JP2001100380A - Color developing composition for silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a color developing composition which shortens the color development time of a silver halide color photographic sensitive material, attains good color balance, is excellent in color reproducibility and gives a processing solution excellent in deposition resistance and to provide a developing method. SOLUTION: The color developing composition contains at least one compound of the formula I [R1-(OC2H4)n-OH] (where R1 is a 1-3C alkyl and (n) is an integer of 4-9) and at least one compound selected from a polyethylene glycol of the formula II [H-(OC2H4)m-OH] (where (m) is an integer of 1-500), ureas and polyvinylpyrrolidones. A silver halide color photographic sensitive material is color-developed with the developing composition.

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 minilabs, silver halide photographic materials (hereinafter referred to as photographic materials or photographic materials for simplicity) have been developed in order to quickly respond to customer processing requests. There is a strong demand for shortening the time required for image processing (also referred to as photosensitive material).

[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 at the time of continuous processing was greatly linked, and the stability of the developing solution was 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, the crystal of the color developing tank rises,
There is also a problem that tar stain is generated on the wall surface of the processing tank and the processing activity of the color developing solution is reduced, and a method for solving this problem is also desired.

Further, when supplying 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. There is a concentrated liquid processing agent system in which a concentrated liquid processing agent is supplied in the form of a concentrated liquid processing agent filled in a container in a concentrated state, and is diluted with water or the like to a predetermined concentration in the developing laboratory and used as a processing liquid. However, it is also desired to provide a processing agent having an excellent effect of preventing precipitation of a developing agent in a concentrated liquid processing agent (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) and polyethylene glycol, urea and polyvinylpyrrolidone represented by the following general formula (II) A color developing composition for a silver halide color photographic light-sensitive material, comprising: at least one compound;

General formula (I) R ^1- (OC ₂ H ₄ ) _n -OH (In the formula (I), R ¹ represents an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 4 to 9) .)

General formula (II) H- (OC ₂ H ₄ ) _m —OH (In the formula (II), m represents an integer of 1 to 500.)

(2) At least one compound selected from the compounds represented by the above general formula (I) and polyethylene glycols, ureas and polyvinylpyrrolidones represented by the above general formula (II) A liquid concentrated 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 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 color development is carried out at a processing temperature of 40 ° C. or more using the development processing composition described in (1) above as a color development replenisher or 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 can be shortened by containing a combination of a compound of the type and at least one compound selected from the group consisting of polyethylene glycol, urea and polyvinylpyrrolidone represented by the general formula (II). The present inventors have found that, even in the development processing, deterioration of the color balance, which has been caused when rapid processing is performed using a conventional color developing solution, is effectively prevented, and the present invention has been achieved. In particular, the above-described effect is effectively exerted in rapid and / or high-temperature color development processing within 2 minutes 30 seconds and / or 40 ° C. or more.

In the present invention, the term "color developing composition" refers to a developing solution (a solution for processing a photographic material, hereinafter also referred to as a processing solution form), a replenishing solution composition for supplying the solution (hereinafter, referred to as a processing solution).
And a processing composition for supplying the developing solution or the replenisher composition (hereinafter, also referred to as a supply processing agent form, which may be either a solid processing agent or a liquid concentrated processing agent).
Any of these may be used.

Furthermore, it has been found that the color developing solution having the above-mentioned structure effectively prevents crystal crawling and tar contamination in the developing tank, and causes little deterioration in photographic performance. Further, when the color developing composition of the present invention is applied as a liquid concentrated processing agent in the above-described supply processing agent form,
Despite containing a high concentration of color developing agent, insolubles do not precipitate during storage and are less susceptible to air oxidation, resulting in improved stability and preservation until use of the color developing agent It was found that there was no coloring due to oxidation of the processing solution and the developing agent in the processing agent container including the period.

As described above, the term "liquid-concentrated processing agent" or "liquid-concentrated 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. In general, the liquid concentrated color developer composition of the present invention is used as a processing liquid after being diluted with water or the like to a concentration determined in a developing laboratory. 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.

[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), (I-
10) and (I-11).

[0021]

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The color-developing composition of the present invention comprises, together with the compound represented by the general formula (I), the compound represented by the general formula (II)
And at least one compound selected from the group consisting of polyethylene glycols, ureas and polyvinylpyrrolidones.

The polyethylene glycol represented by the general formula (II) includes diethylene glycol, triethylene glycol and polyethylene glycol (average molecular weight: 2
00, 300, 400, 600, 1000, 1540,
2000, 4000, 6000, 20000), preferably diethylene glycol, triethylene glycol,
Polyethylene glycol (average molecular weight: 1000 to 20)
00).

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 of the general formula (II) is 1 to 50
g, 1 to 50 g of urea, and 0.1 g of polyvinylpyrrolidone.
It is preferable to contain 1 to 20 g. When the developing composition is in the form of a replenisher, 0.1 to 50 g of the compound of the general formula (I), 1 to 50 g of the polyethylene glycol of the general formula (II), and 0.5 to 50 g of the urea per liter of the processing composition. 5
0 g and 0.05 to 20 g of polyvinylpyrrolidone 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 general formula (I) and 1 to 100 g of the compound of the general formula (II) per liter of the processing composition
5 to 80 g of polyethylene glycol, 5 to 50 ureas
g, 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. .

The color developing composition of the present invention may further contain an alkylsulfonic acid having 4 to 10 carbon atoms. Examples of the alkylsulfonic acid include the following. Among them, preferred compounds are (S-3) and (S-
4), (S-5), (S-9), and (S-11).

[0032]

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Next, other components of the developing composition of the present invention other than those described above will be described. In the processing composition,
Although a color developing agent is contained, 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. In recent years, in black-and-white photosensitive materials, a coupler has been added so as to form black.
Although some black and white images are formed using a general-purpose general color developing solution, the color developing solution of the present invention is also applicable to processing of this type of photosensitive material.

1) N, N-diethyl-p-phenylenediamine 2) 4-amino-N, N-diethyl-3-methylaniline 3) 4-amino-N- (β-hydroxyethyl) -N-
Methylaniline 4) 4-amino-N-ethyl-N- (β-hydroxyethyl) aniline 5) 4-amino-N-ethyl-N- (β-hydroxyethyl) -3-methylaniline 6) 4-amino- N-ethyl-N- (3-hydroxypropyl) -3-methylaniline 7) 4-amino-N-ethyl-N- (4-hydroxybutyl) -3-methylaniline 8) 4-amino-N-ethyl- N- (β-methanesulfonamidoethyl) -3-methylaniline 9) 4-amino-N, N-diethyl-3- (β-hydroxyethyl) aniline 10) 4-amino-N-ethyl-N- (β -Methoxyethyl) -3 methyl-aniline 11) 4-Amino-N- (β-ethoxyethyl) -N-
Ethyl-3-methylaniline 12) 4-amino-N- (3-carbamoylpropyl-
Nn-propyl-3-methylaniline 13) 4-amino-N- (4-carbamoylbutyl-N
-N-propyl-3-methylaniline 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

Of 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 the aforementioned 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.
Nos. 63-44657, 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-1-86939, 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 treatment composition of the present invention. Color developer (especially color
Print material developer) usually contains 3.5 x 10
^{-2 to} 1.5 × 10 ^-1 mol / l
Chlorine ions are usually released to a developer as a by-product of development, and thus often need not be added to a replenisher. 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. If the chloride ion concentration is more than 1.5 × 10 ^-1 mol / liter, it has the disadvantage of delaying the development, and is unfavorable because the speed and color density are impaired. Also, 3.5 × 10
^If it is less than ^-2 mol / l, it is often not preferable for preventing fog.

With regard to the treatment composition, the situation is the same with respect to the content of bromine ions as in the case of chloride ions. The bromine ion in the color developer is 1 to 5 in the processing of the photographic material.
x10 ^-3 mol / l approximately, in the processing of the print material is preferably 1.0 × 10 ^-3 mol / l or less. If necessary, bromine ions may be added to the treatment composition so that the bromine ion concentration falls within this range. When included in the treatment composition, as the chloride ion supply material, sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, among which, preferred are sodium chloride, Potassium chloride. As bromine ion supply substances, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide,
Cerium bromide and thallium bromide are mentioned, and potassium bromide and sodium bromide 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 apparently make it 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, it may be added to a color developing solution having a high pH. Generally, stilbene-based fluorescent brighteners are frequently used, and among them, di (triazylamino)
Stilbene-based and 4,4'-diamino-2,2'-disulfostilbene-based optical brighteners 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.

The pH of the processing composition of the present invention is preferably from 9.5 to 13.5 in the case of a thick liquid processing composition, but a color developer (processing solution form) prepared therefrom is preferred.
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 buffers. Examples of the buffer include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 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. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates have excellent buffering ability in the high pH range of pH 9.0 or higher, and have an adverse effect on photographic performance (fog) even when added to a color developer. ) And the advantage of being inexpensive, and it is particularly preferable to use these buffers. The concentration is 0.01 to 2 mol per liter of the developing replenisher,
Preferably, it is added to the composition so as to be 0.1 to 0.5 mol.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, and 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), 5-sulfo-
Potassium 2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like can be mentioned. However, the invention is not limited to these compounds.
The amount of the buffer is included so that the concentration in the diluted color development replenisher is 0.1 mol / L or more, particularly 0.1 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 alkali 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 also improve 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 can optionally contain an optional 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.

[0049] The treatment composition of the present invention may optionally contain an antifoggant. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole,
5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2
Nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine can be mentioned as typical examples.
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. In the foregoing, the color development supply processing agent of the present invention and the color development replenisher or developer prepared therefrom have been described.

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 concentration is about 1.5 to 10 times, preferably 2 to 8 times, the concentration of the solution in actual use, that is, the development replenisher or the mother liquor (tank solution).
More preferably, it is 3 to 5 times. The concentration of the compound of the general formula (I) in the concentrated treatment composition (when two or more compounds are contained, the total concentration thereof) is 0.01 to 200 g per liter of the concentrated treatment composition, and is preferably 1 to 10
0 g, more preferably 5 to 50 g. Also,
The content of the polyethylene glycol, urea and / or polyvinylpyrrolidone used in combination 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. is there.

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. According to the present invention, the developer can be supplied while being stored in a polyethylene container, which is an advantage. 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 also meet Requirement 4.

In view 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.

Since the color developing solution containing the compound of the present invention has the advantage of being less susceptible to air oxidation as described above, it is practical even without using such a composite material container. Storage stability is obtained. 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 include 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.

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 filled with 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 developer composition into the container, in order to further enhance the safety against air oxidation, the space above the container should be filled as much as possible to minimize the upper space, or the upper 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 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 developing 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 liquid concentrated color developer composition of the present invention is mounted on the developing machine, and the contents are transferred into a developing replenishing tank, and then the inside of the container is spray-washed. The chemical components adhering to the vessel wall are washed away, and the water used for the washing can be subjected to a developing treatment of the 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. The inside of the container is sprayed with washing water by the method disclosed in JP-A-6-82988, JP-A-8-220722 and the like.
As a result, it can be cleaned without human intervention, can be handled cleanly, and recycling of waste containers is easy. 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 an 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 by a resin material. 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 30
The upper end of 6 is open, and the above-mentioned replenisher can be taken in and out through this opening. Also, a polyethylene (LDPE) sheet member 308 is provided on the upper end of the neck 306.
Is arranged. 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.

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.

The 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.

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 (1) according to the present invention is applied as a solid processing agent, as described above, when the processing solution or the developing replenisher is used, 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 the general formula (1) preferably has a particle diameter of 21.
70% by weight or more of particles having a particle size of 0 μm or less, particularly preferably 70% by weight or more, and most preferably 149 μm or less.
4 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 the 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 pulverize the compound represented by the general formula (I) of the present invention into the above-mentioned preferable particle size, a commercially available pulverizer such as a hammer mill, 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-grained crystals, and the term "granules" refers to granules obtained by subjecting a powder to a granulation step and having a particle diameter of 50 to 5000 μm. Powder or granules formed by compression molding 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 formula (I) may be directly added to and mixed with the granular processing 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, thylium 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 preferred because their iron (III) complex salts have good photographic properties. These ferric ion complex salts may be used in the form of a complex salt, or a ferric salt such as ferric sulfate,
A ferric ion complex salt may be formed in a solution using ferric chloride, ferric nitrate, ammonium ferric 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, iron aminopolycarboxylate complexes are preferred, and the amount added is 0.01 to
1.0 mol / liter, preferably 0.05 to 0.50
Mol / l, more preferably 0.10 to 0.50 mol / l, even 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. Compound W represented by (Bb)
It is preferable to contain O. The addition amount of these compounds is
The amount is preferably 0.005 to 3.0 mol, more preferably 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 kinds 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, carbonyl compound and the like 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 and / or stabilization 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 bacteria increase due to an increase in the residence time of water in the tank. 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.

Also, aldehydes such as formaldehyde, acetaldehyde and pyruvaldehyde which inactivate the remaining magenta coupler to prevent fading of the dye and formation of stain, methylol compounds described in US Pat. No. 4,786,583 and hexamethylentetramine Hexahydrotriazines described in JP-A-2-153348, formaldehyde bisulfite adduct described in U.S. Pat. No. 4,921,779, seized patent publication 504609.
And azolylmethylamines described in JP-A Nos. 519190 and 519190 are added.

Further, in the washing water, a surfactant as a draining agent and a chelating agent represented by EDTA as a hardening agent can be used. Continue with the above washing process or
Alternatively, the treatment can be performed directly with the stabilizing solution without going through the 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. Further, in order to prevent the growth of bacteria in the liquid and impart fungicidal properties to the processed photosensitive material, the above-mentioned various bactericides and fungicides can be used.

Further, a surfactant, a fluorescent whitening agent and a hardening agent may be added. In the processing of the light-sensitive material of the present invention, when the stabilization is directly performed without going through a washing step, a known method described in JP-A-57-8543, JP-A-58-14834, JP-A-60-220345 and the like can be used. Can be used. In addition, it is also a preferable embodiment to use a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid or ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound.

A so-called rinsing liquid is also used as a washing liquid or a stabilizing liquid used after the desilvering treatment. The preferred pH of the washing step or the stabilizing step 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.

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 discharged 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, pp. 27-76, for the purpose of improving image sharpness and the like. 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. (For example, trimethylolethane) or the like
It is preferable that the content be at least 10% by weight (more preferably at least 14% by weight).

Further, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, the light-sensitive material according to the present invention is protected by the method described in JP-A-63-271247. 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 0,355,660A2, 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.

[0094]

[Table 1]

Further, as a cyan coupler, JP-A-2-33
No. 144, EP 0,333,185 A2 and JP-A-64-32260 can also be used. Cyan, magenta or yellow couplers can be loaded in the presence (or absence) of the high boiling organic solvents listed in the preceding table (eg, US Pat. No. 4,203,716).
It is preferable to emulsify or disperse in a hydrophilic colloid aqueous solution by dissolving with a water-insoluble and organic solvent-soluble polymer. Preferred water-insoluble and organic solvent-soluble polymers are described in US Pat. No. 4,857,449.
Nos. 7 to 15 of the specification and International Publication WO88 / 00
No. 723, pages 12 to 30 of the homopolymer or copolymer. 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 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.

As the magenta coupler used in the present invention, besides a 5-pyrazolone-based magenta coupler described in the publicly known documents in the above table, International Publication 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 acylacetoanilide-type couplers are preferably used. Among them, European Patent No. EP0447969A and Japanese Patent Application Laid-Open No. Hei 5-1 are preferred.
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 the 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 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:

Dyes: 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 heat-treated 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, it is preferable to perform a surface treatment 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. The particle size is preferably 0.8 to 10 μm, and the particle size distribution is also 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. For example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm) ), Polystyrene particles (0.25
μm) and colloidal silica (0.03 μm).

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.

[0120]

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

2. Method of photographic property test According to the method described in ISO5800 (sensitivity measurement method for color negative film), a standard C light source and a neutral color continuous light wedge (density gradient 0.4ＳＯD / cm, density range 0.0
2 to 4.8) for 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 system. The outline is as follows. The plastic bottle (HDPE) 300 described in the specification text is arranged side by side with the mouth of the bottle facing down, When the bottle is closed, as shown in FIG. 2, the bottle moves from above to the piercing nozzle 188, breaks through the plastic sheet 308 acting as a lid of the bottle, and drains the composition solution therein 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 the countercurrent type (3) → (2) → (1), and the fixing solution is also connected from (2) to (1) by a countercurrent 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 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-2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 5. 5 g 12.5 g Potassium carbonate 39 g 59 g Compound described in Table-A (See Table-A) (See Table-A) 1.0 L 1.0 L pH was adjusted by adding water (adjusted with sulfuric acid and KOH) 10.10 11.20

(Bleaching solution) Tank solution Replenishing solution 1,3-diaminopropanetetraacetic acid ammonium ferric 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 1000 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

(Stabilizer) Common to tank liquid and replenisher p-Toluenesulfonate sodium 0.03 g p-nonylphenoxypolyglycidol (glycidol average polymerization degree 10) 0.4 g ethylenediaminetetraacetic acid disodium salt 0.05 g 1,2 1,4-Triazole 1.3 g 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 g 1,2-benzisothiazolin-3-one 0.10 g Water was added to 1.0 L pH 8.5

[0130] 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. The concentrated developer replenisher composition was added to the plastic bottle (HDPE) for 40 minutes.
Aged at ° C for 10 weeks. It was loaded into the replenisher preparation section of the above-mentioned modified developing machine and diluted with washing water to prepare replenishers in respective replenishment tanks. Each of the separately prepared tank solutions was placed in a developing machine, and a 30% exposed film of the film was processed while replenishing the replenishment tank. 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. Students were compared. 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 Setting (1) 50 seconds 38 ° C. -3.6L fixed (2) 50 seconds 38 ℃ 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. Also, 15 ml of the tank solution of the stabilizing solution (2) flows into the fixing solution (2), which corresponds to the replenishing amount. Further, the color developing solution is replenished by dividing the replenishing solution of the color developing solution (A) and the replenishing solution of the color developing solution (B) of the following formulation into 12 ml and 3 ml, respectively, corresponding to the replenishing amount, to a total of 15 ml. 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 developing solution (A)) 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 ( Sulfonatoethyl) 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 2-methyl-4- [N -Ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.7 g 11.4 g Potassium carbonate 39 g 59 g Water was added to 1.0 L 1.0 L pH (adjusted with sulfuric acid and KOH) 10.007 10 .51 The above tank liquid shows the composition of (color developing solution (A)) when the following (color developing solution (B)) was mixed.

(Color developing solution (B)) Tank solution Replenisher Hydroxylamine sulfate 2.0 g 4.0 g Water was added to 1.0 L 1.0 L pH (adjusted with sulfuric acid and KOH) 10.07 4.0 The tank liquid indicates the composition of the (color developing solution (B)) when the (color developing solution (A)) is mixed.

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 of Log 3.0 during test processing) − (Test processing Log)
G concentration of 3.0)]-[Standard (R concentration of Log 3.0)
-Standard (G concentration of Log 3.0)]

[0137]

[Table 2]

Table A shows that the combination of the compound of the formula (I) with the polyethylene glycol, urea and polyvinylpyrrolidone of the formula (II) improved the color balance of the developer.

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 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 20.0 g In addition, 1.0 liter pH (potassium hydroxide) 11.0

The prepared color developer composition was stored in a glass bottle at -5 ° C. for 4 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 is less effective than Comparative Sample No. 1 in which no suspending agent is added, but Samples 14 to 22 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 ethylene urea).

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 stored at 50 ° C. for 8 weeks. The liquid state of each of the samples subjected to the heating and aging was visually judged, and ◎ indicates that the container and the developer composition did not cause coloring, and ○ indicates that the composition slightly colored, and the bottle △ indicates that some coloring was observed, x indicates that the bottle was clearly colored, and XX indicates that the bottle was markedly colored.
The five-step evaluation was performed. The results are shown in Table-B.

[0143]

[Table 3]

[0144]

[Table 4]

Comparative Samples 2-1 Using Conventionally Known Compounds
No. 2 shows that the thickening agent composition was colored or the container bottle was colored and had no effect or little effect as compared with Comparative Sample 1 in which the suspending agent was not added. Samples 14 to 22 in which glycol (II), ureas, and polyvinylpyrrolidone were used in combination did not show any precipitation, and did not show any coloration in the bottle.
A clear effect was observed for Comparative Examples 2 to 12. In addition, even more effects were observed in comparison with the precipitation inhibitor (ethylene urea of Sample 12) described in JP-A-11-174643.

[0146]

The color developing composition for a silver halide color photographic light-sensitive material contains a compound of the formula (I) in combination with polyethylene glycol, urea and / or polyvinylpyrrolidone of the formula (II). By doing so, the deterioration of the color balance, which tends to occur during rapid processing, is improved. Particularly in a rapid and / or high-temperature color development processing within 2 minutes 30 seconds and / or 40 ° C. or more, the effect of improving the color balance is particularly effectively exhibited.

Further, when the color photographic material is subjected to color development processing using the composition, precipitation and coloring of the composition itself are effectively prevented, and photographic performance is stably maintained. Therefore, it can be used as a concentrated liquid color developer composition with an increased concentration. Further, when used as a concentrated liquid color developer composition, it is possible to use a polyethylene container which could not be used conventionally.

[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

Claims (4)

[Claims] (1) at least one compound selected from the compounds represented by the following general formula (I):
A color developing composition for a silver halide color photographic light-sensitive material, characterized by containing at least one compound selected from the group consisting of polyethylene glycol, urea and polyvinyl pyrrolidone represented by I). General formula (I) R ^1- (OC ₂ H ₄ ) _n -OH (In the formula (I), R ¹ represents an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 4 to 9.) formula _{(II) H- (OC 2 H} 4) m -OH ( in the formula (II), m represents an integer of 1 to 500.) 2. At least one compound selected from the compounds represented by the general formula (I) according to claim 1, and polyethylene glycol and urea represented by the general formula (II) according to claim 1. And at least one compound selected from the group consisting of polyvinylpyrrolidones and polyvinylpyrrolidones. A liquid concentrated color developing composition for a silver halide color photographic light-sensitive material, comprising: 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.