall surface of the developing tank, or the color develops. The developing agent is exposed to air oxidation, causing tar-like stains on the wall of the processing tank, and contaminating the developing device and the developing solution, as well as reducing the processing activity of the color developing solution. There is also a need for a method of doing so.

In order to supply a color developing agent to a developing laboratory, a so-called solid processing in which a powder chemical mixture in which processing chemicals constituting a processing liquid are mixed at a ratio corresponding to the processing liquid composition is prepared and packaged. It is supplied to the developer in the form of an agent, and it is dissolved in water and diluted to an appropriate concentration at the developer to use as a processing solution. A concentrated liquid processing agent method is used in which a concentrated liquid processing agent is supplied in the form of a concentrated liquid processing agent filled in a container, diluted with water, etc. to a specified concentration in the developing site and used as a processing liquid. However, in order to further facilitate the management of a concentrated liquid processing agent having excellent handleability, it is also desired to provide a processing agent having an excellent effect of preventing precipitation of a developing agent (a processing agent having excellent precipitation resistance).

Accordingly, an object of the present invention is to provide a color developing composition and a developing method which are capable of shortening the color developing time of a silver halide color photographic light-sensitive material and having good color balance and excellent color reproducibility. It is in. It is a further object of the present invention to provide a color developing composition and a developing method capable of easily preventing precipitation of a processing solution, that is, easily preventing crystal crawling and tar contamination of a color developing tank. . A further object of the present invention is that despite the high content of the color developing agent, there is no precipitation of insoluble matter during storage, no coloring of the processing solution or the processing agent container due to air oxidation, and photographic processing. It is an object of the present invention to provide a liquid concentrated color developer composition for color photographic light-sensitive materials without deterioration in performance.

[0009]

It has been found that the above object of the present invention can be attained by the following (1) to (4).

(1) At least one compound selected from the compounds represented by the following general formula (I), polyethylene glycol (number average molecular weight of 2,000 or less, hereinafter simply referred to as average molecular weight), urea, A color developing composition for a silver halide color photographic light-sensitive material, which comprises at least one compound selected from polyvinylpyrrolidones.

General formula (I) R ¹ -SO ₃ M In general formula (I), R ¹ represents an alkyl group having 4 to 10 carbon atoms, and M represents a cation.

(2) At least one compound selected from the compounds represented by the above general formula (I) and at least one compound selected from polyethylene glycol (average molecular weight of 2000 or less), ureas and polyvinylpyrrolidones 1. A concentrated liquid color developer composition for a silver halide color photographic light-sensitive material, comprising:

(3) A silver halide color photographic light-sensitive material which performs color development within 2 minutes and 30 seconds using the development processing composition described in (1) above as a color development replenisher or developer. Material development processing method.

(4) A silver halide color photograph characterized in that a color development process is carried out at a processing temperature of 40 ° C. or more using the development processing composition described in the above (1) as a color development replenisher or a developer. Development method of photosensitive material.

The present invention provides, as a color developing composition for a color photographic light-sensitive material, at least one compound selected from the compounds represented by the above formula (I) together with a color developing agent.
The color development time is shortened by using the compound of the present invention in combination with at least one compound selected from the group consisting of polyethylene glycol (however, an average molecular weight of 2,000 or less), ureas and polyvinylpyrrolidones. However, the present inventors have found that the deterioration of the color balance, which is caused when the conventional color developing solution is rapidly processed, can be effectively prevented, and have reached the present invention. Especially 2 min 30
The above effects are effectively exhibited in rapid and / or high-temperature color development processing within seconds and / or 40 ° C. or higher.

In the present invention, the term "color developing composition" refers to a developing solution (a solution for processing a light-sensitive material, hereinafter also referred to as a processing solution form), a replenisher composition for replenishing the solution and maintaining its performance. (Hereinafter, also referred to as a replenisher form), and a processing composition (hereinafter, referred to as a replenisher) for supplying the developing solution or replenisher composition
Also referred to as a supply treatment agent form. Any of a solid processing agent and a liquid concentrated processing agent).

Furthermore, it has been found that the color developing solution having the above-mentioned structure effectively prevents crystal crawling and tar stain in the developing tank, and causes little deterioration in photographic performance. Furthermore, even when the color development processing composition of the present invention is applied as a liquid concentrated processing agent in the above-mentioned supply processing agent form, insoluble matter is stored during storage despite containing a high concentration of the color developing agent. It does not precipitate and is less susceptible to air oxidation, resulting in improved stability and no coloration due to oxidation of the processing solution and the developing agent in the processing agent container, including the storage period before using the color developing agent. Was issued.

As described above, the term "concentrated liquid processing agent" or "concentrated liquid color developer composition" used in the present invention, when supplied to a developing laboratory, dissolves a processing chemical at a high concentration to form a liquid concentrated state. It means a concentrated liquid treatment agent suitable for filling in a container, and is distinguished from a so-called solid treatment agent. Usually, the concentrated liquid color developer composition of the present invention is used as a processing liquid by diluting it with water or the like to a concentration determined in a developer. It may be diluted before being introduced into the treatment bath,
The treatment liquid may be separately added to the treatment bath with the dilution water to form a treatment liquid.

The compound of the general formula (I) of the present invention is
JP-A-62-234161 discloses that it can be used as a developer component for a silver halide color photographic light-sensitive material.
Although described in JP-A-11-149144,
By using the compound (I) in combination with the above-mentioned polyethylene glycol (average molecular weight of 2,000 or less) or the like, the color balance at the time of the above-mentioned rapid processing is greatly improved, and the precipitation resistance is improved. No disclosure or suggestion is made.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. Examples of the compound represented by the general formula (I) include the following. Among them, preferred compounds are (I
-3), (I-4), (I-5), (I-9) and (I-9)
-11).

[0021]

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The color developing composition of the present invention comprises at least one compound selected from the group consisting of polyethylene glycol (not more than 2,000 in average molecular weight), ureas and polyvinylpyrrolidones, together with the compound represented by formula (I). It contains.

Examples of polyethylene glycol having an average molecular weight of 2000 or less include diethylene glycol, triethylene glycol and polyethylene glycol (average molecular weight:
200, 300, 400, 600, 1000, 154
0, 2000), preferably diethylene glycol, triethylene glycol, polyethylene glycol (average molecular weight: 1,000 to 2,000). The average molecular weight is preferably from 100 to 2,000.

Examples of the ureas include the following compounds. Among them, (E-11) is preferable.

[0025]

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[0026]

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The polyvinylpyrrolidone includes poly-
N-vinyl-2-pyrrolidone, poly-N-vinyl-2-
Pyrrolidone / vinyl alcohol.

More preferably, the compound represented by the general formula (I) and diethylene glycol, triethylene glycol and / or polyethylene glycol (average molecular weight: 1)
000-2000), and further poly-N-
It is preferable to use a combination of vinyl-2-pyrrolidone.

The developing composition of the present invention preferably contains 0.01 to 200 g of the compound represented by the general formula (I) per liter of the developing composition. Further, when the developing composition is in the form of a processing solution, the compound of the formula (I) may be used in an amount of 0.1 to 50 per liter of the processing composition.
g, polyethylene glycol 1-50 g, urea 1
-50 g, and preferably 0.1-20 g of polyvinylpyrrolidone. When the development processing composition is in the form of a replenisher, 0.1 to 50 g of the compound of the formula (I) and polyethylene glycol 1 to 5 per liter of the processing composition
0 g, ureas 0.5 to 50 g, and polyvinyl pyrrolidone 0.05 to 20 g are preferably contained.

When the developing composition is in the form of a supply, if it is a concentrated liquid treating agent, 1 to 100 g of the compound of the formula (I), 5 to 80 g of polyethylene glycol, It is preferable to contain 5 to 50 g and 1 to 20 g of polyvinylpyrrolidone. In the case of a solid processing agent, it is preferable to set the concentration of the “replenisher solution” to a concentration of the “replenisher solution” when supplied as a replenisher so that the concentration becomes the “treatment solution” after dissolution. .

Next, components of the developing composition of the present invention other than those described above will be described. Although the development processing composition contains a color developing agent, a preferred example is a known aromatic primary amine color developing agent, particularly a p-phenylenediamine derivative. Representative examples are shown below, but are not limited thereto. Not something. In recent years, some black-and-white light-sensitive materials have been added so that a coupler is added so as to develop a black color, and a black-and-white image is formed using a general-purpose general color developer. Developers are also applied to this type of photosensitive material processing.

1) N, N-diethyl-p-phenylenediamine 2) 4-amino-3-methyl-N, N-diethylaniline 3) 4-amino-N- (β-hydroxyethyl) -N-
Methylaniline 4) 4-Amino-N-ethyl-N- (β-hydroxyethyl) aniline 5) 4-Amino-3-methyl-N-ethyl-N- (β-
Hydroxyethyl) aniline 6) 4-amino-3-methyl-N-ethyl-N- (3-
Hydroxypropyl) aniline 7) 4-amino-3-methyl-N-ethyl-N- (4-
Hydroxybutyl) aniline 8) 4-amino-3-methyl-N-ethyl-N- (β-
Methanesulfonamidoethyl) aniline 9) 4-amino-N, N-diethyl-3- (β-hydroxyethyl) aniline 10) 4-amino-3methyl-N-ethyl-N- (β-
Methoxyethyl) -aniline 11) 4-amino-3-methyl-N- (β-ethoxyethyl) -N-ethylaniline 12) 4-amino-3-methyl-N- (3-carbamoylpropyl-Nn- Propylaniline 13) 4-Amino-3-methyl-N- (4-carbamoylbutyl-Nn-propylaniline 15) N- (4-amino-3-methylphenyl) -3-
Hydroxypyrrolidine 16) N- (4-amino-3-methylphenyl) -3-
(Hydroxymethyl) pyrrolidine 17) N- (4-amino-3-methylphenyl) -3-
Pyrrolidine carboxamide

Among the above-mentioned p-phenylenediamine derivatives, particularly preferred are compounds 5), 6), 7), 8) and 12), among which compounds 5) and 8) are preferred. Also, these p-phenylenediamine derivatives are
In the state of solid material, usually sulfate, hydrochloride, sulfite,
It is in the form of a salt such as naphthalenedisulfonic acid and p-toluenesulfonic acid. The processing composition is used in the form of a development replenisher (or a further diluted developer) by mixing it with water at a predetermined ratio at the time of use, and the aromatic primary amine developing solution in the use solution is used. The concentration of the base is diluted to preferably 2 to 200 mmol, more preferably 12 to 200 mmol, and still more preferably 12 to 150 mmol, per liter of the developer.

The processing composition of the present invention may contain a small amount of sulfite ion or may not substantially contain it depending on the kind of the light-sensitive material to be treated. This is because sulfite ions have a remarkable preservative action, but may adversely affect the photographic performance in the color development process depending on the target photosensitive material. Hydroxylamine may or may not be included in the components of the composition depending on the type of the light-sensitive material to be treated. This is because the photographic properties can be affected because the developer itself has a silver developing activity at the same time as the function as a preservative of the developer.

The treatment composition of the present invention preferably contains an inorganic preservative such as hydroxylamine or sulfite ion or an organic preservative. The organic preservative refers to any organic compound that reduces the deterioration rate of an aromatic primary amine color developing agent by being included in a processing solution for a photosensitive material. That is, organic compounds having a function of preventing air oxidation and the like of a color developing agent, among them, hydroxylamine derivatives, hydroxamic acids, hydrazides,
Phenols, α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, fused amines Are particularly effective organic preservatives. They are,
JP-A Nos. 63-4235, 63-30845, 63-21647, 63
-44655, 63-53551, 63-43140, 63-56654
No. 63-58346, No. 63-43138, No. 63-146041, No. 6
3-44657, 63-44656, U.S. Pat.No. 3,615,503,
No. 2,494,903, JP-A-52-143020, JP-B-48-30496
No. and other publications or specifications.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
No. 0588, salicylic acids, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, U.S. Pat.
An aromatic polyhydroxy compound described in the specification of JP-A No. 4 and the like may be contained as necessary. In particular, other than the above-mentioned alkanolamines, for example, alkanolamines such as triethanolamine and triisopropanolamine, substituted or unsubstituted dialkylhydroxylamine such as disulfoethylhydroxylamine and diethylhydroxylamine, or aromatic polyamines The addition of a hydroxy compound is preferred.

Among the above organic preservatives, hydroxylamine derivatives are particularly preferred. For details, refer to JP-A-1-97953, JP-A-1-186939, JP-A-1-186940, and 1-18.
No. 7557, etc. In particular, it is more preferable to use a hydroxylamine derivative and an amine in combination in view of improving the stability of the color developer and the stability during continuous processing. Examples of the amines include cyclic amines described in JP-A-63-239447, amines described in JP-A-63-128340, and other amines described in JP-A-1-186939. Examples thereof include amines described in JP-A-1-1187557.

If necessary, chloride ions may be added to the concentrated treatment composition of the present invention. Color developers (especially developers for color print materials) usually use chloride ions for 3.
5 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / l in many cases . The amount of chloride ions in the replenisher, and hence in the underlying processing composition, is set such that the chloride ion concentration in the developing tank when the running equilibrium composition is reached is at the above-mentioned concentration level. In many developers for photosensitive materials for printing, if the chloride ion concentration is more than 1.5 × 10 ⁻¹ mol / l, it has the disadvantage of delaying the development, and undesirably impairs the speed and color density. Also, 3.5
If it is less than × 10 ^-2 mol / l, it is often not preferable in preventing fog. Many silver halide photosensitive materials for camera photography usually contain substantially no silver chloride,
Therefore, it is not necessary to control the chloride ion concentration during the development processing, and the treating agent composition used usually does not contain chloride ions as a component.

As for the processing agent composition, bromine ions are also eluted and accumulated in the processing solution from the light-sensitive material in the same manner as in the case of chloride ions, and are therefore controlled at a concentration corresponding to the equilibrium concentration. Color bromide ion in the developing solution is about 1～5X10 ^-3 mol / l in the processing of photographic materials, the processing of the print material is preferably not more than 1.0 × 10 ^-3 mol / liter. If necessary, bromine ions may be added to the treatment composition so that the bromine ion concentration falls within this range. Iodine ions are eluted from a color photographic material for camera photography into a developing solution, but photographic materials for printing usually do not contain silver iodide. The iodine ion concentration in the developer is about 5 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol / liter, and if necessary, iodine ion is added to the processing material composition so as to maintain the concentration. When halide ions are contained in the treating agent composition, as chloride ion supplying substances, sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride,
Manganese chloride and calcium chloride can be mentioned, and preferred are sodium chloride and potassium chloride. Examples of the bromine ion supply material include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cerium bromide, and thallium bromide. Among them, preferred are potassium bromide and sodium bromide. Examples of the supply material of iodide ions include sodium iodide, potassium iodide, lithium iodide, calcium iodide, magnesium iodide, and thallium iodide. Of these, potassium iodide and sodium iodide are preferred.

When the photosensitive material to be developed is color photographic paper, it is important that the white background of the screen is white, so that it is important to make the surface apparently white with a fluorescent whitening agent. Depending on the nature of the fluorescent whitening agent, the fluorescent whitening agent is contained in the light-sensitive material. In some cases, the fluorescent whitening agent permeates the light-sensitive material from the processing solution during the development processing. In that case, an appropriate treatment liquid to be added is selected according to the properties of the fluorescent brightening agent so that a high whitening effect is obtained. Therefore, they may be added to a color developer having a high pH, and thus to a color developer. Generally, stilbene-based fluorescent brighteners are frequently used, and among them,
Di (triazylamino) stilbene-based and 4,4'-diamino-2,2'-disulfostilbene-based fluorescent whitening agents are preferred. In particular, a preferred stilbene-based optical brightener is 4,4'-ditriazinylamino-2,2'-disulfostilbene, but the present invention is not limited thereto.

The stilbene-based fluorescent whitening agent used is a known one, and can be easily obtained or can be easily synthesized by a known method. This stilbene-based fluorescent whitening agent can be added to any of a desilvering solution and a photosensitive material in addition to a color developing solution. When it is contained in a color developing solution, its preferable concentration is 1 × 10 ^{−4 to} 5 ×.
10 ^-2 mol / l, more preferably 2 × 10
⁻⁴ to 1 × 10 ⁻² mol / l. The addition amount of the processing composition of the present invention is determined so that the developing in use contains the optical brightener at this concentration level.

In the case of a concentrated liquid processing composition, the pH of the processing composition of the present invention is preferably from 9.5 to 13.5, but a color developer prepared therefrom (processing liquid form)
Has a pH of 9.0 to 12.2, more preferably 9.9 to 1
1.2 is preferred, and compounds of other known developer components can be included. In order to maintain the above pH, it is preferable to use various alkali agents and buffers.
Examples of the buffer include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, and 3,4- Dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-
1,3-propanediol salt, valine salt, proline salt,
Trishydroxyaminomethane salt, lysine salt and the like can be used. Especially carbonates, phosphates, tetraborate,
Hydroxybenzoate has excellent buffering ability in the high pH range of pH 9.0 or higher, and has the advantage of being inexpensive without any adverse effect on photographic performance (such as fog) even when added to a color developer. It is particularly preferable to use these buffers. The concentration is 0.01 to 1 liter per replenisher.
It is added to the composition in an amount of 2 mol, preferably 0.1 to 0.5 mol. The alkaline agent is added so that the developer in which the buffer is present has a predetermined pH.

Specific examples of these alkali agents and buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, Sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (Sodium 5-sulfosalicylate),
Examples thereof include potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), sodium hydroxide, potassium hydroxide, and lithium hydroxide.
However, the invention is not limited to these compounds. The amount of the buffer is 0.1 mol / L or more, particularly 0.1 mol / L, in the diluted color developing replenisher.
Mol / l to 0.4 mol / l.

Further, in the present invention, it is preferable to use potassium hydroxide in addition to potassium carbonate as the alkaline agent, and it is particularly preferable to use a part of potassium hydroxide by replacing it with lithium hydroxide. Thereby, the kit precipitation preventing effect is further improved.

The processing composition of the present invention may contain other color developing solution components, for example, various chelating agents which are precipitation inhibitors for calcium and magnesium, or which are also agents for improving the stability of the color developing solution. . For example,
Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenesulfonic acid, transsirohexanediaminetetraacetic acid, 1,2 -Diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, ethylenediaminedisuccinic acid (SS
), N- (2-carboxylateethyl) -L-aspartic acid, β-alanine diacetate, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid, 1,2-dihydroxybenzene-4,6-disulfonic acid, and the like. These chelating agents may be used in combination of two or more as necessary. The amount of these chelating agents may be an amount sufficient to block metal ions in the color developer. For example, it is added so as to be about 0.1 g to 10 g per liter.

The processing composition of the present invention may optionally contain any development accelerator. As a development accelerator,
37-16088, 37-5987, 38-7826, 44-12380
Nos. 45-9019 and U.S. Pat.No. 3,813,247 and the like. Quaternary ammonium salts represented by JP-A-50-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429, U.S. Pat.
494,903, 3,128,182, 4,230,796, 3,25
No. 3,919, JP-B-41-11431, U.S. Patent No. 2,482,546
Nos. 2,596,926 and 3,582,346, etc.
No. 42-25201, U.S. Pat.No. 3,128,183, Japanese Patent Publication No. 41-11431
No. 42-23883 and U.S. Pat.No.3,532,501.
In addition, 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as needed.

The treatment composition of the present invention may optionally contain
Optional antifoggants can be added. As the antifoggant, an organic antifoggant can be used in addition to the above-mentioned alkali metal halides such as sodium chloride, potassium bromide and potassium iodide. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine can be mentioned as typical examples. When an organic antifoggant is used, the concentration of the antifoggant in one liter of a developer or a development replenisher adjusted from the composition is 0.05 to 5%.
It is preferable to configure so as to be in the range of mmole. In addition to the surfactant in the present invention, various surfactants such as alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added as necessary. The color developing composition of the present invention and the color developing replenisher or developer prepared therefrom have been described above.

The processing temperature of color development applied to the present invention is 30 to 55 ° C., preferably 35 to 55 ° C., and more preferably 40 to 55 ° C. when the photosensitive material to be developed is a color print material. 55 ° C. The development processing time is 5 to 90 seconds, and preferably 15 to 60 seconds. The replenishment amount is preferably small, but it is suitably ^{20 to} 600 ml per 1 m ^{2 of} the light-sensitive material, and preferably 30 to 600 ml.
It is 120 ml, particularly preferably 15 to 60 ml.

On the other hand, in the case of color development of a color negative or color reversal film, the development temperature is 30 to 55, preferably 35 to 55 ° C, more preferably 40 to 55 ° C. . The development processing time is 20 seconds to 6 minutes, preferably 30 to 200 seconds, more preferably 60 seconds.
１５０150 seconds. Also, especially for color negatives, 1-4
Minutes are preferred. The replenishment amount is preferably small, but is suitably 20 to 1000 ml, preferably 50 to 600 ml, and particularly preferably 10 to 1000 ml per m ^{2 of} the light-sensitive material.
0-400 ml. This replenishing amount is the total amount of the replenisher composition and water when the concentrated replenisher composition and water are separately added to the developing tank. The present invention is particularly preferably applied to color negative processing.

One of the features of the developing composition of the present invention is that it can be highly concentrated, and one of its technical features is that it overcomes the restriction of thickening.
Therefore, it is suitable for the supply form of the thick processing agent. The degree of enrichment is determined by the fact that the concentration ratio with respect to the liquid in actual use, that is, the development replenisher or the mother liquor (tank liquid) is 1.5.
It is about 10 to 10 times, preferably 2 to 8 times, and more preferably 3 to 5 times. The concentration of the compound of the general formula (I) in the concentrated processing composition (when two or more compounds are contained, the total concentration thereof) is defined as follows:
It is 0.01 to 200 g, preferably 1 to 100 g, and more preferably 5 to 50 g. Moreover, the polyethylene glycol (average molecular weight 200
0 or less), the content of urea and / or polyvinylpyrrolidone is not particularly limited, but is 0.1 to 100 g, 1 to 50 g and 5 to 20 g, respectively, per liter of the concentrated developer composition.

It is advantageous that the concentrated developer composition of the present invention has a form in which all the components contained in the working solution are contained in one composition, that is, a so-called one-component constitution. When it is not desirable to keep the components in contact with each other, the components may be separated into two or more liquids to form a two- or three-part developer composition (usually international standard IS
According to the name of O 5989, it is called a 1, 2, 3 part configuration, etc.), and the effects and features of the invention are not lost by dividing into parts. The developer composition of the present invention preferably has a one-part structure.

Next, the container for the concentrated liquid developer of the present invention will be described. An advantage of the present invention is that the developer can be supplied in a polyethylene container. Typically, liquid developer compositions are transported, stored, and used in suitable containers. It goes without saying that the first requirement for the material of the developer container is that it must be inert and sufficiently stable with respect to the developer composition (Requirement 1). Aside from this, an important requirement is sufficient oxygen barrier properties so that air oxidation does not occur during the period from production to use of the developer composition (requirement 2). It must be recyclable (Requirement 3). Further, since the concentrated liquid developer decreases the developing activity when the pH is lowered during storage, it is preferable to avoid contact with carbon dioxide in the air. Therefore, the material of the container must be such that carbon dioxide is hardly permeated through the vessel wall together with the oxygen barrier property (requirement 4). Many materials that meet Requirement 2 are Requirement 4
Also satisfies.

From the viewpoint of the requirements 2 and 4, the developer composition
Filled with oxygen and carbon dioxide gas barrier container and store,
It is effective to store and transport. Practical use of developer composition
The material and thickness of the container must be at room temperature and pressure for
In, the air permeation speed per unit time per unit area
2.5 × 10^-7 cm^Three/cm^Two/ Sec / atm or less, preferably
2.5 × 10^-8 cm^Three/cm^Two/ Sec / atm or less
It is desired to design. On the other hand, from the viewpoint of requirement 4,
The permeation rate of the wall against carbon dioxide is 7 × 10 ^-7 cm^Three/
cm^TwoContainer made of a material of less than / sec / atm is desirable
And has been. For this reason, material restrictions were great.

In view of gas impermeability, liquid developing agents were often supplied in a sealed state in a glass bottle at the beginning of practical use. However, there are drawbacks such as large weight and easy breakage. Is being used.
Although this known composite plastic material effectively blocks air to prevent air (oxygen) oxidation and enhances the storage stability of the liquid developer, it is difficult to recycle it because it is a composite material. However, they are discarded after each use, increasing the environmental burden.

The color developing solution containing the compound of the present invention including the compound of the general formula (I) has an advantage that it is hardly subjected to air oxidation as described above.
Practical storage stability can be obtained without using such a composite material container. The material of the plastic container suitable for the present invention may have an air permeation speed 10 times higher than the above value, and a single-piece plastic that satisfies the above requirements 2 and 4 can be selected. One of the characteristic advantages of the present invention is that requirement 3 can be easily satisfied by using a single product. A particularly great advantage is that polyethylene, which was previously unusable due to insufficient air barrier properties while being easy to recycle, has protection that can be practically used as a container in the liquid developer of the present invention. .

Preferred container materials for the color developing agent of the present invention are polyester resins, acrylic resins, ABS resins, epoxy resins, polyamide resins such as nylon, polyurethane resins, polystyrene resins, polycarbonate resins, PVA, and poly (vinyl alcohol). Vinyl chloride, polyvinylidene chloride,
It is a polyethylene resin, and among them, a container composed of a polyester resin such as polyethylene terephthalate and polyethylene naphthalate and a polyolefin resin such as polyethylene and polypropylene as a single material is preferable. Among them, polyethylene is preferable, and among polyethylene, a high-density type, so-called HDPE, is preferable as the container material. Among them, preferred HDPE has a density of 0.951 to 0.9769 g / cm ³ . Having a density in this range and a melt index of 0.3
HDPE in the range of -7.0, more preferably in the range of 0.3-5.0, is advantageous in both gas permeability and moldability. The molding of the container is preferably performed by a hollow molding method in order to maintain the dimensional accuracy and the uniformity of the thickness of the container.

The polyethylene used in the container of the concentrated liquid developer composition of the present invention may contain pigments such as carbon black and titanium white which do not adversely affect the alkaline developing composition, calcium carbonate, and a plasticizer compatible with polyethylene, if necessary. May be. Preferably, the ratio of polyethylene is 85% or more and no plasticizer is contained, and more preferably, the ratio of polyethylene is 95% or more and no plasticizer is contained.

The shape and structure of the container for filling the concentrated liquid developer composition of the present invention can be arbitrarily designed according to the purpose.
Nos. 7046 and 63-50839, JP-A-1-235
No. 950, JP-A-63-45555, etc .;
Nos. 61 and 62-134626 and the like having a flexible partition can also be used.

When filling the container with the developer composition, in order to further increase the safety against air oxidation, the space above the container should be filled as much as possible to minimize the head space, or the head space should be filled with nitrogen. It is preferable to perform the filling so as to eliminate the contact with the oxygen in the air, but the present invention is not necessarily limited to such a filling method.

When the developer composition of the present invention is used in an automatic developing machine, a container filled with the developer composition is mounted on the developing machine, and the composition inside the container is placed in a developing replenishing tank or directly in a developing tank. After the injection, the container is washed with a certain amount of water, and the water used for washing is introduced into a replenishing tank, used as water for preparing a replenishing solution, and developed using the replenishing solution thus obtained. The operation method is a method that particularly effectively utilizes the advantages of the present invention. In order to wash the inside of the container with a certain amount of water, spray-type washing is particularly preferable, but is not necessarily limited to this. With this replenisher preparation method, the washing water is effectively used, and the amount of wastewater discharged from the developing station can be reduced.

Accordingly, a particularly advantageous embodiment of the present invention is a development processing system which is simple and has high environmental and operational safety by incorporating the above-mentioned developer composition. For example, using an automatic developing machine, a container filled with the developing developer composition of the present invention is mounted on the developing machine, the contents are transferred into a developing replenishing tank, and the inside of the container is sprayed.
After washing, the chemical components adhering to the vessel wall are washed away, and the water used for washing can be subjected to a developing treatment of a silver halide color light-sensitive material by a method used for preparing a replenisher or the like. In this case, when the container of the developer composition is loaded into the automatic developing machine, a mechanism is provided in which the lid of the container is automatically opened and the fluid content is smoothly discharged. In addition, Japanese Unexamined Patent Publication No.
According to the methods disclosed in Japanese Patent Application No. 82988, JP-A-8-220722 and the like, the inside of the container can be cleaned without human intervention by spraying the washing water, and the container can be handled cleanly and the recycling of the waste container is simplified. In addition, since the washing water is used as a part of the dissolved water of the developer, it does not become waste liquid. The concept of such a system can be realized only by the highly concentrated small-volume developer composition embodied in the present invention, which has sufficient fluidity for easy handling and long-term maintenance.

Next, as one embodiment of the present invention, the structure of a bottle 300 as a container for a photographic processing agent suitable for the processing method of the system incorporating a processing agent composition described above will be described with reference to FIG. However, the container for the composition of the present invention is not limited to this bottle. As shown in FIG. 1, the bottle 300 includes a container body 302. The container main body 302 is formed in a hollow box shape from a resin material (high-density polyethylene, ie, HDPE in this embodiment). The upper end of the container body 302 has a tapered shape whose diameter is gradually reduced, and a cylindrical neck portion 306 formed with a male screw 304 is formed on the outer peripheral portion. This neck 306
Is open at the upper end thereof, and the above-mentioned replenisher can be taken in and out through this opening. Further, a polyethylene (LDPE) sheet member 308 is disposed at an upper end of the neck 306. The sheet 308 member is provided with a cross-shaped thin notch, which is designed to be easily broken by a constricted hole nozzle for pouring out the contents of the bottle. Further, the fact that the sheet member 308 is LDPE and the bottle main body 302 is HDPE further ensures the sealing property of the liquid content.

The bottle 300 has a cap 310 as a fixing member. This cap 310
It is formed in a cylindrical shape with a bottom opening toward the neck portion 306, and has a male screw 30 formed on the neck portion 306 on its inner peripheral portion.
The female screw 318 corresponding to 4 is screwed into the neck 306, and by screwing into the neck 306, the polyethylene sheet 308 can be pressed by the bottom 312 of the cap 310 and the polyethylene sheet 308 can be fixed to the neck 306. Further, a circular opening 314 is formed in the bottom 312 of the cap 310 so that the sheet 308 can be perforated with the cap 310 fitted.

This bottle is mounted upside down in the replenishing section of the developing machine, and the constricted nozzle breaks the polyethylene sheet member 308 from below to put the contents into the replenishing tank. The constriction nozzle is a member having both the function of constricting and opening the seal portion of the bottle and the function of a water injection nozzle for cleaning the inner wall of the container from which the content liquid has been discharged.

There are several methods for producing a developing solution or a developing replenisher using the above-mentioned concentrated processing composition, but the following three methods give good results. However, the method of manufacturing the present invention is not limited to the following three methods. [Method A] A method in which a small amount of water is introduced into a mixing tank in advance, and constituent chemicals are sequentially charged therein with stirring. [Method B] A method in which the constituent chemical powders are mixed in advance, and then are poured into a small amount of water in the mixing tank at once. [Method C] A method in which constituent chemicals are divided into two or more groups in which components that can be conveniently combined in advance are dissolved in water or a hydrophilic mixed solvent to form a concentrated solution, and then each concentrated liquid is mixed. In addition, a combined manufacturing method partially incorporating each method can also be performed.

On the other hand, when the compound represented by the general formula (I) according to the present invention is applied as a solid processing agent, as described above, when used as a development processing solution or a development replenisher, It is preferable to set each component so that the concentration is in the form of a replenisher.

When used as a solid processing agent, the compound represented by formula (I) preferably has a particle size of 210
70% by weight or more, particularly preferably
70 μ% or more, most preferably 74 μm or less,
The value of μm or less is 70% by weight or more. The particle size was measured using a JIS (Japanese Industrial Standard) standard sieve and a gravimetric method.

For compression molding of the solid processing agent according to the present invention,
From the viewpoint of the effects of the present invention, a general rotary tableting machine, a single-shot tableting machine, an oil press, a briquette machine, a solid processing agent can be manufactured using a roller compactor and the like, but preferably, a rotary tableting machine is used. good.

In order to grind the compound represented by the general formula (I) of the present invention to the preferred particle size of the present invention, a hammer mill is used.
A commercially available pulverizer such as a roll mill, a screen mill, and a pin mill can be used. If necessary, a portion having a required particle size can be used by sieving with a sieve.

The term "powder" as used in the present invention refers to an aggregate of fine crystals, and the term "granules" refers to a substance obtained by adding a granulating step to a powder and has a particle diameter of 50 to 5000 μm. Powder or granules are compression molded into a certain shape.
From the viewpoint of the effect of the present invention, it is preferable to form all or a part except for the general formula (I) after granulating.

As a granulation method for forming granules, known methods such as tumbling granulation, extrusion granulation, compression granulation, pulverization granulation, and fluidized bed granulation can be used. For tablet formation, the average particle size of the obtained granules is 100 to 2000 μm, because the granules are mixed and compression-molded. It is preferably used, and more preferably 200 to 1500 μm.

The compound represented by the general formula (I) may be directly added to and mixed with the granular treating agent produced by the above method, or may be added and mixed with other components. Further, it may be used by directly applying it to a compressor of pressurized compression, but it is preferable to use it directly added to and mixed with the granular processing agent in view of the effects of the present invention and workability. As a mixing method, a commercially available container mixer, V-type mixer, cross-rotary mixer, Nauter mixer, or the like can be used.

In practicing the present invention, a desilvering step is carried out after a developing step using a color developing solution prepared using the developing composition of the present invention, and processing with a bleaching solution and a bleach-fixing solution is performed. . In the case of a photographic material to be subjected to color printing, this processing solution often contains an appropriate compound of the above-described fluorescent whitening agent, preferably a stilbene-based fluorescent whitening agent. As the bleaching agent used in the bleaching solution or the bleach-fixing solution, a known bleaching agent can be used. In particular, organic complex salts of iron (III) (for example, complex salts of aminopolycarboxylic acids) or citric acid, tartaric acid, malic acid Organic acids, such as persulfates and hydrogen peroxide, are preferred.

Of these, organic complex salts of iron (III) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Iron (III)
Aminopolycarboxylic acids or salts thereof useful for forming an organic complex salt of the following are listed: biodegradable ethylenediaminedisuccinic acid (SS form), N- (2-carboxylateethyl) -L-asparagine Acid, beta-alanine diacetate, methyliminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3
-Diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid,
Iminodiacetic acid, glycol ether diamine tetraacetic acid, and the like. These compounds may be any of the sodium, potassium, lithium or ammonium salts. Among these compounds, ethylenediaminedisuccinic acid (SS form), N- (2-carboxylateethyl)
-L-aspartic acid, β-alanine diacetate, ethylenediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferable because their iron (III) complex salt has good photographic properties (in the above compound, (SS
Body) has two incorrect carbon atoms,
Each of them means that the absolute configuration is S-type). These ferric ion complex salts may be used in the form of a complex salt or a ferric salt such as ferric sulfate, ferric chloride,
A ferric ion complex salt may be formed in a solution using ferric nitrate, ferric ammonium sulfate, ferric phosphate, and a chelating agent such as aminopolycarboxylic acid. In addition, the chelating agent may be used in excess of forming a ferric ion complex salt. Among the iron complexes, an aminopolycarboxylate iron complex is preferable, and the amount of addition is 0.01 to 1.0 mol / mol.
Liter, preferably 0.05 to 0.50 mol / l, more preferably 0.10 to 0.50 mol / l, and still more preferably 0.15 to 0.40 mol / l.

The bleaching time is usually 30 seconds to 6 minutes and 30 seconds, preferably 1 to 4 minutes and 30 seconds. In the case of bleaching for color printing materials, it is 30 seconds to 2 minutes. Various known organic acids (for example, glycolic acid, succinic acid, maleic acid, malonic acid, citric acid,
Organic bases (eg, imidazole,
Dimethylimidazole, etc.) or 2-picolinic acid and other compounds represented by general formula (A-a) described in JP-A-9-212819, and general formulas described in the same publication including cordic acid and the like. It is preferable to contain the compound represented by (Bb). The addition amount of these compounds is preferably from 0.005 to 3.0 mol, more preferably from 0.05 to 1.5 mol, per liter of the treatment liquid.

The fixing agent used in the bleach-fixing solution or the fixing solution includes known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate;
Ethylenebisthioglycolic acid, 3,6-dithia-1,
Thioether compounds such as 8-octanediol and water-soluble silver halide dissolving agents such as thioureas;
These can be used alone or in combination of two or more. Also, a special bleach-fixing solution comprising a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of the fixing agent per liter is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.0 mol.

The pH range of the bleach-fixing solution or fixing solution used in the present invention is preferably from 3 to 8, more preferably from 4 to 7. When the pH is lower than this, the desilvering property is improved,
The deterioration of the solution and the leuco conversion of the cyan dye are promoted. Conversely, if the pH is higher than this, desilvering will be delayed and stain will easily occur. The pH range of the bleaching solution used in the present invention is 8
It is the following, 2-7 are preferred, and 2-6 are especially preferred. If the pH is lower than this, the deterioration of the solution and the leuco-formation of the cyan dye are promoted. To adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate and the like can be added as necessary.

Further, the bleach-fixing solution may contain other various types of fluorescent whitening agents, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol. The bleach-fixing solution and the fixing solution include sulfites (for example, sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives, Sulfite ion releasing compounds such as metabisulfite (for example, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) and arylsulfinic acids such as p-toluenesulfinic acid and m-carboxybenzenesulfinic acid It is preferable to contain the like. These compounds are preferably contained in an amount of about 0.02 to 1.0 mol / liter in terms of sulfite ion or sulfinate ion.

As a preservative, in addition to the above, ascorbic acid, carbonyl bisulfite adduct, or carbonyl compound may be added. Further, a buffer, an optical brightener, a chelating agent, an antifoaming agent, a fungicide, and the like may be added as necessary. The bleach-fix processing according to the present invention requires a processing time of 5
２４０240 seconds, preferably 10-60 seconds. The processing temperature is from 25C to 60C, preferably from 30C to 50C.
The replenishing rate is ²⁰ ml to 250 per m ² of the photosensitive material.
ml, preferably 30 ml to 100 ml, particularly preferably 15 ml to 60 ml.

After desilvering such as fixing or bleach-fixing, washing with water and / or processing with a stabilizing solution are generally performed. The amount of rinsing water in the rinsing step can be set in a wide range depending on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (the number of stages), and various other conditions.
Among them, the relationship between the number of washing tanks and water volume in the multi-stage countercurrent method is described in Journal of the Society of Motion Picture and Television Engineers (Journal of the Society of Motion Picture).
and Television Engineers) Vol. 64, pp. 248-253 (1955
May issue). Usually, the number of stages in the multistage countercurrent system is preferably 3 to 15, and particularly preferably 3 to 10.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, and the increase in the residence time of water in the tank causes bacteria to propagate and the resulting suspended matter to adhere to the photosensitive material. Occurs. As a solution to such a problem, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively.
Further, chlorinated fungicides such as isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorinated sodium isocyanurate described in JP-A-61-120145, and JP-A-61-26761. Benzotriazole, copper ion, and others described in the official gazette.
1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Fungicide, "Encyclopedia of Antifungal Agents" (1986) Can be used.

Since the amount of washing water can be greatly reduced by the multi-stage countercurrent washing method as much as the conventionally used stable liquid,
This is sometimes called a washing substitute stabilizer. On the other hand, a stabilizing solution conventionally used for stabilizing an image may be used, and therefore, a normal washing method,
A combination treatment of one or more of a washing alternative stabilizing method and an image stabilizing method is performed.

The treatment with the stabilizing solution may be continued to the washing step or
Alternatively, it can be performed directly without going through the water washing step. A compound having an image stabilizing function is added to the stabilizing solution, and examples thereof include an aldehyde compound represented by formalin, a buffering agent for adjusting a membrane pH suitable for stabilizing a dye, and an ammonium compound. Particularly, aldehydes such as formaldehyde, acetaldehyde and pyruvaldehyde are used to inactivate the remaining magenta coupler to prevent fading of the dye and generation of stain, US Pat. No. 478.
No. 6583, methylol compounds and hexamethylenetetramine, JP-A-2-153348, hexahydrotriazines, U.S. Pat. Azolylmethylamines described in JP-A-519190 and the like are added. However, all of the above-mentioned water-washing and stabilizing liquids have a water-washing action, and have substantially the same function except that an image stabilizer is particularly added. .

In the stabilizing solution and the washing water, a surfactant as a draining agent and a chelating agent represented by EDTA as a hardening agent can be used. Further, a fluorescent whitening agent and a hardening agent may be added. In the processing of the light-sensitive material of the present invention, when stabilization is directly performed without going through a washing step, JP-A-57-8543, JP-A-58-14834, JP-A-60-22.
All known methods described in, for example, Japanese Patent Publication No. 0345 can be used. In addition, 1-hydroxyethylidene-1,1-
It is also a preferred embodiment to use a chelating agent such as diphosphonic acid or ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound.

Preferred p in the water washing step or the stabilizing solution treatment step
H is 4 to 10, and more preferably 5 to 8. The temperature can be set variously depending on the use and characteristics of the photosensitive material, but is generally 20 ° C to 50 ° C, preferably 25 ° C to 45 ° C.

[0086] Following the washing and / or stabilizing step, drying is performed. From the viewpoint of reducing the amount of water carried into the image film, it is possible to speed up drying by absorbing water with a squeeze roller or cloth immediately after leaving the washing bath. As a means of improvement from the dryer side, as a matter of course, it is possible to speed up the drying by increasing the temperature or changing the shape of the spray nozzle to increase the drying air. Further, as described in Japanese Patent Application Laid-Open No. 3-157650, it is possible to adjust the angle at which dry air is blown to the photosensitive material,
Drying can be accelerated by the method of removing the exhaust air.

The photosensitive material that can be used in the present invention will be described. As the silver halide used in the light-sensitive material according to the present invention, silver chloride, silver bromide, silver (iodo) chlorobromide, silver iodobromide and the like can be used. It is preferable to use a silver chlorobromide or silver chloride emulsion containing substantially no silver and having a silver chloride content of 98 mol% or more. The phrase "substantially free of silver iodide" means that the silver iodide content is preferably 0.1 mol% or less, more preferably 0.0 mol% or less.
It is preferably at most 1 mol%, and particularly preferably contains no silver iodide at all. For a color light-sensitive material for photographing purposes, for example, a multilayer color negative film or a color reversal film, tabular grains having a silver iodobromide internal structure or non-tabular multi-structure grains are mainly used.

The light-sensitive material according to the present invention can be decolorized on a hydrophilic colloid layer by a process described in EP 0,337,490A2, pages 27 to 76, for the purpose of improving the sharpness of the image. Dyes (especially oxonol dyes) so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, or when dihydric alcohols are added to the water-resistant resin layer of the support. (E.g., trimethylolethane) or the like.
It is preferable that the content be at least 10% by weight (more preferably at least 14% by weight).

The light-sensitive material according to the present invention is provided with a protective material such as that described in JP-A-63-271247 in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. It is preferred to add a fungicide. In the case of a photographic film photosensitive material, cellulose triacetate, poly (ethylene terephthalate) or poly (ethylene naphthalate) is used as a support for the photosensitive material according to the present invention. Is paper (resin-coated paper) laminated with white pigment-kneaded polyethylene,
A support such as a poly (ethylene terephthalate) film kneaded with a white pigment for display is used.

The photosensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure. In the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ^-4 seconds is preferred.

The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the light-sensitive material according to the present invention, and processing methods applied for processing this light-sensitive material And processing additives, EP 0,355,660 A2, JP-A-2-33144 and JP-A-62-2
Those described in the specification of No. 15272 or those listed in the following Table 1 are preferably used.

[0092]

[Table 1]

Further, as a cyan coupler, JP-A-2-33
Nos. 144, EP0,333,185A2 and JP-A-64-32260 can also be used. The cyan, magenta or yellow coupler is impregnated with a loadable latex polymer (eg, US Pat. No. 4,203,716) in the presence (or absence) of a high boiling organic solvent as described in the preceding table, or It is preferable to dissolve it together with a water-insoluble and organic solvent-soluble polymer and emulsify and disperse in a hydrophilic colloid aqueous solution. Preferred water-insoluble and organic solvent-soluble polymers are described in U.S. Pat. No. 4,857,449, columns 7 to 15 and in WO 88/007.
Homopolymers or copolymers described on pages 12 to 30 of the specification of JP-A No. 23 are mentioned. In particular, a methacrylate or acrylamide polymer is particularly preferred in terms of color image stability and the like.

The photosensitive material according to the present invention includes European Patent E
It is preferable to use a color image preservability improving compound as described in P0,277,589A2 in combination with a pyrazoloazole coupler, a pyrrolotriazole coupler, or an acylacetamide type yellow coupler.

Examples of the cyan coupler include phenol couplers and naphthol couplers described in the publicly known documents listed in the above table, as well as JP-A-2-33144.
JP, EP 0333185 A2, JP-A-6
4-32260, European Patent EP 0 456 226 A1, European Patent EP 0 484 909, European Patent EP
Preference is given to using the cyan couplers described in US Pat. No. 4,488,248 and EP0491197A1.

The magenta couplers used in the present invention include 5-pyrazolone-based magenta couplers described in the publicly known documents listed in the above table, as well as WO92.
/ 18901, WO92 / 18902 and WO9
The thing described in 2/18903 is also preferred. These 5
In addition to pyrazolone magenta couplers, known pyrazoloazole type couplers can be used in the present invention. Among them, in terms of hue, image stability, color development, etc., JP-A-61-652.
No. 45, JP-A-61-65246, JP-A-61-65246
No. 14254, European Patent Nos. 226,849A and 2nd.
The use of pyrazoloazole couplers described in 94,785A is preferred.

As the yellow coupler, known acylacetanilide-type couplers are preferably used.
07701, JP-A-5-113642, European Patent E
The couplers described in P-0482552A and EP-0524540A are preferably used.

Examples of couplers in which a coloring dye has an appropriate diffusivity include US Pat. No. 4,366,237, GB 2,125,
570, EP 96,873B, DE 3,234,533
Are preferred. Couplers for correcting unnecessary absorption of color-forming dyes are yellow colored cyan couplers represented by the formulas (CI), (CII), (CIII) and (CIV) described on page 5 of EP 456,257A1 (particularly Y on page 84).
C-86), yellow colored magenta coupler ExM-7 (p. 202) and EX-1 (249) described in the EP.
EX-7 (page 251), US 4,833,069
Magenta colored cyan coupler CC-9 (column 8), CC-13 (column 10) described in US Pat.
7,136 (2) (column 8), WO92 / 1157
Colorless masking couplers of formula (A) of claim 1 of claim 5 (especially the exemplified compounds on pages 36 to 45) are preferred.

Examples of compounds (including couplers) which react with oxidized developing agents to release photographically useful compound residues include the following. Development inhibitor releasing compound: E
Formulas (I), (II), and P378, 236A1 on page 11;
Compounds represented by (III) and (IV) (particularly T-101
(Page 30), T-104 (page 31), T-113 (36
Page), T-131 (page 45), T-144 (page 51),
T-158 (p. 58)), EP 436, 938 A2, 7
Compounds represented by formula (I) described on page (particularly D-49)
(Page 51)), compounds represented by formula (1) of EP568,037A (especially (23) (page 11)), EP44
Formulas (I), (II) and (II) described on pages 5 to 6 of U.S. Pat.
A compound represented by I) (especially I- (1) on page 29);

Bleaching accelerator releasing compound: EP 310,12
Compounds represented by formulas (I) and (I ') on page 5 of 5A2 (especially (60) and (61) on page 61) and JP-A-6-59.
411. The compound represented by formula (I) of claim 1 (particularly (7) (p. 7); Ligand releasing compound: US 4,55
Compound represented by LIG-X described in claim 1 of 5,478 (especially, a compound on lines 21 to 41 of column 12); Leuco dye-releasing compound: US 4,749,641
Compounds 1 to 6 of columns 3 to 8; fluorescent dye releasing compounds:
C0UP-DY of claim 1 of US 4,774,181
Compound represented by E (particularly, compound 1 in columns 7-10)
-11); Development accelerator or fogging agent releasing compound: US
Formulas (1), (2) in column 3 of 4,656,123,
The compound represented by (3) (particularly, (I-2) in column 25
2)) and EP450, 637A2, page 75, 36-38.
ExZK-2 in row: Compound which releases a group which becomes a dye only after leaving: Compound represented by formula (I) in claim 1 of US Pat. No. 4,857,447 (especially, Y-1 to Y- 19).

The following additives are preferred as additives other than the coupler. Dispersion medium of oil-soluble organic compound: JP-A-62-215272
P-3, 5, 16, 19, 25, 30, 42, 49,
54, 55, 66, 81, 85, 86, 93 (140 to
144)); Latex for impregnation of oil-soluble organic compound: U
Latex described in S4, 199, 363; oxidized developing agent scavenger: a compound represented by the formula (I) in column 2, lines 54 to 62 of US 4,978,606 (especially I- (1), (2), (6), (12) (columns 4-5), U
S4, 923, 787, column 5, lines 5 to 10 (especially compound 1 (column 3); stain inhibitor: EP298)
Formulas (I) to (III) on page 4, lines 30 to 33 of 321A, particularly I-47, 72, III-1, 27 (pages 24 to 48);
Anti-fading agent: A-6,7,20 of EP298321A
21,23,24,25,26,30,37,40,4
2,48,63,90,92,94,164 (69-1)
18), columns 25-38 of US 5,122,444.
II-1 to III-23, especially III-10, EP 47134
7A, pages 8 to 12 I-1 to III-4, especially II-2, U
A-1, 1-4 of columns 32 to 40 of S5, 139, 931
8, in particular A-39, 42; a material for reducing the amount of the coloring enhancer or the color mixing inhibitor used:
Formalin scavenger: SCV-1 to 28, especially SCV-8, pages 24 to 29 of EP 477932A;

Hardener: H-1, 4, 6, 8, 14, US Pat. No. 4,618,573 on page 17 of JP-A-1-214845.
(H-1 to 54) represented by formulas (VII) to (XII) in columns 13 to 23 of JP-A-2-214852.
Compounds represented by the formula (6) at the lower right of the page (H-1 to 7)
6), especially compounds described in claim 1 of H-14, US Pat. No. 3,325,287; Development inhibitor precursors:
Compounds described in claim 1 of US Pat. No. 5,019,492, especially 28, 29 of column 7; preservative, fungicide: U
I-4 to I-3 of columns 3 to 15 of S4,923,790
-43, especially II-1, 9, 10, 18, III-25; stabilizers, antifoggants: I-1 to (14) of columns 6 to 16 of US 4,923,793, especially I-1,60 ,
(2), (13), column 25 of US 4,952,483
Compounds 1 to 65, especially 36: Chemical sensitizer: triphenylphosphine selenide, JP-A-5-40324
Compound 50 of the formula:

Dye: 15-1 of JP-A-3-156450
A-1 to b-20 on page 8, especially a-1, 12, 18, 2
7, 35, 36, b-5, pp. 27 to 29, V-1 to V-2
3, especially F-1, I-F-II-43 on pages 33 to 55 of EP 445627A, especially F-I-11 and F-II.
VIII, pages III-I to EP-157153A, pages 17-28.
36, especially III-1,3, WO88 / 04794, 8-
26, a fine crystal dispersion of Dye-1 to 124, EP319
Compounds 1 to 22 of 999A, pages 6 to 11, especially compounds 1, compounds D-1 to 87 of formulas (1) to (3) of EP519306A (pages 3 to 28), US Pat.
68,622 compounds of formula (I) 1-22
(Columns 3 to 10), compounds (1) to (31) represented by formula (I) of US Pat. No. 4,923,788 (column 2
9); UV absorber: Formula (1) of JP-A-46-3335
Compounds (18b) to (18r), 101-
427 (pages 6 to 9), compounds (3) to (66) (pages 10 to 44) represented by formula (I) and compounds HBT-1 to 10 (1) represented by formula (III) in EP520938A.
4), compounds (1) to (31) represented by the formula (1) in EP521823A (columns 2-9).

The present invention can be applied to general-purpose or movie general-purpose color negative films. Further, it is suitable for a film unit with a lens described in Japanese Patent Publication No. 2-3615 and Japanese Utility Model Publication No. 3-39784. Suitable supports that can be used in the present invention are described, for example, in RD. N
o. No. 17643, page 28; 647 of 18716
From the right column of page 648 to the left column of page 648, and the same No. 307105
On page 879, it is preferable to use a polyester support.

Color negative film used in the present invention
Preferably has a magnetic recording layer. Used in the present invention
The magnetic recording layer obtained will be described. Used in the present invention
A magnetic recording layer is a layer in which magnetic particles are dispersed in a binder.
Aqueous or organic solvent-based coating liquid was applied on the support
Things. The magnetic particles used in the present invention are γFe
_TwoO_ThreeSuch as ferromagnetic iron oxide, Co-coated γFe_TwoO_Three, Co
Magnetite, Co-containing magnetite, ferromagnetic dioxide
Chromium, ferromagnetic metal, ferromagnetic alloy, hexagonal BaFe
Light, Sr ferrite, Pb ferrite, Ca ferrite
Can be used. Co deposited γFe_TwoO_ThreeSuch as Co
Deposited ferromagnetic iron oxide is preferred. Needle shape, rice grain
Shape, spherical shape, cubic shape, plate shape, etc. Specific surface area
Then S_BETAt 20m^Two/ g or more, preferably 30 m^Two/ g or more
Particularly preferred. The saturation magnetization (σs) of the ferromagnetic material is preferable.
Or 3.0 × 10^Four~ 3.0 × 10^FiveA / m, especially
Preferably 4.0 × 10^Four~ 2.5 × 10^FiveA / m
You. Ferromagnetic particles, such as silica and / or alumina
Surface treatment with an organic material may be performed. In addition, magnetic
The body particles are formed as described in JP-A-6-160332.
Silane coupling agent or titanium coupling agent on the surface
May be processed. JP-A-4-259911, 5
No. 81652 coated with inorganic or organic material
Magnetic particles can also be used.

The binder used for the magnetic particles may be a thermoplastic resin, a thermosetting resin, a radiation-curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer, or a natural material described in JP-A-4-219569. Combinations (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. Tg of the above resin is −40 ° C. to 300 ° C.,
The weight average molecular weight is from 2,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins, and polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. As the isocyanate-based crosslinking agent, isocyanates such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate,
Reaction products of these isocyanates with polyalcohols (for example, a reaction product of 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane), and polyisocyanates formed by condensation of these isocyanates are mentioned. No. 6-59357.

As a method for dispersing the above-mentioned magnetic substance in the binder, a kneader, a pin type mill, an annular type mill and the like are preferably used, as in the method described in JP-A-6-35092. JP-A-5-088283
And other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm, more preferably 0.3 μm to
3 μm. The weight ratio between the magnetic particles and the binder is preferably 0.5: 100 to 60: 100, and more preferably 1: 100 to 30: 100. The coating amount of the magnetic particles is 0.005 to 3 g / m ² , preferably 0.01 to ³ g / m ² .
2 g / m ^2, more preferably from 0.02 to 0.5 g / m ^2. The transmission yellow density of the magnetic recording layer is 0.01 to 0.5.
50 is preferable, and 0.03 to 0.20 is more preferable.
0.04 to 0.15 is particularly preferred. The magnetic recording layer may be provided on the entire back surface of the photographic support by coating or printing, or in a stripe shape. As a method for applying the magnetic recording layer, an air doctor, a blade, an air knife, a squeeze, an impregnation, a reverse roll, a transfer roll, a gravure, a kiss, a cast, a spray, a dip, a bar, an extrusion, and the like can be used. The coating solution described in 341436 or the like is preferable.

In the magnetic recording layer, lubricity improvement, curl control,
It may have functions such as antistatic, antiadhesion, and head polishing, or may provide another functional layer to provide these functions. At least one of the particles has a Mohs hardness of 5 or more. Abrasives of the above non-spherical inorganic particles are preferred. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide, silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. US Pat. Nos. 5,336,589 and 5,25 for photosensitive materials having a magnetic recording layer
0,404, 5,229,259, 5,215,8
74, EP 466,130.

The polyester support used in the present invention will be described. For details including photosensitive materials, treatments, cartridges, and examples described later, see Japanese Patent Publication No.
4-6023 (Invention Association; 1994.3.15.). The polyester used in the present invention is formed with diol and aromatic dicarboxylic acid as essential components,
2,6-, 1,5-, 1,4 as aromatic dicarboxylic acids
-And 2,7-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, and diols such as diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol. Examples of the polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene 2,6-naphthalate is particularly preferred. The average molecular weight ranges from about 5,000 to 200,000. The Tg of the polyester of the present invention is 50 ° C. or higher, preferably 90 ° C. or higher.

Next, the polyester support is subjected to a heat treatment at a heat treatment temperature of 40 ° C. or more and less than Tg, more preferably Tg−20 ° C. or more and less than Tg in order to make it difficult to form a curl. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. The heat treatment time is 0.1 hour or more and 1500 hours or less, and more preferably 0.5 hour or more and 200 hours or less. The heat treatment of the support may be performed in the form of a roll, or may be performed while transporting the support in the form of a web. The surface is provided with irregularities (for example, Sn
(Conductive inorganic fine particles such as O ₂ and Sb ₂ O ₅ may be applied) to improve the surface condition. It is also desirable to take measures such as applying knurls to the ends and making the ends slightly higher so as to prevent the cut end of the core from appearing. These heat treatments may be performed at any stage after the formation of the support, after the surface treatment, after the application of the back layer (antistatic agent, slip agent, etc.), and after the application of the undercoat. Preferably after application of the antistatic agent. An ultraviolet absorber may be incorporated into this polyester. In order to prevent light piping, the purpose can be achieved by kneading a commercially available dye or pigment for polyester, such as Diaresin manufactured by Mitsubishi Kasei or Kayaset manufactured by Nippon Kayaku.

Next, in the present invention, surface treatment is preferably performed in order to bond the support and the light-sensitive material constituting layer. Chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
Surface activation treatments such as laser treatment, mixed acid treatment, ozone oxidation treatment and the like can be mentioned. Among the surface treatments, preferred are an ultraviolet irradiation treatment, a flame treatment, a corona treatment, and a glow treatment. Next, the undercoating method is described.
It may be more than layers. As the binder for the undercoat layer, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, including copolymers starting from monomers selected from maleic anhydride, as a starting material,
Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin. Compounds that swell the support include resorcinol and p-chlorophenol. In the undercoat layer, gelatin hardeners such as chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, and active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine) And the like, epichlorohydrin resin, active vinyl sulfone compound and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethyl methacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

In the present invention, an antistatic agent is preferably used. Examples of such antistatic agents include polymers containing carboxylic acid and carboxylate and sulfonate, cationic polymers, and ionic surfactant compounds. The most preferred antistatic agent is Zn
O, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , Si
Particle size of at least one selected from O ₂ , MgO, BaO, MoO ₃ and V ₂ O ₅ having a volume resistivity of 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less. .00
Fine particles of crystalline metal oxides or composite oxides thereof (Sb, P, B, In, S, Si, C, etc.), furthermore, sol-like metal oxides or composite oxides thereof Particles. 5 to 5%
500 mg / m ² is preferred, particularly preferably 10 to 350 mg / m ²
a m ^2. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is preferably from 1/300 to 100/1, more preferably from 1/100 to 100/5.

The light-sensitive material of the present invention preferably has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.25 or less and 0.01 or more. The measurement at this time represents the value when the stainless steel ball having a diameter of 5 mm was conveyed at 60 cm / min (25 ° C., 60% PH). In this evaluation, even when the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level. Examples of the slipping agent usable in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes such as polydimethylsiloxane, polydiethylsiloxane, and polystyrylmethyl. Siloxane, polymethylphenylsiloxane, or the like can be used. The additional layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable.

The light-sensitive material of the present invention preferably contains a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side. The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethyl methacrylate, poly (methyl methacrylate /
Methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles, and the like are preferable. 0.8 to 10 as particle size
μm is preferable, and the particle size distribution is preferably narrow,
It is preferable that 90% or more of the total number of particles is contained between 0.9 and 1.1 times the average particle size. It is also preferable to simultaneously add fine particles having a size of 0.8 μm or less in order to enhance the matting property.
m), poly (methyl methacrylate / methacrylic acid = 9)
/ 1 (molar ratio), 0.3 µm)), polystyrene particles (0.25 µm), colloidal silica (0.03 µm)
Is mentioned.

Next, the film cartridge used in the present invention will be described. The main material of the patrone used in the present invention may be metal or synthetic plastic. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the patrone of the present invention may contain various antistatic agents, carbon black, metal oxide particles, nonions, anions,
Cationic and betaine-based surfactants or polymers can be preferably used. These anti-charged patrones are disclosed in JP-A 1-312537 and JP-A 1-312553
8. Particularly, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded in order to impart light shielding properties. The size of the patrone may be 135 size at present,
To reduce the size of the camera, it is also effective to reduce the diameter of the current 135-size 25 mm cartridge to 22 mm or less.
The volume of the patrone case is 30 cm ³ or less, preferably 2
It is preferred to be 5 cm ³ or less. Weight of plastic used for patrone and patrone case is 5g
~ 15 g is preferred.

Further, a patrone used in the present invention to feed a film by rotating a spool may be used. Further, a structure may be employed in which the leading end of the film is housed in the cartridge body, and the leading end of the film is sent out from the port portion of the cartridge by rotating the spool shaft in the film sending direction. These are US 4,834,306 and 5,2
26, 613. The photographic film used in the present invention may be a so-called raw film before development,
A photographic film that has been processed may be used. Also, the raw film and the developed photographic film may be stored in the same new patrone or different patrones.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less, more preferably 16 μm or less.
Further, the film swelling speed T _1/2 is preferably 30 seconds or less, and more preferably 20 seconds or less. T _1/2 is a color developer at 30 ° C., 3
When 90% of the maximum swollen film thickness reached when the treatment is performed for 15 minutes is defined as the saturated film thickness, it is defined as the time until the film thickness itself reaches 1/2. The film thickness means a film thickness measured at 25 ° C. and a relative humidity of 55% under humidity control (2 days), and T _1/2 is a value obtained by Photographic Science and Engineering (A. Green) et al. Photogr.Sci.En
g.), Vol. 19, pages 2, 124-129. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. In addition, the swelling ratio is 150 ~
400% is preferred. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above by the formula: (maximum swelling film thickness-film thickness) / film thickness. The photosensitive material of the present invention has a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer.
It is preferable to provide a hydrophilic colloid layer (referred to as a back layer). In this back layer, the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener,
It is preferable to include a binder, a plasticizer, a lubricant, a coating aid, and a surfactant. The swelling ratio of this back layer is 1
50-500% is preferred.

[0118]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 Photographic Performance Test Tested Color Negative Film Commercially available films (all manufactured by Fuji Photo Film Co., Ltd.) were used in the following ratios.・ Film A: FUJICOLOR SUPER100 (24 shots) serial number V09140 ・ Film B: FUJICOLOR SUPER400 (24 shots) serial number N24112 ・ Film C: FUJICOLOR SUPER G ACE800 (24 shots)
Serial No. M74128 ・ Film D: FUJICOLOR nexia H400 (40 shots) Serial No. CA56-303 These photographic materials were processed at the following ratio. Film A: Film B: Film C: Film D =
4: 4: 1: 1

[0120] 2. Method of photographic property test A standard C light source and a continuous wedge of neutral color (density gradient 0.4 △ D / cm, density range 0.02) were applied to the sample film according to the method described in International Standard ISO5800 (sensitivity measuring method for color negative film). To 4.8) to perform sensitometric exposure. In the following development processing, photographic characteristics (sensitivity, gradation and fog) were obtained using this exposed sample.

3. Developing Process The developing process was performed using the following color negative developing machine and processing specifications. As a processor, an experimental machine obtained by modifying the processing time of an automatic developing machine FP-363SC manufactured by Fuji Photo Film Co., Ltd. was used. This machine is equipped with a refilling system of the automatic opening and dispensing method. The outline of the refilling system is described in the plastic (HDPE) bottle (300 in FIG. 2; Are placed side by side with the mouth of the bottle facing down, and the lid of the dispensing unit is closed, as shown in FIG. 2, the bottle moves from above to the piercing nozzle 188, and acts as a lid for the bottle. The piercing plastic sheet 308 is pierced, and the internal composition solution is poured into the replenishing tank. Thereafter, a certain amount of washing water is jetted from the nozzle hole 214 of the squeezing nozzle in a jet manner to wash the inside of the bottle. You.

The processing steps and the composition of the processing solution are shown below. (Processing step) Step Processing time Processing temperature Replenishment amount * Tank capacity Color development 2 minutes 30 seconds 41.0 ° C 15 ml 10.3 L Bleaching 25 seconds 40 ° C 5 ml 3.6 L Setting (1) 25 seconds 40 ° C -3. 6L fixed (2) 25 seconds 40 ° C 7.5ml 3.6L stable (1) 14 seconds 40 ° C-1.9L stable (2) 13 seconds 40 ° C-1.9L stable (3) 13 seconds 40 ℃ 30ml 1.9L Drying 30 seconds 60 ℃ * Replenishment amount per photosensitive material 35mm width 1.1m (equivalent to 24 Ex. 1 bottle)

The stabilizing solution is of a counterflow type (3) → (2) → (1), and the fixing solution is also connected from (2) to (1) by a countercurrent pipe. Further, 15 ml corresponding to the replenishment amount of the tank solution of the stabilizing solution (2) is allowed to flow into the fixing solution (2). The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were all 2.0 ml per 1.1 mm width of 35 mm photosensitive material.
The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developer) Tank solution Replenisher Diethylenetriaminepentaacetic acid 2.0 g 4.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.4 g 0.5 g Disodium-N, N-bis (sulfonateethyl ) Hydroxylamine 10.0 g 15.0 g Sodium sulfite 4.0 g 9.0 g Potassium bromide 1.4 g-4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 5.5 g 12.5 g Potassium carbonate 39 g 59 g Compounds described in Table-A (See Table-A) (See Table-A) Hydroxylamine sulfate 2.0 g 4.0 g Water was added to 1.0 L 1.0 L pH (sulfuric acid) And KOH) 10.10 11.20

(Bleaching solution) Tank solution Replenisher 1,3-diaminopropanetetraacetic acid ferric ammonium ammonium monohydrate 120 g 180 g Ammonium bromide 50 g 70 g Succinic acid 30 g 50 g Maleic acid 40 g 60 g Imidazole 20 g 30 g Add water. 0L 1.0L pH (adjusted with ammonia water and nitric acid) 4.6 4.0

(Fixing solution) Tank solution Replenisher Ammonium thiosulfate (750 g / L) 280 ml 750 ml Ammonium bisulfite aqueous solution (72%) 20 g 80 g Imidazole 5 g 45 g 1-mercapto-2- (N, N-dimethylaminoethyl) tetrazole 1 g 3 g Ethylenediaminetetraacetic acid 8 g 12 g Water was added to add 1 L 1 L pH (adjusted with ammonia water and nitric acid) 7.0 7.0

(Stabilizing solution) Common to tank solution and replenishing solution Sodium p-toluenesulfinate 0.03 g p-nonylphenoxypolyglycidol (glycidol average polymerization degree 10) 0.4 g Disodium ethylenediaminetetraacetate 0.05 g 1,2 1,4-Triazole 1.3g 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75g 1,2-Benzoisothiazolin-3-one 0.10g Water was added to 1.0 L pH 8.5

4. Tests and test results 3. A two-fold concentrated solution of the color developing replenisher formulation shown in the section of development processing conditions was prepared. Which is unrelated to concentration by evaporation or the like). The concentrated developer replenisher composition was placed in the plastic bottle (HDPE) and aged at 40 ° C. for 10 weeks. It is loaded into the replenisher preparation section of the remodeled developing machine, and the concentrated developer replenisher composition is discharged from the plastic bottle to the replenishment tank in the manner described above, diluted with washing water, and replenished in each replenishment tank. Was prepared. Each of the separately prepared tank solutions was placed in a developing machine, and a 30% exposure film of the film was processed while being replenished from a replenishment tank (note that 30% exposure was performed under an average photographing condition of a color negative film). The sensitivity of the silver halide grains is 30%. When the used developer replenisher reached 1.0 times the capacity of the developing tank, the light wedge-exposed sample for sensitometry of the film B was developed to obtain photographic properties. And gender. The processing steps and liquid composition of the standard processing are shown below. The processing was performed using the same composition as the processing solution except for the color developing solution.

(Processing step) Step Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 05 seconds 38.0 ° C. 15 ml 10.3 L Bleaching 50 seconds 38 ° C. 5 ml 3.6 L Settling (1) 50 seconds 38 ° C. -3.6L fixed (2) 50 seconds 38 ° C 7.5ml 3.6L stable (1) 30 seconds 38 ° C-1.9L stable (2) 20 seconds 38 ° C-1.9L stable (3) 20 seconds 38 ° C 30ml 1.9L Drying 1 minute 30 seconds 60 ° C * Replenishment amount per photosensitive material 35mm width 1.1m (equivalent to 24Ex. 1 bottle)

The stabilizing solution is of a counterflow type (3) → (2) → (1), and the fixing solution is also connected from (2) to (1) by a countercurrent pipe. Further, 15 ml corresponding to the replenishment amount of the tank solution of the stabilizing solution (2) is allowed to flow into the fixing solution (2). The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were all 2.0 ml per 1.1 mm width of 35 mm photosensitive material.
The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the processing solution is shown below. (Color developing solution) Tank solution Replenisher Diethylenetriaminepentaacetic acid 2.0 g 4.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.4 g 0.5 g Disodium-N, N-bis (sulfonateethyl ) Hydroxylamine 10.0 g 15.0 g Sodium sulfite 4.0 g 9.0 g Potassium bromide 1.4 g-Diethylene glycol 10.0 g 17.0 g Ethylene urea 3.0 g 5.5 g 4-Amino-3-methyl-N-ethyl -N- (β-hydroxyethyl) aniline sulfate 4.7 g 11.4 g Potassium carbonate 39 g 59 g Hydroxylamine sulfate 2.0 g 4.0 g Water was added to 1.0 L 1.0 L pH (with sulfuric acid and KOH) Adjustment) 10.07 10.51

(Stabilizing solution) Common to tank solution and replenisher sodium p-toluenesulfinate 0.03 g p-nonylphenoxypolyglycidol (glycidol average degree of polymerization 10) 0.4 g disodium ethylenediaminetetraacetate 0.05 g 1,2 -Benzisothiazolin-3-one 0.10 g Water was added to make 1.0 L pH 8.5

The photographic properties were compared as follows. That is, the processed sample pieces (light wedge exposed samples for sensitometry) were represented by the following color balance differences. This "color balance difference" indicates that the closer to zero, the more the color balance in the test processing is finished equal to the standard processing. The results are shown in Table-A.

Color balance difference: Δ (R−G) = [(R density during test processing) − (G density during test processing)] − [(R density during standard processing) − (G density during standard processing) Density)] The R and G densities are densities at a log exposure amount (LogE) of 3.0 (the exact numerical value of the exposure amount is 1000 cms).

[0135]

[Table 2]

From Table A, it can be seen that the compound represented by the general formula (I) and the average molecular weight 2
The effect of improving the color balance of the developer was observed when used in combination with polyethylene glycols, polyvinylpyrrolidones and ureas of 000 or less.

Example 2 Stability to Precipitation Precipitation To test the stability to precipitation, a color developer composition having the following composition was prepared. (Color developer composition) Diethylenetriaminepentaacetic acid 6.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 1.0 g Sodium sulfite 15.0 g Potassium carbonate 100.0 g Compound shown in Table-B (Table-B) B) disodium-N, N-bis (sulfonatoethyl) hydroxylamine 24.0 g 4-amino-3-methylN-ethyl-N- (β-hydroxyethyl) aniline sulfate 20.0 g 1.0 liter pH (potassium hydroxide) 11.0

The prepared color developer composition was stored in a glass bottle at -5 ° C. for 6 weeks. The liquid was visually judged, ◎ indicates that no precipitation occurred, ○ indicates that slight turbidity occurred, Δ indicates that slight precipitation was observed,
A five-step evaluation was performed in which a substance having a clear precipitate was x and a substance having a remarkable precipitate was xx. Table B
Shown in

Comparative Samples 2-1 Using Conventionally Known Compounds
Sample No. 2 has no effect or little effect as compared with Comparative Sample No. 1 in which no suspending agent is added, but Samples 15 to 21 in which compound (I) of the present invention and polyethylene glycol are added.
No precipitate was observed in any of the samples.
No. 174643 (Sample 1)
2 and ethylene urea), or the effects of Samples 13 and 14 out of the present invention using the exemplified compounds of the present invention were observed.

Example 3 Storage stability over time The concentrated developer composition of Example 2 was replaced with polyethylene (HDP)
E) The bottle was put up to the mouth and sealed. This at 40 ° C
And 50 ° C for 10 weeks each. The liquid state of each of the samples subjected to the heating and aging was visually judged, and those which did not cause coloring in any of the container and the developer composition were evaluated as ◎
も の indicates that the composition slightly colored, △ indicates that the bottle was slightly colored, x indicates that the bottle was clearly colored, and x indicates that the bottle was markedly colored.
A five-point evaluation was performed with the symbol x. The results are shown in Table-B.

[0141]

[Table 3]

Comparative Samples 2-1 Using Conventionally Known Compounds
4 shows that the thickening agent composition is colored or the container bottle is colored and has no effect or little effect as compared with Comparative Sample 1 in which the suspending agent is not added, but the compound (I) of the present invention and polyethylene Sample 1 in combination with glycols
No precipitation was observed in any of Sample Nos. 5 to 21, and no coloring was observed in the bottle, and a clear effect was observed for Comparative Samples 2 to 12. Also, JP-A-11-174643
The effect of the precipitation inhibitor (ethylene urea of Sample 12) described in Japanese Patent Application Publication No. H11-15011 or Samples 13 and 14 out of the present invention using the exemplified compound of the present invention was recognized.

[Embodiment 4] 1. Preparation of Color Negative Film Sample for Testing US Pat.
The following test was performed using the sample 101 described in Example 1 of Japanese Patent Publication No. 26-26.

2. Preparation of a concentrated color developer and stability test of the composition A color development replenisher formulation described later in the section of the development test and the above compound such as the general formula (I) related to the present invention shown in Table-C or a comparison For each color developing replenisher to which the compound was added, a concentrated color developing composition (one-part configuration) in an HDPE bottle three-fold concentrated was prepared, and the resultant was designated as Composition Samples 31 to 52. Samples 31 to 52 were tested for stability against precipitation during storage over time in a bottle-enclosed state and stability against air oxidation coloring by the methods described in Examples 1 and 2, respectively. However, for the test for stability against coloring, a test condition of 40 ° C. was selected. The test results are shown in Table-C.

[0145] 3. Development Processing Test The photosensitive material sample 001 was used for exposure for sensitometry and for achieving the running equilibrium of the tank liquid in the developing machine, respectively, and the transport speed of the automatic developing machine used in Example 3 was further increased by 10%. The temperature of each process was changed accordingly, and the bottle of the following color developing solution formulation was used for the color developing tank solution, and the color developing replenisher was prepared based on the following replenishing solution formula. The same developing machine, processing steps, exposure and processing operations as in Example 3 were used, except that the replenisher containing the concentrated color developing agent was charged into the developing machine according to the method described in Example 3, and a replenisher that was automatically prepared was used. A photographic property test with pre-processing running was performed, and the photographic property was evaluated by the same method as in Example 3 in which the representative value of the photographic property was evaluated based on the change in the color balance from the standard development described above. I went. The test results are also shown in Table-C.

The processing steps and the composition of the processing solution are shown below. (Processing step) Step Processing time Processing temperature Replenishment amount * Tank capacity Color development 135 seconds 42.0 ° C 15ml 10.3L Bleaching 22.5 seconds 41 ° C 5ml 3.6L Settling (1) 22.5 seconds 41 ° C- 3.6L Settling (2) 22.5 seconds 41 ° C 7.5ml 3.6L Stability (1) 12.6 seconds 41 ° C-1.9L Stability (2) 11.7 seconds 41 ° C-1.9L Stability (3) 11.7 seconds 41 ° C 30 ml 1.9 L Drying 27 seconds 62 ° C * The replenishment amount is 35 mm width of photosensitive material and 1.1 m width (equivalent to 24 Ex. 1 bottle).

The stabilizing solution is of a counterflow type (3) → (2) → (1), and the fixing solution is also connected from (2) to (1) by a counterflow pipe. Also, 15 ml of the tank solution of the stabilizing solution (2) flows into the fixing solution (2), which corresponds to the replenishing amount. The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were all 2.0 ml per 1.1 mm width of 35 mm photosensitive material. The crossover time is 5.4 seconds in each case, and this time is included in the processing time of the previous process.

The composition of the processing solution is shown below. (Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.8 3.4 Catechol-3,5-disulfonate disodium 0.27 0.35 Sodium sulfite 3.9 5.3 Potassium carbonate 39.0 39.0 Compounds described in Table-C (see Table-C) 6.0 10.0 Disodium-N, N-bis (2-sulfonatoethyl) hydroxylamine 1.5 2.0 Potassium bromide 1.3 0.3 Potassium iodide 1.3 mg-4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.05-hydroxylamine sulfate 2.4 3.3 4-amino- 3-methyl N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 6.5 Add water 1.0 L 1.0 L pH (adjusted with potassium hydroxide and sulfuric acid) 10.0 5 10.18.

Processing solution formulation after bleaching step (including replenisher)
Is the same as in the third embodiment.

[0150]

[Table 4]

4. Test Results Table C shows that Samples 36 to 50, which are examples of the present invention, were processed under the standard development conditions shown as Comparative Examples, despite that high-speed, short-time rapid processing was performed for Samples 36 to 50. Is within 0.14, indicating good image quality. On the other hand, comparative samples 32-35
Indicates that any of the compounds of the general formula (I), polyethylene glycols, ureas, and polyvinylpyrrolidone are effective. It is also shown that the effect of each embodiment using any one of the combinations is not reached. In addition, even when samples 51 and 52, which are comparative examples, are added in combination, if the compound of the general formula (I) is not included in the combination, the effect as in the present invention example is obtained. It cannot be obtained. Further, regarding the precipitation resistance and the coloration resistance of the crystals, Comparative Samples 32 to 35 were obtained by comparison with Standard Sample 31.
However, all of the compounds of the general formula (I), polyethylene glycols, ureas, and polyvinylpyrrolidone have been shown to be effective. Samples 36 to 36 of Examples using a combination of any one of
It also shows that the effect of 50 is not reached. In addition, even when samples 51 and 52, which are comparative examples, are added in combination, if the compound of the general formula (I) is not included in the combination, the effect as in the present invention example is obtained. It cannot be obtained.

[0152]

The compound of the formula (I) and at least one of polyethylene glycols, ureas and polyvinylpyrrolidone are added to a color developing composition for a silver halide color photographic light-sensitive material in combination. Even when the color development time is shortened and / or when high-temperature development is performed, a photographic image with good color reproducibility with little change in color balance can be obtained. Therefore, 2/3
A development processing method and a processing composition for the same that do not degrade the photographic properties even in rapid and / or high-temperature processing within 0 seconds and / or 40 ° C. or higher can be obtained. Further, the processing composition having the above composition prevents precipitation and coloration of the composition itself or the container during storage of the composition, and also stably maintains photographic performance. Therefore, it is possible to increase the concentration of the color developer composition. Further, it is possible to use a polyethylene container which could not be used for a color developing composition in the past.

[Brief description of the drawings]

FIG. 1 shows a treatment agent composition container (bottle) according to one embodiment of the present invention.

FIG. 2 shows a state where a piercing nozzle breaks a seal portion of a treatment agent composition container (bottle) according to one embodiment of the present invention.

[Explanation of symbols]

 188 Hole Nozzle 214 Nozzle Hole 300 Bottle (Photo Processing Agent Container) 302 Container Main Body 304 Male Thread (Screw) 308 Polyethylene Sheet with Notched Groove 310 Cap (Fixing Member) 312 Bottom (When Loaded) 314 Opening

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[Procedure amendment]

[Submission date] August 29, 2000 (2008.2.
9)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0120

[Correction method] Change

[Correction contents]

[0120] 2. Method of photographic property test Standard C was applied to the sample film B according to the method described in International Standard ISO5800 (sensitivity measuring method for color negative film).
Sensitometry exposure was performed through a light source and a neutral color continuous light wedge (density gradient: 0.4 D / cm, density range: 0.02 to 4.8). In the following development processing, photographic characteristics (sensitivity, gradation and fog) were obtained using this exposed sample.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0145

[Correction method] Change

[Correction contents]

[0145] 3. Development Processing Test The photosensitive material sample 101 was used for exposure for sensitometry and for reaching the running equilibrium of the tank liquid in the developing machine, respectively, and the transport speed of the automatic developing machine used in Example 3 was further increased by 10%. The temperature of each process was changed accordingly, and the bottle of the following color developing solution formulation was used for the color developing tank solution, and the color developing replenisher was prepared based on the following replenishing solution formula. The same developing machine, processing steps, exposure and processing operations as in Example 3 were used, except that the replenisher containing the concentrated color developing agent was charged into the developing machine according to the method described in Example 3, and a replenisher that was automatically prepared was used. A photographic property test with pre-processing running was performed, and the photographic property was evaluated by the same method as in Example 3 in which the representative value of the photographic property was evaluated based on the change in the color balance from the standard development described above. I went. The test results are also shown in Table-C.

Claims (4)

[Claims] 1. At least one compound selected from the compounds represented by the following general formula (I), and at least one compound selected from polyethylene glycol (number average molecular weight: 2,000 or less), ureas and polyvinylpyrrolidones.
A color developing composition for a silver halide color photographic light-sensitive material, comprising: Formula (I) R ¹ —SO ₃ M (In the formula (I), R ¹ represents an alkyl group having 4 to 10 carbon atoms, and M represents a cation.) 2. A compound selected from at least one compound selected from the compounds represented by the general formula (I) according to claim 1 and polyethylene glycol (number average molecular weight: 2,000 or less), ureas, and polyvinylpyrrolidones. A concentrated liquid color developer composition for a silver halide color photographic light-sensitive material, comprising at least one compound selected from the group consisting of: 3. A silver halide color photographic light-sensitive material, wherein a color development process is performed within 2 minutes and 30 seconds using the development processing composition according to claim 1 as a color development replenisher or a developer. Development processing method. 4. A silver halide color photographic photosensitive material, wherein the color development processing is carried out at a processing temperature of 40 ° C. or more using the development processing composition according to claim 1 as a color development replenisher or a developer. Material development processing method.