JP2612205B2 - Color image forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a color developing method in which a color developing solution is applied to a color photographic light-sensitive material containing a photosensitive silver halide such as color paper and a coupler in the form of a thin film and developed. The present invention relates to a method of forming an image, particularly a method suitable for developing using a small amount of a color developing solution, and a color image forming method capable of obtaining a sufficient image density in a short time.

[Prior art and its problems]

In developing a silver halide color photographic light-sensitive material, various attempts have been made to reduce the amount of waste liquid by reducing the amount of a processing solution such as a developing solution, a bleaching solution and a fixing solution as much as possible. As one of these methods, a method has been proposed in which a developer is applied to a photosensitive material to reduce a waste liquid accompanying the development processing. This method is carried out by a viscomat method in which a processing solution is hopper-coated, a bi-mart method in which a thin layer of a processing solution is coated on a light-sensitive material, and the like. Examples of the above-mentioned method include Von Nost rand Reinhold. c
o.NY), published in 1977, Neblette's Handbook of Photography and Reprogr
aphy), 7th edition, Chapters 11 and 12, and JP-A-61-20236. According to these methods, the development waste solution can be eliminated, but the stirring of the developer solution and the accumulation of the development inhibitory components (particularly iodine ions and bromide ions) released during the development and the acid generated by the development reaction occur. As a result, the development reaction is remarkably slowed due to a decrease in pH in the film and a consumption of a base by gelatin, a coupler or the like, and a sufficient image density cannot be obtained. In addition, a small amount of liquid must contain an amount of a developing agent necessary for image formation (for example, the amount of a coupler to be applied).

However, when a silver halide emulsion or a silver iodobromide emulsion having a high silver bromide content is used, since the amount of liquid outside the film surface is extremely small, bromine ions or iodide ions released by color development are extremely high in concentration. It was found that it was accumulated in the film, development was greatly delayed, and favorable tone reproduction could not be performed. In particular, it was found that development in the lowermost layer was significantly delayed. It has been found for the first time that such development is not accompanied by tank processing, but occurs with the progress of development because bromine ions or iodine ions generated do not diffuse out of the photosensitive material.

The second problem is that there is no or very little external replenishment of bases as in ordinary tank development, so the color development reaction is greatly reduced, resulting in a low-sensitivity, low-concentration color development solution. It has been found that the application gives rise to a specific problem.

With respect to the above second, JP-A-63-11940 and JP-A-63-23149 describe a method of generating a base in a light-sensitive material film in order to improve the stability over time of a developer or a replenisher. . Although these methods certainly compensate for the decrease in film pH due to the development reaction, when processing with a small amount of developing solution, a long processing time is required, the maximum density is low, and the gradation is low. Only poor images were obtained.

[Problems to be solved by the invention]

In this way, unlike the system in which the used solutions are mixed like the tank processing system, it is completely unexpected that the above-mentioned problem occurs when a small amount of a new solution or an unused developer is used. Met.

Therefore, in order to obtain a sufficient photographic image in a short time using a small amount of the developing solution, it is necessary to reduce the color development inhibiting component, replenish the alkali, select the color developing agent, and increase the concentration as described above. It has been found that the technology to achieve the above at the same time is important.

As is apparent from the above description, an object of the present invention is to apply a small amount of a color developing solution in a thin layer on a silver halide light-sensitive material, thereby reducing the waste of the color developing solution,
In some cases, it is an object of the present invention to provide a color image forming method capable of eliminating waste liquid and stably performing color development processing in a short time.

[Means for solving the problem]

An object of the present invention is to develop a photographic material containing at least one kind of coupler which forms a dye by a coupling reaction with an oxidized form of an aromatic primary amine developing agent, a photosensitive silver halide and a binder by color development processing. In a method for forming a color image, the silver halide is 80 mol%
A silver halide substantially free of silver iodide comprising the above silver chloride, wherein the photosensitive material contains a basic metal compound which is hardly soluble in water, and a basic metal compound which is hardly soluble in water; It contains a compound that releases a base when complexed with a constituent metal ion (hereinafter, referred to as a complex-forming compound), and contains 3-methyl-
4-amino-N-ethyl-N-β-hydroxyethylaniline to 3-methyl-4-amino-N-ethyl-N
This is achieved by a color image forming method, which comprises applying a color developer containing -β-hydroxypropylaniline or a salt thereof in a thin layer on the surface of a photosensitive layer and subjecting it to color development.

The method of the present invention is a method which is particularly effective in a method in which a newly prepared and unused color developing solution is used once, and is not used again, that is, a so-called use-type developing method.

Hereinafter, a specific configuration of the present invention will be described in detail.

First, it is substantially free of silver iodide and has a silver chloride content of 80
More than mol% of silver halide emulsion is used. Here, "substantially free of silver iodide" means that the silver iodide content is 1.0 mol%.
Or less, preferably 0.2 mol% or less. If the silver chloride content is lower than this or the silver iodide content is higher than this range, development is delayed, and favorable tone reproduction cannot be obtained. Therefore, the silver chloride content is preferably higher. That is, it is preferably at least 90 mol%, more preferably at least 95 mol%. An emulsion of substantially pure silver chloride containing no silver iodide and having a silver chloride content of 98 to 99.9 mol% is also preferably used. However, the use of pure silver chloride emulsions is disadvantageous in that high sensitivity can be obtained and fogging that occurs when pressure is applied to the photosensitive material can be prevented.

By using such a high silver chloride, the amount of the developing solution can at least delay the development and improve the tone reproduction.

In the silver halide grains used in the present invention, most of the remaining composition other than silver chloride consists of silver bromide. In this case, the silver bromide may be uniformly contained in the silver halide grains (one grain is formed by a uniform solid solution of silver chlorobromide) or forms different phases in the silver bromide content. It may be contained in the form. In the latter case, the core (core) inside the particle,
So-called laminated grains having a different halogen composition from one or more shells surrounding the layer may be used, or different silver bromide contents (preferably high silver bromide contents).
The localized phase may be a particle formed discontinuously on the surface and / or inside of the particle. These localized phases having a high silver bromide content can be present inside the grains, at the edges, corners, or planes of the grain surfaces. One preferred example is that in which the grains are epitaxially bonded to the corners of the grains. be able to.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0.1 μm to 2 μm. preferable.

In addition, their particle size distribution is 20% of variation count (standard deviation of particle size distribution divided by average particle size).
In the following, a so-called monodispersed one of desirably 15% or less is preferable. At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating.

The silver halide grains contained in photographic emulsions have a regular (regular, cubic, tetradecahedral or octahedral) shape.
r) Those having a crystal form, those having an irregular crystal form such as a sphere or a plate, or those having a complex form thereof can be used. Also,
It may be composed of a mixture having various crystal forms. In the present invention, among these, the particles having the above-mentioned regular crystal form should be contained in 50% or more, preferably 70% or more, and more preferably 90% or more.

In addition, emulsions in which tabular grains having an average aspect ratio (diameter / circle diameter in circle) of 5 or more, preferably 8 or more, as projected area exceeds 50% of all grains can be preferably used.

In the silver halide emulsion used in the present invention, various polyvalent metal ion impurities can be introduced during the process of forming emulsion grains or physical ripening. Examples of the compound to be used include salts of cadmium, zinc, lead, copper, thallium and the like, or salts or complex salts of Group VIII element iron, ruthenium, rhodium, palladium, osmium, iridium and platinum. it can. Especially above VI
Group II elements can be preferably used. The addition amount of these compounds varies widely depending on the purpose, but is preferably from 10 ^-9 to 10 ^-2 mol based on silver halide.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization.

As the chemical sensitization method, sulfur sensitization represented by addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compounds used for chemical sensitization, those described in JP-A-62-221527, page 18, lower right column to page 22, upper right column are preferably used.

Spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye that absorbs light in a wavelength range corresponding to the intended spectral sensitivity—a spectral sensitizing dye. Examples of spectral sensitizing dyes used at this time include, for example, Heterocyclic compo by FM Harmer.
unds-Cyanine dyes and related compounds (John Wil
ey & Sons [New York, London], 1964). As specific examples of the compounds, those described in the above-mentioned JP-A No. 62-215172, from page 22, upper right column to page 38, are preferably used.

To the silver halide emulsion used in the present invention, various compounds or their precursors are added for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. be able to. As specific examples of these compounds, those described on page 39 to page 72 of JP-A-62-215272 described above are preferably used.

Here, the amount of silver applied to the light-sensitive material is preferably 0.9 g / m ² or less from the viewpoint of rapid processing property and suitability for thin layer development, and is preferably 0.4 g / m ² or more from the viewpoint of image density.

Second, the silver halide photographic material contains a basic metal compound which is hardly soluble in water, and forms a complex forming reaction with the metal ion constituting the hardly water-soluble basic metal compound in the developer. A compound (hereinafter, referred to as a complex-forming compound) is contained therein, and a base (alkali) is generated in the film of the photosensitive material by performing a complex-forming reaction during the processing. This makes it possible to compensate for a decrease in film pH due to the development reaction.

Examples of the basic metal compound which is hardly soluble in water to be contained in the light-sensitive material in the present invention include those having a solubility in water at 20 ° C. (grams of a substance dissolved in 100 g of water) of 0.5 or less and a formula of T _m X _n Those represented are preferred.

Where T is a transition metal such as Zn, Ni, Cu, Al, Co, F
e represents an alkaline earth metal such as Mn, for example, Ca, Ba, Mg, etc., wherein X can be a counter ion of M in water in the description of a complex-forming compound described below, and Represents, for example, a carbonate ion, a phosphate ion, a silicate ion, a borate ion, an aluminate ion, a hydroxy ion, and an oxygen atom. m and n are
It represents an integer such that the valence of each of T and X can balance.

 Preferred specific examples are listed below.

Calcium carbonate, barium carbonate, magnesium carbonate,
Zinc carbonate, strontium carbonate, calcium calcium carbonate, (CaMg (CO ₃ ) ₂ ), magnesium oxide, zinc oxide, tin oxide, cobalt oxide, zinc hydroxide, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, antimony hydroxide , Tin hydroxide, iron hydroxide, bismuth hydroxide, manganese hydroxide, calcium phosphate, magnesium phosphate, magnesium borate, calcium silicate, magnesium silicate, zinc aluminate, calcium aluminate, basic zinc carbonate (2ZnCo _{3 · 3Zn (OH) 2 · H} 2 O), basic magnesium carbonate _{(3MgCO 3 · Mg (OH)} 2 · 3H 2 O), basic nickel carbonate _{(NiCO 3 · 2Ni (OH)} 2), basic bismuth carbonate (Bi ₂ (CO ₃ ) O ₂ · H ₂ O), basic cobalt carbonate (2CoCO
_{3 · 3Co (OH) 2)} , magnesium aluminum oxide, copper hydroxide, basic copper carbonate and the like.

Of these compounds, those that are not colored are particularly preferred.

In the present invention, the complex forming compound to be contained in the treatment liquid is
It forms a complex salt having a stability constant of 1 or more in logK with a metal ion constituting the basic metal compound.

For these complex forming compounds, for example,
AE Martell, RMSm
ith), “Critical Stability Constants, 1st-5th
Vol., "Plenum Press.

Specifically, amino carboxylic acids, iminodiacetic acid and derivatives thereof, aniline carboxylic acids, pyridine carboxylic acids, amino phosphoric acids, carboxylic acids (mono, di, tri, tetracarboxylic acids and also phosphono, hydroxy, oxo, ester, amide And compounds having a substituent such as alkoxy, mercapto, alkylthio, and phosphino), alkali metals such as hydroxamic acids, polyacrylates, and polyphosphoric acids, and salts such as guanidines, amidines, and quaternary ammonium salts.

Preferred specific examples include picolinic acid, 2,6-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 4-dimethylaminopyridine-2,6-dicarboxylic acid, quinoline-2-carboxylic acid, 2-pyridylacetic acid, Oxalic acid, citric acid, tartaric acid, isocitric acid, malic acid, gluconic acid,
EDTA, NTA, CyDTA, hexametaphosphoric acid, tripolyphosphoric acid, tetraphosphoric acid, polyacrylic acid, And the like, salts of guanidines, salts of amidines, and quaternary ammonium salts.

Among them, an aromatic heterocyclic compound having at least one —CO ₂ M and having one nitrogen atom in the ring is preferable. The ring may be a single ring or a condensed ring, and examples thereof include a pyridine ring and a quinoline ring. And it is particularly preferable that the position where —CO ₂ M is bonded to the ring is α-position to the N atom. M is any of alkali metal, guanidine, amidine and quaternary ammonium ions.

More preferred compounds include those represented by the following formula.

In the above formula, R represents any one of a hydrogen atom, an aryl group, a halogen atom, an alkoxy group, -CO ₂ M, a hydroxycarbonyl group, and an electron donating group such as an amino group, a substituted amino group, and an alkyl group. . Two Rs may be the same or different.

Z ₁ and Z ₂ are the same as defined for R, respectively, and Z ₁ and Z ₂ may form a ring fused to a pyridine ring.

 Next most preferred basic metal compounds that are hardly soluble in water and their complex forms
Examples of combinations with synthetic compounds are listed (where M Is
Alkali metal ion, substituted or unsubstituted guanidini
Ion, amidinium ion or quaternary ammonium
Um ion).

Calcium carbonate M O_TwoC-CO_Two M  Barium carbonate M O_TwoC-CO_Two M  M of calcium carbonate-tripolyphosphate Salt calcium carbonate-citric acid M Salt calcium carbonate-M of polyacrylic acid salt Basic magnesium carbonate  M O_TwoC ・ CO_Two M  Zinc hydroxide-3M of ethylenediaminetetraacetic acid Salt zinc hydroxide-3M of 1,2-cyclohexanediaminetetraacetic acid salt  These combinations can be used alone or in combination of two or more.
Can be used even if.

Here, the mechanism of generating a base in the film of the photosensitive material in the present invention will be described by taking a combination of potassium picolinate and zinc hydroxide as an example.

 The reaction between the two is represented by the following formula, for example.

That is, when water in the treatment liquid is involved, picolinate ion causes a complex formation reaction with zinc ion, and the reaction represented by the above formula proceeds, so that a base is generated.

 The progress of this reaction is due to the stability of the resulting complex.
But the picolinate ion (L ) And zinc ion
(M ) Generated ML, ML_Two, ML_ThreeOf the complex represented by
The stability constant is very large as shown below.
The progress of the reaction is well explained.

Basic metal compounds that are poorly soluble in water are disclosed in JP-A-59-174830,
It is desirable to contain as a fine particle dispersion prepared by the method described in JP-A-53-102733 and the average particle size is
It is preferably 50 μm or less, particularly preferably 5 μm or less.

The addition position of the basic metal compound in the light-sensitive material in the present invention may be any layer such as an emulsion layer, an intermediate layer, a protective layer, an antihalation layer, a white pigment layer, and a back layer. Further, it may be contained in one layer or in two or more layers.

The amount to be added depends on the type of the processing solution, the pH, the complex forming compound type, the compound type of the basic metal compound, the particle size, the processing temperature, etc., and cannot be unconditionally specified, but is 0.01 to 20 g / m ² ,
Preferably, it is good to be about 0.1 to 5 g / m ² .

The amount of the complex-forming compound to be contained in the processing solution varies depending on the type of the processing solution, the pH, the type of the complex-forming compound, etc.
It is preferable that the number of moles of the basic metal compound to be reacted is 1/10 or more.

 Generally, it is good to be about 0.01 to 5 mol / l.

The silver halide color photographic light-sensitive material used in the present invention must contain a so-called color coupler capable of forming a dye by a coupling reaction with an oxidized aromatic primary amine developing agent. As these couplers, compounds having an active methylene group and forming an azomethine dye after coupling with an oxidized form of a developing agent are usually used. And, as described above, compounds are selected so as to obtain three kinds of these dyes, yellow, magenta and cyan.

As the yellow coupler that can be used in the present invention, acylacetamide derivatives such as benzoylacetanilide and pivaloylacetoanilide are preferable.

Among them, the following general formula [Y
-1] and [Y-2] are preferred.

For details of the pivaloyl acetanilide type yellow coupler, see US Pat. No. 4,622,287, column 3, column 15.
Line-column 1, line 39 and column 14, line 50 of the specification of JP 4,623,616
It is described at column 19, line 41.

For details of the benzoylacetanilide type yellow coupler, see U.S. Pat.Nos. 3,408,194, 3,933,501,
Nos. 4,046,575, 4,133,958, and 4,401,752.

Specific examples of the pivaloyl acetanilide type yellow coupler include the above-mentioned U.S. Pat.
Examples of the compounds (Y-1) to (Y-39) described in Columns to 54 can be cited, among which (Y-1), (Y-4) and (Y
-6), (Y-7), (Y-15), (Y-21), (Y-
22), (Y-23), (Y-26), (Y-35), (Y-3
6), (Y-37), (Y-38), (Y-39), and the like are preferable.

In addition, columns 19 to 24 of the above-mentioned U.S. Pat.
Examples of the compounds in the column are (Y-1) to (Y-33), among which (Y-2), (Y-7), (Y-8),
(Y-12), (Y-20), (Y-21), (Y-23),
(Y-29) and the like are preferable.

Other preferred are U.S. Pat.
Specific examples (34) and 3,93 in column 6 of the specification
Compound examples (16) and (1) described in column 8 of the specification of US Pat.
9), compound examples (9) described in columns 7 to 8 of JP-A-4,046,575, compound examples (1) described in columns 5 to 6 of JP-A-4,133,958, and compound (1) of JP-A-4,401,752. The compounds described in column 5 can be mentioned.

Among the above couplers, those having a nitrogen atom as a leaving atom are particularly preferred.

Examples of the magenta coupler used in the present invention include oil-protected, pyrazoloazole-based couplers such as indazolone-based or cyanoacetyl-based, preferably 5-pyrazolone-based and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of a coloring dye, and typical examples thereof are U.S. Pat. Nos. 2,311,082 and 2,343,703.
No. 2,600,788, No. 2,908,573, No. 3,062,65
No. 3, No. 3,152,896 and No. 3,936,015. As the leaving group of the 2-equivalent 5-pyrazolone coupler, a nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or an arylthio group described in U.S. Pat. No. 4,351,897 is preferable. Also, 5-pitizolone-based couplers having a ballast group described in EP 73,636 can provide high color density.

Pyrazoloazole-based couplers include U.S. Pat.
Pyrazolobenzimidazoles described in US Pat. No. 369,879, preferably pyrazolo [5,1-c] [1,2,4] triazoles described in US Pat. No. 3,725,067, Research Disclosure 24220 (June 1984). Pyrazolotetrazole described and Research Disclosure 24
230 (June 1984). Any of the couplers described above may be a polymer coupler.

These compounds are specifically represented by the following general formula (M-
1), (M-2) or (M-3).

Among the pyrazoloazole couplers, U.S. Pat.
Imidazo [1,2-b] pyrazoles described in 500,630 are preferred, and pyrazolo [1,5-b] [1,2,4] triazole described in U.S. Pat. No. 4,540,654 is particularly preferred.

Other pyrazolotriazole couplers in which a branched alkyl group is directly linked to the 2,3 or 6-position of the pyrazolotriazole ring as described in JP-A-61-65245.
Pyrazoloazole couplers containing a sulfonamide group in the molecule as described in JP-A-246, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, and European Patent (Publication) It is preferable to use a pyrazolotriazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No. 226,849.

As the cyan coupler used in the present invention, a phenol cyan coupler and a naphthol cyan coupler are the most representative.

Phenolic cyan couplers include U.S. Pat.
9,929, 4,518,687, 4,511,647 and 3,772,002
And phenolic nuclei having an acylamino group at the 2-position and an alkyl group at the 5-position (including polymer couplers). Typical examples thereof include those described in Canadian Patent No. 625,822. Coupler of Example 2, compound (1) described in U.S. Pat. No. 3,772,002, compounds (I-4) and (I-5) described in 4,564,590, JP-A-61-39
Compounds (1), (2), (3) and (2) described in No. 045
4) and compound (C-2) described in JP-A-62-70846.

U.S. Patent
2,772,162, 2,895,826, 4,334,011, 4,50
There are 2,5-diacylaminophenol-based couplers described in U.S. Pat. No. 6,653 and JP-A-59-164555, and typical examples thereof include compounds (V) described in U.S. Pat.
Compound (17) described in JP-A-4,557,999, compounds (2) and (12) described in JP-A-4,565,777, compound (4) described in JP-A-4,124,396, and compound (I-1) described in JP-A-4,613,564.
9) and so on.

U.S. Patent
No. 4,372,173, No. 4,564,586, No. 4,430,423, JP-A-6
No. 1,390,441 and Japanese Patent Application No. 61-100222, in which a nitrogen-containing heterocyclic ring is condensed with a phenol nucleus. Typical examples thereof include couplers (1) described in US Pat. No. 4,327,173. (3) Compounds (3) and (16) described in 4,564,586, and compounds described in 4,430,423 and (1) and (3) can be mentioned.

As phenolic cyan couplers, other U.S. Pat.Nos. 4,333,999, 4,451,559, 4,444,872, 4,4
27,767, 4,579,813, European Patent (EP) 067,689B1
And the like. Typical examples thereof include couplers (7) described in US Pat. No. 4,333,999, couplers (1) described in US Pat. No. 4,451,559, and couplers described in US Pat.
Couplers (14) described in 4,444,872, couplers (3) described in 4,427,767, couplers (6) and (24) described in 4,609,619, and couplers (1) and (11) described in 4,579,813. And couplers (45) and (50) described in European Patent No. (EP) 067,689B1, and a coupler (3) described in JP-A-61-42658.

As the naphthol cyan coupler, those having an N-alkyl-N-arylcarbamoyl group at the 2-position of the naphthol nucleus (for example, US Pat. No. 2,313,586) and those having an alkylcarbamoyl group at the 2-position (for example, US Pat.
Nos. 474,293 and 4,282,312) those having an arylcarbamoyl group at the 2-position (for example, Japanese Patent Publication No. 50-14523) and those having a carboxamide or sulfonamide group at the 5-position (for example, JP-A-60-237448; 61-145557, 61-1536
No. 40), those having an aryloxy leaving group (for example, US Pat. No. 3,476,563), those having a substituted alkoxy leaving group (for example, US Pat. No. 4,296,199), and those having a glycolic acid leaving group (for example, Japanese Patent Publication No. 60-39217). )and so on.

These couplers are usually contained in the silver halide emulsion layer constituting the photosensitive layer in an amount of 0.1 to 1.0 mol, preferably 0.1 to 0.5 mol, per mol of silver halide.

In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by an oil-in-water dispersion method known as an oil protection method, and after being dissolved in a solvent, it is emulsified and dispersed in a gelatin aqueous solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water dispersion with phase inversion. The alkali-soluble coupler can also be dispersed by a so-called Fisher dispersion method. After removing the low-boiling organic solvent from the coupler dispersion by a method such as distillation, noodle washing or ultrafiltration, it may be mixed with a photographic emulsion.

Dielectric constant (25 ° C) as a dispersion medium for such couplers
It is preferable to use a high-boiling organic solvent having a refractive index of 2 to 20 and a refractive index (25 ° C.) of 1.5 to 1.7 and / or a water-insoluble polymer compound.

As the high boiling point organic solvent, preferably, the following general formula (A)
The high-boiling organic solvent represented by (E) is used.

General formula (B) W ₁ -COO-W ₂ Formula (E) W ₁ —O—W ₂ (wherein W ₁ , W ₂ and W ₃ each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group; W ₄ is W ₁ , OW ₁ or S
It represents -W _1, n is 1 to 5 integer, n is 2
In the above case, W ₄ may be the same as or different from each other, and in formula (E), W ₁ and W ₂ may form a condensed ring).

The high-boiling organic solvent that can be used in the present invention is a compound that is not miscible with water having a melting point of 100 ° C. or less and a boiling point of 140 ° C. or more other than the general formulas (A) to (E). Can be used. The high boiling point organic solvent preferably has a melting point of 80 ° C. or lower. The boiling point of the high boiling organic solvent is preferably 160 ° C.
And more preferably 170 ° C. or higher.

Details of these high-boiling organic solvents are described in
No. 215272, page 137, lower right column to page 144, upper right column.

These couplers may be impregnated with a loadable latex polymer (for example, U.S. Pat.No. 4,203,716) in the presence or absence of the high boiling organic solvent or dissolved in a water-insoluble and organic solvent-soluble polymer. It can be emulsified and dispersed in a hydrophilic colloid aqueous solution.

Preferably, pages 12 to 30 of WO 88/00723
The homopolymers or copolymers described on the page are used, and the use of an acrylamide polymer is particularly preferred for stabilizing a color image.

The light-sensitive material prepared by using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, and the like as a color fogging inhibitor.

Various anti-fading agents can be used in the light-sensitive material of the present invention. That is, hydroquinones as organic anti-fading agents for cyan, magenta and / or yellow images,
6-hydroxychromans, 5-hydroxycoumarins, spirochromans, p-alkoxyphenols,
Representative examples include hindered phenols, mainly bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. No. Further, metal complexes represented by "bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Specific examples of the organic anti-fading agent are described in the specifications of the following patents.

Hydroquinones are disclosed in U.S. Pat.Nos. 2,360,290 and 2,4
No. 18,613, No. 2,700,453, No. 2,701,197, No. 2,
No. 728,659, No. 2,732,300, No. 2,735,765, No.
No. 3,982,944, No. 4,430,425, UK Patent No. 1,363,921
No., U.S. Pat.Nos. 2,710,801 and 2,816,028,
6-Hydroxychromans, 5-hydroxycoumarins, and spirochromans are described in U.S. Pat.
No. 3,573,050, No. 3,574,627, No. 3,698,909, No. 3,764,337, JP-A-52-152225, Spiroindanes in U.S. Pat.No. 4,360,589, p-Alkoxyphenols in U.S. Pat. UK Patent 2,0
No. 66,975, JP-A-59-10539, JP-B-57-19765, and the like, hindered phenols are disclosed in U.S. Pat.
No., JP-A-52-72224, U.S. Pat.
No. 52-6623, gallic acid derivatives, methylenedioxybenzenes and aminophenols are described in U.S. Pat.
Nos. 3,457,079, 4,332,886 and JP-B-56-21144, hindered amines are disclosed in U.S. Pat.
No. 4,268,593, British Patent No. 1,326,889, No. 1,354,
No. 313, No. 1,410,846, JP-B-51-1420, JP-A-58
Nos. 1-114036, 59-53846 and 59-78344, metal complexes are disclosed in U.S. Pat.Nos. 4,050,938 and 4,241,155.
And British Patent No. 2,027,731 (A). These compounds can achieve the object by adding usually 5 to 100% by weight of the corresponding color coupler to the photosensitive layer after co-emulsification with the coupler. In order to prevent the deterioration of the cyan dye image due to heat and particularly to light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent thereto.

Examples of the ultraviolet absorber include benzotriazole compounds substituted with an aryl group (for example, those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (for example, those described in U.S. Pat. Nos. 3,314,794 and 3,352,681),
Benzophenone compounds (for example, those described in JP-A-46-2784) and cinnamate compounds (for example, US Pat.
3,705,805 and 3,707,395), butadiene compounds (described in U.S. Pat. No. 4,045,229),
Alternatively, benzooxide compounds (for example, US Pat.
3,406,070, 3,677,672 and 4,271,307) can be used. UV-absorbing couplers (for example, α-naphthol-based cyan dye-forming couplers)
Alternatively, an ultraviolet absorbing polymer or the like may be used. These ultraviolet absorbers may be mordanted to a specific layer.

Above all, a benzotriazole compound substituted with the above-mentioned aryl group is preferable.

It is particularly preferable to use the following compounds together with the above-mentioned coupler. In particular, combination use with a pyrazoloazole coupler is preferred.

That is, the compound (F) which forms a chemically inert and substantially colorless compound by chemically bonding with the aromatic amine-based developing agent remaining after the color developing process and / or the aromatic compound remaining after the color developing process. The compound (G) which forms a chemically inert and substantially colorless compound by chemically bonding with an oxidized form of an aromatic amine color developing agent can be used simultaneously or alone, for example, in storage after processing. It is preferable in order to prevent the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent or its oxidized product and the coupler remaining in the film.

Preferred as the compound (F) is a secondary reaction rate constant K ₂ (in trioctyl phosphate at 80 ° C.) of 1.0 l / mol · sec to 1 × 10 ⁻⁵ l / mol · sec with p-anisidine. Is a compound that reacts with The secondary reaction rate constant can be measured by the method described in JP-A-63-158545.

If K ₂ is greater than this range, the compound itself becomes unstable, resulting in decomposition reacts with gelatin or water. On the other hand, if K ₂ is smaller than this range, the reaction with the remaining aromatic amine-based developing agent is slow, and as a result, side effects of the remaining aromatic amine-based developing agent may not be prevented.

More preferable compound (F) can be represented by the following general formula (FI) or (FII).

General formula (FI) R _1- (A) _n -X General formula (FII) In the formula, R ₁ and R ₂ each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0. A represents a group which forms a chemical bond by reacting with an aromatic amine-based developer, and X represents a group which is eliminated by reacting with an aromatic amine-based developer. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y promotes addition of an aromatic amine-based developing agent to the compound of the general formula (FII). Represents a group. Here, R ₁ and X, Y and R ₂ or B may be bonded to each other to form a cyclic structure.

Representative methods of chemically bonding with the residual aromatic amine-based developing agent are a substitution reaction and an addition reaction.

Specific examples of the compounds represented by the general formulas (FI) and (FII) are described in specifications such as JP-A-63-158545, JP-A-62-283338, EP-A-298321, and 277589. Are preferred.

On the other hand, the compound (G) which forms a chemically inert and colorless compound by chemically bonding with the oxidized form of the aromatic amine developing agent remaining after the color development processing is more preferably represented by the general formula (GI) Can be represented by

Formula (GI) RZ In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group. Z represents a nucleophilic group or a group which decomposes in the light-sensitive material to release a nucleophilic group. In the compound represented by the general formula (GI), Z is a nucleophilic ⁿ CH ₃ I value of Pearson (RGPearson,
et al., J. Am. Chem, Soc., 90 , 319 (1968)), or a group derived therefrom is preferred.

Specific examples of the compound represented by the general formula (GI) are described in EP-A-255722, JP-A-62-143048 and JP-A-62-143048.
No. 229145, Japanese Patent Application Nos. 63-136724 and 62-214681, and European Patent Publications 298321 and 277589 are preferred.

The details of the combination of the compound (G) and the compound (F) are described in EP-A-277589.

The light-sensitive material prepared according to the present invention contains a water-soluble dye or a dye which becomes water-soluble by photographic processing as a filter dye in the hydrophilic colloid layer, or for various purposes such as prevention of irradiation or halation. You may. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, gelatin is lime-treated,
Either one treated with an acid may be used. The details of the method for producing gelatin are described in The Macromolecular Chemistry of Gelatin (Academic Press, 1964), by Arthur Byes.

As the support used in the present invention, a transparent film such as a cellulose nitrate film or a polyethylene terephthalate, which is usually used for a photographic light-sensitive material, or a reflective support can be used. For the purposes of the present invention, the use of a reflective support is more preferred.

The term "reflective support" used in the present invention refers to a material which enhances reflectivity and sharpens a dye image formed in a silver halide emulsion layer. Examples include those coated with a hydrophobic resin dispersedly containing a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin dispersedly containing a light-reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer or combined with a reflective substance, such as a glass plate, polyethylene terephthalate, a polyester film such as cellulose triacetate or cellulose nitrate, Examples include a polyamide film, a polycarbonate film, a polystyrene film, and a vinyl chloride resin.

Other reflective supports include specular or secondary
A support having a seed diffuse reflective metal surface can be used. The metal surface has a spectral reflectance of 0.5 in the visible wavelength range.
The above materials are preferred, and the metal surface is preferably roughened or diffusely reflective using metal powder. As the metal, aluminum, tin, silver, magnesium or an alloy thereof is used, and the surface may be the surface of a metal plate, a metal foil, or a metal thin layer obtained by rolling, vapor deposition, plating, or the like.
Above all, it is preferable to obtain a metal by vapor deposition on another substrate. It is preferable to provide a water-resistant resin, especially a thermoplastic resin layer, on the metal surface. An antistatic layer is preferably provided on the side of the support of the present invention opposite to the side having the metal surface. For details of such a support, see, for example, JP-A-61-210346.
Nos. 63-24247, 63-24251 and 63-24255.

 These supports can be appropriately selected depending on the purpose of use.

As the light-reflective substance, it is preferable to sufficiently knead a white pigment in the presence of a surfactant.
It is preferable to use those treated with a to tetravalent alcohol.

Next, when a developer is applied on a thin layer on a photosensitive material in the present invention, the total liquid film thickness (including the swelling of the film) is 500 μm.
m or less, more preferably 10 to 300
μm. As a treatment method, a coating method described below,
There are a method of passing through a slit and a method of spraying with a spray.

Further, in the present invention, a method in which the developer is repeatedly applied many times may be used. Further, after applying and developing the developing solution, simple washing is performed to reduce the influence in the next step.

By repeating the application, the uniformity of the liquid film is improved. The higher the number of repetitions, the higher the image density uniformity (no development unevenness) and the higher the image density. However, since this brings complexity, the number of repetitions or the number of coatings can be adjusted according to the purpose. You can choose. Of course, the advantages and disadvantages of repeated application vary depending on the application type, and the optimum conditions are selected according to each case.

For the application step, a known arbitrary method such as a method of applying a liquid contained in a material for absorbing a processing liquid such as a roller coat, a dip coat, a slide hopper coat, a hopper coat, a kiss coat, a felt cloth or a sponge sheet, or the like is used. be able to.

Details are described in Yuji Harazaki's "Coating Studies" (especially pages 253-255), Asakura Shoten (Showa 46), and "Paper Processing Handbook" edited by Paper Industry Times, pages 129-138 (Showa 48). Specifically, the following method can be used.

(1) air doctor coater (2) blade coater (blade coater) (3) rod coater (rod coater) (4) knife coater (knife coater) (5) squeeze coater (6) Impregnation coater (7) Reverse roll coater
r) (8) Transfer roll coater
coater) (9) gravure coater (10) kiss roll coater (kiss roll coater) (11) cast coater (cast coater) (12) spray coater (spray coater) (13) curtain coater (cucrtain coater) ( 14) Calendar coater (calender coater) (15) Extrusion coater Other methods such as visco-coating, in which the processing solution is hopper-coated,
Also, a bicoat method in which a web coated with a thin layer of a processing solution is overlaid on a photosensitive material can be used.

Generally, it is not necessary to thicken the developer. When the viscosity is increased by using gelatin, a thickener, etc., there are no advantages due to the increase in viscosity, disadvantages such as the fact that the developer itself does not easily proceed, an unnecessary film is formed after coating, and the like. Is caused.

However, when the coating thickness greatly depends on the viscosity as in dip coating, it may be preferable to add a slight thickener (for example, carboxymethyl cellulose).

In this case, the viscosity is 1 to 10 centipoise at 20 ° C., more preferably 1 to 5 centipoise.

When the developer is applied on the photosensitive material, if the thickness exceeds 300 μm, it becomes impossible to apply the developer as a liquid film on the photosensitive material. It becomes difficult to leave as a membrane, 10μ
If it is less than m, it is difficult to perform coating uniformly.

In the present invention, a processing liquid used in a step subsequent to the color development step can also be applied. This method is preferable because the amount of waste liquid can be significantly reduced. Specifically, after a color developing solution is applied to a photosensitive material, a bleaching solution, a bleach-fixing solution, a fixing solution, etc. are similarly coated to a thickness of 1 to 200 μm, preferably 10 to 100 μm, more preferably 20 to 70 μm. Then, apply an aqueous solution or a stable liquid to the same thickness,
Finally, the processing solution remaining on the photosensitive material is removed by a roller coater or the like. In addition, the desilvering step and / or the water-solubility and stabilization step can be performed in a tank by a conventional method.

The color developing solution contains p as described above having a hydrophilicity-imparting group.
-It is preferable to use an aqueous solution containing a phenylenediamine type developing agent since the solution can be greatly concentrated.

Examples of the salt of the above-mentioned main drug include a sulfate, a hydrochloride, a p-toluenesulfonate, a phosphate and the like.

The content of the developing agent in the developing agent is generally 5 mM or more, preferably 0.01 to 0.2 M, more preferably 0.02 to 0.
1M. For example, a photosensitive material having a silver amount of 0.6 g / m ² and a film thickness of 10 μ
When processing a small amount of the developer 0 cc / m ^2, it should be a concentration of about 0.09～0.1M, the highly concentrated amount 7-8 times the amount used generally in the development processing of color paper Equivalent to.

In general, the amount is preferably 1 to 3 equivalents, preferably 1 to 2 equivalents, per the amount of silver applied to the light-sensitive material. The ratio (molar ratio) to the coupler in the light-sensitive material is 2.5 or less, and preferably 1 or less.
~ 2.

High concentration can be achieved only by applying the above-mentioned developing agent having a hydrophilic group. It was also found that the development delay in the lowermost layer was small, and the development characteristics were greatly improved as compared with a developing agent having no hydrophilic group.

In the embodiments of the present invention, it is preferable to use a developer substantially free of benzyl alcohol. Here, substantially not containing, preferably 2 ml / l or less,
More preferably, the benzyl alcohol concentration is 0.5 ml / l or less, and most preferably, it contains no benzyl alcohol at all.

More preferably, the developer used in the present invention does not substantially contain sulfite ions. Sulfite ions have a function of dissolving silver halide and reacting with an oxidized form of the developing agent, and at the same time, function as a preservative of the developing agent to reduce the dye-forming efficiency. Such an effect is presumed to be one of the causes of the increase in the fluctuation of the photographic characteristics due to the continuous processing.
Here, substantially not containing, preferably 3.0 × 10 ^-3
It has a sulfite ion concentration of not more than mol / l, and most preferably contains no sulfite ion. However, in the present invention, a very small amount of sulfite ion used for preventing oxidation of a processed kit in which a developing agent is concentrated before preparing a working solution is excluded.

The developer used in the present invention preferably does not substantially contain sulfite ions, and more preferably does not substantially contain hydroxyamine. This is because hydroxylamine itself has silver developing activity at the same time as functioning as a preservative of the developer, and fluctuations in the concentration of hydroxylamine are considered to greatly affect photographic characteristics. The term "substantially free of hydroxylamine" as used herein means that the hydroxylamine concentration is preferably 5.0 × 10 ⁻³ mol / l or less, and most preferably contains no hydroxylamine at all.

More preferably, the developer used in the present invention contains an organic preservative in place of the hydroxylamine and sulfite ions.

Here, the organic fragrance refers to all organic compounds that reduce the deterioration rate of an aromatic primary amine color developing agent by being added to a processing solution of a color photographic light-sensitive material. That is, organic compounds having a function of preventing oxidation of a color developing agent by air or the like, among which hydroxylamine derivatives (excluding hydroxylamine; the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxy ketones, α-amino ketones,
Sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines, and the like are particularly effective organic preservatives. These are disclosed in
−4235, 63−30845, 63−21647, 63−4465
No. 5, 63-53551, 63-43140, 63-56654,
63-58346, 63-43138, 63-146041, 63
-44657, 63-44656, U.S. Patent No. 3,615,503,
No. 2,494,903, JP-A-52-143020, JP-B-48-30496
No., etc.

Other preservatives include JP-A Nos. 57-44148 and 57-5.
Various metals described in 3749, salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, U.S. Pat. An aromatic polyhydroxy compound described in 3,746,544 or the like may be contained as necessary. In particular, addition of alkanolamines such as triethanolamine, dialkylhydroxylamine such as diethylhydroxylamine, hydrazine derivatives or aromatic polyhydroxy compounds is preferred.

Among the above organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides)
Are particularly preferred, and for details, see Japanese Patent Application No. 62-2552.
No. 70, No. 63-9713, No. 63-9714, No. 63-11300 and the like.

It is more preferable to use the above-mentioned hydroxyamine derivative or hydrazine derivative in combination with an amine from the viewpoint of improving the stability of the color developing solution and further improving 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 disclosed in Japanese Patent Application No. 63-9713. 63
Amines as described in JP-11300.

In the present invention, 1 × 10 chlorine ions are contained in the color developer.
Up to ^-1 mol / l can be contained. Chloride ion concentration is 1.5 × 10 ^-1
If it is more than 10 ^-1 mol / l, it has the disadvantage of delaying the development, and is not preferred for achieving the object of the present invention of rapid and high density.

In the present invention, bromine ions are contained in a color developer at 5 ×
It can contain up to 10 ^-4 mol / l. It is more preferable not to contain bromine ions because they delay development and lower the maximum density and sensitivity.

Here, chlorine ions and bromine ions may be directly added to the developer or may be eluted from the photosensitive material into the developer during the development processing.

When directly added to the color developer, examples of the chloride ion supply material include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, with the preferred ones being preferred. Are sodium chloride and potassium chloride.

Further, it may be supplied from a fluorescent whitening agent added to the developer.

Sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, thallium bromide Among them, preferred are potassium bromide and sodium bromide.

When eluted from the light-sensitive material during the development processing, both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from sources other than the emulsion.

The color developer used in the present invention is preferably pH 9
To 12, more preferably 9 to 11.0, and the color developer may further contain a compound of a known developer component.

In order to maintain the above pH, it is preferable to use various buffers. Buffers 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 salts, trishydroxyaminomethane salts, lysine salts, and the like. In particular, carbonate, phosphate, tetraborate, and hydroxybenzoate are soluble and have a high pH of 9.0 or more.
It is excellent in the buffering capacity in the H region, has no adverse effects on photographic performance (such as fog) even when added to a color developer, and has the advantages of being inexpensive, and it is particularly preferable to use these buffers.

Specific examples of these buffers include sodium carbonate,
Potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), tetraborate Potassium, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-
Sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate)
And so on. However, the invention is not limited to these compounds.

The amount of the buffer added to the color developer is preferably from 0.01 to 0.4 mol / l, particularly from 0.02 mol / l to 0.2 mol / l.
Particularly preferred is l.

In addition, various chelating agents can be used in the color developer as a precipitation inhibitor for calcium or magnesium, or for improving the stability of the color developer.
For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenesulfonic acid, transsilohexanediaminetetraacetic acid, 1 , 2-Diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'- Bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid and the like can be mentioned.

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

These chelating agents may be added in an amount sufficient to block the metal ions in the color developer. For example, 1
It is about 0.1g to 10g per unit.

An optional development accelerator can be added to the color developer as needed.

As development accelerators, JP-B-37-16088 and JP-B-37-598
No. 7, No. 38-7826, No. 44-12380, No. 45-9919, and thioether compounds represented in U.S. Pat.No. 3,813,247, and p-type compounds described in JP-A Nos. 52-49829 and 50-15554. Phenylenediamine compounds, JP-A-50-137726
JP-B-44-30074, JP-A-56-156826 and 52
-43429 and the like, quaternary ammonium salts, U.S. Patent Nos. 2,494,903, 3,128,182, 4,230,796,
No. 3,253,919, JP-B-41-11431, U.S. Pat.
Nos. 546, 2,596,926 and 3,582,346, amine compounds described in JP-B-37-16088, JP-B-42-25201, U.S. Pat.No. 3,128,183, JP-B-41-11431, JP-B-42-2388.
No. 3, US Pat. No. 3,532,501, etc., polyalkylene oxides, 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as necessary.

In the present invention, an optional antifoggant can be added as required. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-
Nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-
Representative examples include nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer applicable to the present invention preferably contains a fluorescent whitening agent. 4,4 'as fluorescent whitening agent
-Diamino-2,2'-disulfostilbene compounds are preferred. The addition amount is 0 to 5 g / l, preferably 0.1 g to 4 / l.

Further, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added as needed.

The processing temperature of the color developer applicable to the present invention is 20 to
80 ° C, preferably 30 to 60 ° C. The processing time is 5 seconds to 2 minutes, preferably 10 seconds to 40 seconds.

As described above, in the processing method of the present invention, after the exposed photosensitive material is processed in the color developing step, it can be processed in a usual method, for example, a desilvering step, a washing and / or stabilizing step, and a drying step. it can. Further, the subsequent process can be performed by a coating method. After the developing agent is removed in the stabilization step, the desilvering step may be started.

Next, the desilvering step applicable to the present invention will be described. As the desilvering step, generally, any steps such as a bleaching step-fixing step, a fixing step-bleach-fixing step, a bleaching step-bleach-fixing step and a bleach-fixing step may be used.

The bleaching solution, bleach-fixing solution and fixing solution applicable to the present invention will be described below.

As the bleaching agent used in the bleaching solution or the bleach-fixing solution, any bleaching agent can be used. In particular, organic complex salts of iron (III) (for example, ethylenediaminetetraacetic acid,
Preferred are aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid and complex salts such as aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as citric acid, tartaric acid and malic acid; persulfates; hydrogen peroxide and the like. .

Among these, organic complex salts of iron (III) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming organic complex salts of iron (III) include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropane. Examples thereof include tetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, and glycol ether diaminetetraacetic acid. These compounds may be any of the sodium, potassium, thylium or ammonium salts. Among these compounds, ethylenediaminetetraacetic acid,
Iron (III) complex salts of diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred because of their high bleaching power. These ferric ion complex salts may be used in the form of complex salts or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. And a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.
An iron ion complex salt may be formed. In addition, the chelating agent may be used in excess of forming a ferric ion complex salt. Among the iron complexes, aminopolycarboxylate iron complexes are preferable, and the added amount is 0.01 to 1.0 mol / l, preferably 0.0
It is 5 to 0.50 mol / l.

In the bleaching solution, the bleach-fixing solution and / or the prebath thereof,
Various compounds can be used as a bleaching accelerator.
For example, U.S. Pat.No. 3,893,858, German Patent No.
No. 1,290,812, JP-A-53-95630, and compounds having a mercapro group or a disulfide bond described in Research Disclosure No. 17129 (July, 1978); -20832, 53-327
No. 35, U.S. Pat. No. 3,706,561, and the like, thiourea-based compounds or halides such as iodine and bromine ions are preferred because of their excellent bleaching power.

Other bleaching solutions or bleach-fixing solutions applicable to the present invention include bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride) or iodine. A rehalogenating agent such as an iodide (eg, ammonium iodide). One or more inorganic acids having a pH buffering capacity such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, if necessary; Organic acids and their alkali metal or ammonium salts or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

Fixing agents used in the bleach-fixing solution or the fixing solution include known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylenebisthioglycolic acid Thioether compounds such as 3,6-dithia-1,8-octanediol and water-soluble silver halide dissolving agents such as thioureas, which 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 one 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 is preferably 3 to 10, more preferably 5 to 9.

Further, the bleach-fixing solution may contain other various types of fluorescent whitening agents, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fixing solution and the fixing solution include sulfites (for example, sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives, It preferably contains a sulfite ion releasing compound such as metabisulfite (for example, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are converted to sulfite ions
The content is preferably 0.02 to 0.05 mol / l, more preferably 0.04 to 0.40 mol / l.

As a preservative, sulfite is generally added,
In addition, you may add ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound, etc.

Further, a buffer, an optical brightener, a chelating agent, an antifoaming agent, a fungicide, and the like may be added as necessary.

After desilvering such as fixing or bleach-fixing, washing and / or stabilization are generally performed.

The amount of rinsing water in the rinsing process can vary widely depending on the characteristics of the photosensitive material (for example, the material used such as a coupler), the application, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set. 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 (Journa
l of the Society of Motion Picture and Television
Engineers), Vol. 64, pp. 248-253 (May, 1955). Usually, the number of stages in the multistage countercurrent system is preferably 2 to 6, particularly preferably 2 to 4.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced,
For example, 0.5 l to 1 or less per m ^{2 of the} photosensitive material is possible, and the effect of the present invention is remarkable, but bacteria increase due to an increase in the residence time of water in the tank, and the generated suspended matter adheres to the photosensitive material. Problems occur. As a solution to such a problem, the method of reducing calcium and magnesium described in JP-A-62-2288838 can be used very effectively. In addition, the inchazolone compounds and thiabendazoles described in JP-A-57-8542, and
Chlorinated fungicides such as chlorinated sodium isocyanurate described in JP-120145, benzotriazole, the same ion described in JP-A-61-26761, and others, Hiroshi Horiguchi, "Bactericidal and antifungal chemistry" (1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Disinfection, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Antimicrobial and Antifungal Society, "Dictionary of Antifungal and Antifungal Agents" (1986). A bactericide can also be used.

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.

It is possible to carry out the treatment with the stabilizing solution directly after the washing step or without the washing step. A compound having an image stabilizing function is added to the stabilizing solution, for example, an aldehyde compound represented by formalin, or a film suitable for stabilizing a dye.
Examples include a buffer for adjusting the pH, 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 stabilization is directly performed without going through a washing step, a method disclosed in
Known methods described in JP-A Nos. 8543, 58-14834, 60-220345, etc. can all be used.

In addition, it is also a preferred embodiment to use a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid, 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 stabilization step is 4 to 10, more preferably 5 to 8. The temperature can be set variously depending on the use and specification of the photosensitive material, but is generally 15 to 45 ° C, preferably 20 to 40 ° C. The time can be set arbitrarily, but a shorter time is desirable from the viewpoint of reducing the processing time. It is preferably from 5 seconds to 1 minute and 45 seconds, more preferably from 10 seconds to 1 minute. It is preferable that the replenishing amount is small in view of running cost, reduction of discharge amount, handleability, and the like.

A specific preferable replenishing amount is 0.5 to 50 times, preferably 3 to 4 times the amount of light-sensitive material and the amount brought in from the previous bath per unit area.
It is 0 times. Alternatively, the amount is 1 or less, preferably 500 ml or less per 1 m ^{2 of the} photosensitive material. Replenishment may be performed continuously or intermittently.

The liquid used in the water washing and / or stabilizing step can be further used in the previous step. As an example of this, the overflow of the washing water is reduced by a multi-stage countercurrent method, and is allowed to flow into a bleach-fix bath preceding the bath, and the bleach-fix bath is replenished with a concentrated solution to reduce the amount of waste liquid.

After the above-mentioned water washing and / or stabilization treatment,
For example, the photosensitive material is preferably dried at room temperature to 90 degrees for 10 seconds to 10 minutes. Incidentally, the drying can be omitted.

[Effects of the Invention] According to the present invention, it is possible to process with a small amount of a developing solution as compared with the conventional method, and in some cases, a non-waste liquid developing process can be performed, and sufficient gradation reproduction and image can be achieved in a short processing time. A color image forming method for giving a density is obtained. Further, the space for the processing and waste liquid tanks is reduced, and the processing apparatus can be made compact.

(Specific embodiments of the invention)

Hereinafter, specific examples of the present invention will be shown, and the present invention will be described in detail.

Example 1 The following first layer (lower layer) and second layer (upper layer) were coated on a paper support laminated on both sides with polyethylene to prepare photosensitive material-1. The coating amount is shown in parentheses and the average particle size is shown in <>. First layer gelatin (1.3 g / m ² ) zinc hydroxide <average particle size 0.35 μm> 0.5 g / m ² ) hardener [1-oxy-3,5-dichloro-s-triazine sodium salt] (0.03 g / m ²⁾ Second layer gelatin (1.2 g / m ² ) Silver chlorobromide emulsion <average particle size 0.9 μm (AgBr 0.7 mol%, cubic)> (silver 0.27 g / m ² ) Yellow coupler [ExY] (0.82 g / m ² ) ² ) Solvent [solvent-1] (0.35 g / m ² ) Support Photosensitive material 2 was prepared with the same composition except that zinc hydroxide was omitted.

After subjecting each material to image exposure, it was developed according to the following developing process.

 Next, the composition of each processing solution is shown.

Color developer-1 Ethylenediamine-N, N, N, N tetramethylenephosphonic acid 1.5 g Triethanolamine 8 g Sodium chloride 1.4 g Potassium carbonate 5.0 g 3-Methyl-4-amino-N-ethyl-N-β-hydroxyethyl Aniline 3/2 sulfate monohydrate 15 g N, N-bis (carboxymethyl) hydrazine 5.5 g 2,6 pyridinedicarboxylic acid 12.4 g Fluorescent whitening agent (WHITEX4B, manufactured by Sumitomo Chemical) 1.0 g Water was added and the pH was adjusted to 10.05 at 25 ° C. with 1000 ml potassium hydroxide.

Bleaching / fixing solution Ammonium thiosulfate (79%) 100 ml Sodium sulfite 17 g Iron (III) ethylenediaminetetraacetate 55 g Ethylene diaminetetraacetate 5 g Ammonium bromide 40 g Add water 1000ml pH (25 ℃) 6.0 Stabilizing solution 0.1N hydrochloric acid 350ml Sodium citrate dihydrate 4.4g Add water 1000ml pH (25 ℃) 3.2 Using the above processing solution, apply a color developing solution
Was applied so as to obtain a thickness. (40 ° C, 15 seconds)
35 ° C, 15 seconds with bleach-fix solution and 25-45 ° C, 15 seconds with stabilizing solution
Treated in tank for seconds.

After drying, the maximum density (Dmax) and the minimum density (Dmin) of each of the obtained yellow images were measured through a B filter.

According to the method of the present invention, an image having a uniform and high Dmax was obtained despite a small amount of liquid and a short processing time.

Example 2 A multilayer color photographic paper photosensitive material-3 having the following layer constitution was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

Preparation of first layer coating solution 19.1 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) To 4.4 g of the color image stabilizer (Cpd-7) and 0.7 g of the color image stabilizer (Cpd-7), 27.2 cc of ethyl acetate and 8.2 g of the solvent (Solv-3) were added and dissolved.
It was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing c. On the other hand, a silver chlorobromide emulsion (cubic, 3: 7 mixture of 0.88 μm and 0.70 μm in average grain size (silver molar ratio). The variation coefficient of grain size distribution is 0.08 and 0.10, and each emulsion is silver bromide.
The following blue-sensitive sensitizing dyes are added to the large-sized emulsion in an amount of 2.0 × 10 ⁻⁴ mol per mol of silver, and the small-sized emulsion is added to the small-sized emulsion. , Each of which was subjected to sulfur sensitization after addition of 2.5 × 10 ^-4 mol. The above-mentioned emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the following composition.

Coating solutions for the second to seventh layers were prepared in the same manner as for the first layer and the coating solution. As the gelatin hardener for each layer, 1
-Oxy-3,5-dichloro-s-triazine sodium salt was used.

 The following were used as spectral sensitizing dyes for each layer.

(Per mol of silver halide, 2.0 × 10 ^-4 mol for large-size emulsion, and each for small-size emulsion
2.5 × 10 ^-4 mol) (Per mole of silver halide, for large emulsions
4.0 × 10 ^-4 mol, 5.6 × 10 ^-4 mol for small size emulsion) and (Per mole of silver halide, for large emulsions
7.0 × 10 ^-5 mol, and 1.0 × 10 ^-5 for small size emulsions
Mole) (Per mole of silver halide, for large emulsions
0.9 × 10 ^-4 mol, and 1.1 × 10 ^-4 for small size emulsions
The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Also, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mole of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

The following dyes were added to the emulsion layer to prevent irradiation.

(Layer Configuration) The composition of each layer is shown below. The numbers indicate the attached amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [The first layer side polyethylene contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0.35 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixture prevention layer) Gelatin 0.99 Zinc hydroxide (average particle size 0.35 μm) 0.50 Color mixture inhibitor (Cpd-5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (green sensitive layer) Silver chlorobromide emulsion (cubic, having an average particle size of 0.55 μm, 0.39 μm 1: 3 mixture (Ag molar ratio) with the ones with a variation in grain size distribution of 0.10 and 0.08, with AgBr 0.
0.12 Gelatin 1.24 Magenta coupler (ExM) 0.20 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.15 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0.02 Solvent (Solv-2) 0.40 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Zinc hydroxide (average particle size 0.35 μm) 0.50 Ultraviolet absorbing agent (UV-1) 0.47 Mixed color Inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of 0.58 μm and 0.45 μm) (Ag mole ratio) The variation system of the grain size distribution was 0.09 and 0.11, and each emulsion had an AgBr0.
6 mol% was locally contained in a part of the particle surface. 0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-7) 0.40 Color image stabilizer (Cpd-8) 0.04 Solvent (Solv-6) 0.15 Sixth layer (UV absorbing layer) Gelatin 0.53 UV absorbing agent (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (protective layer) Gelatin 1.33 Zinc hydroxide (average particle size 0.35 μm) 0.50) Acrylic-modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03 (Solv-3) solvent O = PO-C ₉ H ₁₉ (iso)) ₃ Photosensitive material-4 having exactly the same composition except that zinc hydroxide in the second, fourth and seventh layers was omitted was prepared.

First, each sample was subjected to gradation exposure of a three-color separation filter for sensitometry using a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K).
The exposure at this time was performed so that the exposure amount was 250 CMS with an exposure time of 0.1 second.

The sample after the exposure was processed using a liquid having the following processing step and processing liquid composition. The color development was carried out by coating, and the bleach-fixing and washing were carried out in a tank. The compositions of the processing steps Temperature Time 30μm thickness of the thin layer color development 38 ° C. 15 seconds blix 33 ° C. 15 seconds Washing 25 to 45 ° C. 20 seconds Drying 70 to 80 ° C. 40 seconds color developing solution as follows, bleach-fixing The same liquid as in Example 1 was used.

Color developing solution-2 Ethylenediamine-N, N, N, N-tetramethylenephosphonic acid 1.5 g Triethanolamine 8.0 g Sodium chloride 1.4 g Potassium carbonate 5.0 g 3-Methyl-4-amino-N-ethyl-N-β -Hydroxypropylaniline sulfate 20.0 g 3-Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline 3/2 sulfate monohydrate 7.5 g N, N-bis- (carboxy Methyl) hydrazine 5.5 g 2,6-pyridinedicarboxylic acid 12.4 g Optical brightener (WHITEX 4B, manufactured by Sumitomo Chemical) 1.0 g Water was added, and 1000 ml of pH (25 ° C.) 10.05 The obtained yellow, magenta, and cyan color images were subjected to B, G, and R filters corresponding to each dye, and the maximum density (Dmax) and the minimum density (Dmin) were measured. .

By this processing method, an image having a uniform and high Dmax was obtained in all layers despite the small amount of liquid and the short processing time. In particular, it can be seen that the concentration of the lowermost layer is sufficiently high.

Next, the action of the complex-forming compound used in the present invention will be described.

First, 10 μl per 0.5 cm ² of the color developing solution-2 was dropped on the exposed photosensitive material-3 using a micropipette,
Immediately (equivalent to about 100 ml / m ² ), a flat type pH electrode was pressed on the membrane surface, and the pH was measured. Also from the color developing solution-2
A liquid having exactly the same composition (hereinafter referred to as "color developing solution-2A") was used, except that 2,6 pyridinedicarboxylic acid was added, and the same operation as described above was performed. The movement of pH on the membrane surface is shown in FIG.

As is apparent from FIG. 1, a complex forming compound (2,6 pyridinedicarboxylic acid) which coordinates with a metal ion was added.
When a color developing solution is used, the alkali (OH
^- ) Ions are generated, and the decrease in pH is small. Conversely, the pH tends to increase. On the other hand, when there is no complex-forming compound, it can be seen that the pH greatly decreases with time due to H ⁺ generated in the development reaction.

This suggests that the same phenomenon occurs in the photosensitive layer, and it is understood that replenishment of the base is important when processing with a small amount of liquid.

Example 3 Photosensitive materials 5 to 21 were prepared in exactly the same manner as in Example 2 except that the halogen composition and the presence or absence of the basic metal compound in the photosensitive material were as shown in Table 3.

Color developing solutions 3 and 4 were prepared using exactly the same components except that the type of the developing agent and the amount of potassium carbonate in the color developing solution 2 of Example 2 were changed as follows.

The same operation as in Example 2 was carried out using the liquid amounts shown in Table 3, and
evaluated.

In order to obtain an image having a high Dmax without image unevenness in a small amount of liquid and short-time processing in the present invention, 1) use a high silver chloride silver halide emulsion; 2) generate a base in the light-sensitive material. Preferably, 3) use of a developing agent having a hydrophilicity-imparting group It is understood that it is necessary to satisfy all of the above conditions 1) and 2). When even one of the conditions 1) and 2) did not satisfy the conditions, the insufficient yellow density of the lowermost layer was particularly noticeable, and it was found that the image had a color balance largely deviated. Further, satisfying the condition of 3) is not only more preferable, but also does not cause a problem of precipitation of a color developing solution component.

[Brief description of the drawings]

FIG. 1 shows changes in the film pH of the photosensitive material of Example 2. The vertical axis indicates the pH value, and the horizontal axis indicates time.

Claims (1)

(57) [Claims] 1. A color image is developed by developing a light-sensitive material containing at least one kind of coupler which forms a dye by a coupling reaction with an oxidized form of an aromatic primary amine developing agent, a light-sensitive silver halide and a binder. A method wherein the silver halide is substantially silver iodide-free silver halide comprising at least 80 mol% of silver chloride;
The photosensitive material contains a basic metal compound which is hardly soluble in water, and a compound which releases a base when complexed with a metal ion constituting the basic metal compound which is hardly soluble in water; and -Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline or 3-methyl-4-amino-
A color image forming method, comprising applying a color developing solution containing N-ethyl-N-β-hydroxypropylaniline or a salt thereof in a thin layer on the surface of a photosensitive material to perform color developing processing.