JPH0827511B2 - Method of forming dye image - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application] The present invention develops a dye image by subjecting a silver halide color photographic light-sensitive material (hereinafter referred to as a color light-sensitive material) to color development processing and then bleach-fixing processing. More particularly, the present invention relates to a method for forming a dye image, which significantly reduces the pollution load, performs a rapid processing, and imparts excellent dye image fastness.

PRIOR ART Conventionally, for example, benzyl alcohol has been preferably added and used in a color developer for a light-sensitive material for color photographic paper for the purpose of promoting development or improving the reactivity of a photographic coupler with quinone diimine. It was It is known that when benzyl alcohol is added to the color developing solution, the speed of penetration of the color developing agent into the color light-sensitive material can be increased and the development speed of the silver halide emulsion can be increased. The benzyl alcohol also has an action of accelerating the coupling reaction between the quinonediimine, which is an oxidized product of the color developing agent as a result of color development, and the photographic coupler. This is particularly preferable from the viewpoint of silver saving, since the use of benzyl alcohol results in maximum utilization of quinonediimine.

On the other hand, the amount of benzyl alcohol generally used for color development processing of the present light-sensitive materials for color photographic paper is 10
It is used at a ratio of at least 15 ml / l to 15 ml / l, and at such an amount, the solubility of benzyl alcohol in a color developing solution is remarkably reduced, and as a cosolvent for improving this, for example, ethylene glycol, It is necessary to add a considerable amount of diethylene glycol, triethylene glycol, triethanolamine or the like to dissolve benzyl alcohol.

The use of such a large amount of benzyl alcohol and a cosolvent is contrary to its photographic usefulness, and is extremely unfavorable in terms of pollution.

Many attempts have heretofore been made to reduce or remove benzyl alcohol in a color developing solution. Most of them use a compound having a higher color developability as a hydrophobic coupler, but particularly in a color printing paper used as a final print image, it is necessary to obtain good color developability even if benzyl alcohol is removed. In addition, the fastness of the obtained dye image to light, temperature or humidity is strongly required. Further, the spectral absorption characteristics of the dye image formed by the coupler and the stability of the emulsion dispersion in an aqueous binder such as gelatin for stable production are also very important characteristics. From this point of view,
Looking at various couplers that have been proposed so far, good color forming properties, that is, high maximum density, gradation and sensitivity are maintained even when benzyl alcohol in the color developing solution is removed, and light, temperature and humidity are maintained. In contrast, the dye image that has strong fastness is provided, the color reproduction has preferable spectral absorption characteristics, the stability of the emulsion dispersion of the coupler is good, and the number of couplers that can be obtained at low cost is limited. there were.

By the way, in recent years, it has been strongly desired to rapidly carry out color development processing (usually according to the processing steps of color development-bleaching-fixing-washing, or color developing-bleaching fixing-washing). And in color photographic paper, color development-bleach-fixing-washing (or stabilization) is the most common,
It is necessary to perform each process quickly.

The most common way to speed up color development is
Means are used to increase the development temperature, increase the pH of the developer, decrease the bromide ion concentration, which is the main component of the development inhibitor, or increase the concentration of the color developing agent.

However, raising the temperature of the developer rapidly accelerates the oxidation of the color developing agent by oxygen, and is not suitable for continuous processing over a long period of time, especially above about 40 ° C. Then, this deterioration becomes extremely large. Also, when the pH of the color developing solution is raised, the coupling reaction between the oxidant of the color developing agent and the coupler becomes lower when the pH is higher than a certain value, and the color developing solution can be used indefinitely.
It is also impossible to raise the pH. Generally, the pH of the color developing solution is about 12 or less. Further, the bromide ion concentration in the color developing solution is generally determined by the bromide ion eluted from the color light-sensitive material by the development of silver halide and the replenishment rate of the color developing replenishing solution. In order to reduce the bromide ion concentration in the solution, it is necessary to increase the replenishment rate of the replenisher or to use a silver halide composition having a lower silver bromide composition used in the color light-sensitive material. However, the former is not preferable in terms of pollution control because it increases the amount of developing waste liquid, and the latter is inconvenient for a color light-sensitive material which requires high sensitivity because the silver halide composition used is limited. That is.

On the other hand, the concentration of the color developing agent generally can greatly vary depending on pH, temperature and the presence or absence of benzyl alcohol, but in particular, when benzyl alcohol is substantially removed, it can be dramatically increased. Conventionally, the concentration of the color developing agent in the color developing solution of color photographic paper has been about 0.01 mol / l, but by removing benzyl alcohol, it is possible to dissolve it at about 0.02 mol / l or more. As a result, by removing the benzyl alcohol and increasing the concentration of the color developing agent, it is possible to simultaneously achieve pollution control and speeding up of the color development.

On the other hand, in order to shorten the total processing time, it is necessary to shorten bleach-fixing and water washing (or stabilization) following color development.

Bleach-fixing generally involves a desilvering reaction of developed silver and a dye image once formed with a color developer during bleaching of silver.
The rate of reaction that is partially converted to a leuco dye (bleaching) and then returns to the dye image (color restoration) becomes the rate-determining effect.

In recent years, significant progress has been made compared to the past, due to the progress of gelatin hardening technology, the adoption of various 2-equivalent couplers, and the development of couplers which are more difficult to form leuco dyes. In bleach-fixing, the fading-recoloring reaction is becoming rate-determining, but this fading-recoloring reaction is usually a particularly serious problem for cyan couplers forming an indoaniline dye. The fading-recoloring reaction markedly lowers benzyl alcohol in the bleach-fix solution due to the presence of the color developing agent, and is improved by removing benzyl alcohol from the color developing solution, and increases in the color developing agent (benzyl alcohol). Also, the color developing agent is brought into the bleach-fixing solution from the color developing solution during continuous processing and is accumulated in the bleach-fixing solution. Therefore, a cyan coupler which does not cause discoloration with respect to speeding up of the bleach-fixing process or which recovers color in a short time even if it occurs is essential.

Furthermore, it is necessary to remove unnecessary processing chemicals (color developing agent, thiosulfate, ethylenediaminetetraacetate iron salt, etc.) remaining in the color light-sensitive material by washing or stabilizing processing, which is low in a short time and low. It is necessary to remove almost completely with the amount of washing water or the replenishment rate of the stabilizing solution. Above all, the residual amount of the color developing agent and the fastness of the resulting dye image to light, heat, and humidity are significantly affected, and therefore it is necessary to reduce it as much as possible. Preferably, it should be about 1 mg or less per 1 m ² of the processed color light-sensitive material.

However, the increase in the concentration of the color developing agent in the color developing solution increases the amount of the color developing agent remaining in the color light-sensitive material after the processing, and significantly deteriorates the fastness of the dye image to light, heat and humidity. The amount of the color developing agent remaining in the color light-sensitive material after the processing is further increased not only by washing with water or stabilization but also by bleach-fixing. The color developing agent remaining after this treatment is
In particular, the cyan coupler forming an indoaniline dye has a great influence on the fastness of the dye image.

[Object of the Invention] Therefore, the first object of the present invention is to speed up the color developing process by substantially removing benzyl alcohol from the color developing solution and increasing the concentration of the color developing agent. Even if the sensitivity, gradation, and maximum density are sufficiently maintained, and the bleach-fixing treatment does not cause fading to the leuco dye, or even if it occurs, a dye image forming method capable of quickly achieving color restoration is provided. It is in.

A second object of the present invention is to provide a color developing agent remaining after the processing with respect to the light, heat, and humidity of the dye image, even when the color developing, the bleach-fixing, and the washing or stabilizing processing are rapidly performed. It is an object of the present invention to provide a method for forming a dye image that has a small effect on the fastness.

[Construction of the Invention] The above-mentioned object of the present invention is to provide a silver halide color photographic light-sensitive material having a silver halide emulsion layer containing at least one diffusion-resistant hydrophobic coupler on a support after imagewise exposure. In a method for forming a dye image by performing color development processing with a color developing solution containing substantially no benzyl alcohol, and then performing bleach-fixing processing within 60 seconds,
The color developer contains 0.02 mol / l or more of a color developing agent,
At least one of the diffusion-resistant hydrophobic couplers is represented by the following general formula [I] or [II], and the hydrophobic couplers are dissolved in a phthalate ester high-boiling point organic solvent to form a silver halide emulsion layer. It is achieved by a method of forming a dye image characterized by being dispersed.

General formula [I] [In the formula, R ₁ represents an alkyl group having 1 to 6 carbon atoms, and R ₂ represents a ballast group having 10 or more carbon atoms. Z
Represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. ] General formula [II] [In the formula, R ₃ represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group, or an atom group necessary for bonding with R ₄ to form a 6-membered ring. R ₄ represents an alkyl group or an aryl group. R ₄ may combine with R ₃ to represent an atomic group necessary for forming a 6-membered ring. R ₅ is an alkyl group,
It represents a cycloalkyl group, an aryl group, an alkylamino group, an arylamino group or a heterocyclic group. Z'is synonymous with Z. The present invention will be described in more detail below.

In the general formula [I], the number of carbon atoms represented by R ₁ is 1
-6 alkyl groups are linear or branched alkyl groups, such as ethyl group, propyl group, butyl group, i-
A propyl group, an n-pentyl group, and the like, which may have a substituent. Examples of the substituent include an acylamino group (eg, an acetylamino group) and an alkoxy group (eg, a methoxy group). However, R ₁ is preferably an unsubstituted alkyl group.

The ballast group represented by R ₂ is an organic group having a size and shape that provides the coupler molecule with sufficient bulk to prevent the coupler from substantially diffusing the coupler from the layer to which it is applied. .

Representative ballast groups include alkyl or aryl groups having 8 to 32 total carbon atoms.

These alkyl group and aryl group may have a substituent, and examples of the substituent of the aryl group include an alkyl group, an aryl group, an alkoxy group, an aryloxy group,
Carboxy group, acyl group, ester group, hydroxy group,
Cyano group, nitro group, carbamoyl group, carbonamido group, alkylthio group, arylthio group, sulfonyl group,
Examples thereof include a sulfonamide group, a sulfamoyl group, and a halogen atom, and examples of the substituent of the alkyl group include the substituents of the aryl group except the alkyl group.

Particularly preferred as the ballast group are those represented by the following general formula [III].

General formula [III] R ₆ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, Ar represents an aryl group such as a phenyl group, and this aryl group may have a substituent. Examples of the substituent include an alkyl group, a hydroxy group, an alkylsulfonamide group and the like, and the most preferable one is a branched alkyl group such as a t-butyl group.

In the present invention, the alkyl group represented by R ₄ in the general formula [II] is a linear or branched one, and for example, a methyl group, an ethyl group, an iso-propyl group, a butyl group, a pentyl group, an octyl group, Examples thereof include nonyl group and tridecyl group, and examples of aryl group include phenyl group and naphthyl group. The group represented by R ₄ may have a single or a plurality of substituents. For example, a typical example of the substituent introduced into the phenyl group is a halogen atom (for example, fluorine or chlorine). , Each atom such as bromine), alkyl group (for example, methyl group, ethyl group, propyl group, butyl group, dodecyl group), hydroxyl group, cyano group, nitro group, alkoxy group (for example, methoxy group, ethoxy group), Alkyl sulfonamide group (eg, methyl sulfonamide group, octyl sulfonamide group, etc.), aryl sulfonamide group (eg, phenyl sulfonamide group, naphthyl sulfonamide group, etc.), alkylsulfamoyl group (eg, butylsulfamoyl group) Groups, etc.), arylsulfamoyl groups (eg, phenylsulfamoyl groups, etc.), alkyloxycals Nyl group (for example, methyloxycarbonyl group), aryloxycarbonyl group (for example, phenyloxycarbonyl group), aminosulfonamide group (for example, N, N-dimethylaminosulfonamide group), acylamino group, carbamoyl group ,
Examples thereof include a sulfonyl group, a sulfinyl group, a sulfooxy group, a sulfo group, an aryloxy group, an alkoxy group, a carboxyl group, an alkylcarbonyl group and an arylcarbonyl group. Two or more kinds of these substituents may be introduced into the phenyl group.

The halogen atom represented by R ₃ is, for example, each atom of fluorine, chlorine, bromine and the like, the alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a dodecyl group and the like, and an alkoxy group. Is, for example, a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, or the like. R ₃
May combine with R ₄ to form a ring.

In the present invention, the alkyl group represented by R ₅ in the general formula [II] is, for example, a methyl group, an ethyl group, a butyl group, a hexyl group, a tridecyl group, a pentadecyl group, a heptadecyl group, or a so-called polysubstituted with a fluorine atom. And a fluoroalkyl group.

The aryl group represented by R ₅ is, for example, a phenyl group or a naphthyl group, preferably a phenyl group. The heterocyclic group represented by R ₅ is, for example, a pyridyl group or a furan group. The cycloalkyl group represented by R ₅ is, for example, a cyclopropyl group or a cyclohexyl group. these
The group represented by R ₅ may have a single or a plurality of substituents. For example, as a substituent introduced into a phenyl group, a typical one is a halogen atom (for example, fluorine, chlorine, bromine). Etc.), alkyl group (eg methyl group, ethyl group, propyl group, butyl group, dodecyl group etc.), hydroxyl group, cyano group, nitro group, alkoxy group (eg methoxy group, ethoxy group etc.), alkyl sulfone Amido group (eg, methylsulfonamide group, octylsulfonamide group, etc.), arylsulfonamide group (eg, phenylsulfonamide group, naphthylsulfonamide group, etc.), alkylsulfamoyl group (eg, butylsulfamoyl group, etc.), Arylsulfamoyl group (eg, phenylsulfamoyl group etc.), alkyloxycarbonyl group (eg For example, methyloxycarbonyl group etc.), aryloxycarbonyl group (eg phenyloxycarbonyl group etc.), aminosulfonamide group, acylamino group, carbamoyl group, sulfonyl group, sulfinyl group, sulfooxy group, sulfo group, aryloxy group, Examples thereof include an alkoxy group, a carboxyl group, an alkylcarbonyl group and an arylcarbonyl group. Two or more kinds of these substituents may be introduced into the phenyl group.

Preferred groups represented by R ₅ are a polyfluoroalkyl group, a phenyl group or a halogen atom, an alkyl group, an alkoxy group, an alkylsulfonamido group, an arylsulfonamido group, an alkylsulfamoyl group, an arylsulfamoyl group, an alkyl group. A phenyl group having one or more sulfonyl groups, arylsulfonyl groups, alkylcarbonyl groups, arylcarbonyl groups, or cyano groups as substituents.

In the general formulas [I] and [II], the groups capable of splitting off upon reaction with an oxidized product of an aromatic primary amine type color developing agent represented by Z or Z ′ are well known to those skilled in the art. , In the coating layer or other layer containing the coupler in the silver halide color photographic light-sensitive material by modifying the reactivity of the coupler or leaving the coupler.
By exerting functions such as development suppression, bleaching suppression, and color correction, it acts advantageously. Typical examples include halogen atoms typified by chlorine and fluorine, substituted / unsubstituted alkoxy groups, aryloxy groups, arylthio groups, carbamoyloxy groups, acyloxy groups, sulfonyloxy groups, sulfonamide groups or heteroylthio groups. , A heteroyloxy group and the like. Particularly preferred Z or Z'is a hydrogen atom or a chlorine atom, most preferably a chlorine atom.

More specifically, JP-A-50-10135 and 50-120334.
No. 50, No. 50-130441, No. 54-48237, No. 51-146828, No.
54-14736, 47-37425, 50-123341, 58-9534
No. 6, JP-B-48-36894, U.S. Patents 3,476,563, 3,73
It is described in the respective gazettes of 7,316 and 3,227,551.

The specific examples of the couplers represented by formula (I) are shown below, but the couplers are not limited to these.

General formula [I] The typical examples of the cyan coupler represented by the general formula [II] are shown below, but the cyan coupler is not limited thereto.

These cyan couplers are used in an amount of 0.05 to 0.7 mol, preferably 0.1 to 0.6 mol, per mol of silver halide emulsion.

As a method of adding these cyan couplers to the silver halide emulsion layer of the color light-sensitive material according to the present invention, the boiling points of dibutyl phthalate, dioctyl phthalate, dilauryl phthalate, diamyl phthalate, tricresyl phthalate, dibenzyl phthalate, etc. Each of the above couplers is dissolved in a phthalate ester high boiling organic solvent at about 170 ° C. or higher and finely dispersed in a hydrophilic colloid such as gelatin in the presence of a surfactant.

In the color light-sensitive material of the present invention, a color antifoggant, an image stabilizer and an ultraviolet absorber can be appropriately used together with the cyan coupler.

As the color antifoggant, a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative and the like are preferable, and specific examples thereof include US Pat.
0,290, 2,336,327, 2,403,721, 2,418,613
No., No. 2,675,314, No. 2,701,197, No. 2,704,713,
2,728,659, 2,732,300, 2,735,765, 3,7
00,453, JP-A-50-92988, 50-92989, 50-939
No. 28, No. 50-110337, No. 50-156438, No. 52-146235
No. 55-95948, No. 59-5247, and Japanese Patent Publication No. 50-23813.

As the image stabilizer, for example, a hydroquinone derivative,
Gallic acid derivative, phenol derivative and its bis form, hydroxycoumarane and its spiro form, hydroxychroman and its spiro form, piperidine derivative, aromatic amine compound, benzodioxane derivative, benzdioxole derivative, silicon atom-containing compound, thioether compound Etc. are preferred. As a specific example, British Patent No. 1,410,846
JP-A-49-134326, JP-A-52-35633, JP-A-52-147434
No. 52-150630, No. 54-145530, No. 55-6321, No. 5
5-21004, 55-124141, 59-3432, 59-5246
No. 59-10539, Japanese Patent Publication No. 48-31625, 49-20973,
No. 49-20974, No. 50-23813, No. 52-27534, U.S. Patent Nos. 2,360,290, 2,418,613, 2,675,314, and 2,7.
01,197, 2,704,713, 2,710,801, 2,728,65
No. 9, No. 2,732,300, No. 2,735,765, No. 2,816,028,
3,069,262, 3,336,135, 3,432,300, 3,4
57,079, 3,573,050, 3,574,627, 3,698,90
No. 9, No. 3,700,455, No. 3,764,337, No. 3,935,016,
3,982,994, 4,013,701, 4,113,495, 4,1
20,723, 4,155,765, 4,159,910, 4,254,21
No. 6, No. 4,268,593, No. 4,279,990, No. 4,332,886,
No. 4,360,589, No. 4,430,425, No. 4,452,884, etc.

As the ultraviolet absorber, a benzophenone compound (for example, JP-A-46-2784, U.S. Pat. Nos. 3,215,530 and 3,698,
No. 907), butadiene compounds (for example, those described in US Pat. No. 4,045,229), 4-thiazolidone compounds (for example, US Pat. Nos. 3,314,794 and 3,352,6).
81), and benzotriazole compounds substituted with an aryl group (for example, Japanese Examined Patent Publication Nos. 36-10466 and 41-168).
No. 7, No. 42-26187, No. 44-29620, No. 48-41572, JP-A No. 54-95233, No. 57-142975, U.S. Patent No. 3,253,921.
No., No. 3,533,794, No. 3,754,919, No. 3,794,493,
4,099,038, 4,220,711, 4,323,633, Research Disclosure 225
19), benzooxide compounds (for example, those described in US Pat. No. 3,700,455), cinnamic acid ester compounds (for example, US Pat. No. 3,705,805,
3,707,375, those described in JP-A-52-49029) can be used. Further, those described in US Pat. No. 3,499,762 and JP-A-54-48535 can also be used. Ultraviolet absorbing couplers (for example, α-naphthol type cyan dye forming couplers) and ultraviolet absorbing polymers (for example, JP-A-58-111942, 178351 and 181041).
No. 59-19945, No. 23344, and those described in the official gazette). These ultraviolet absorbers may be mordanted to a specific layer.

The binder used in the constituent layers of the color light-sensitive material of the present invention is most commonly gelatin such as alkali-treated gelatin or acid-treated gelatin. A part of this gelatin and phthalated gelatin, phenylcarbamoyl gelatin, etc. Derivative gelatin can be used.

When the silver halide color photographic light-sensitive material of the present invention is a multicolor element, the layers necessary for the photographic element, including the layers of the image-forming constituent units described above, can be in various orders as known in the art. Can be arranged. A typical multicolor silver halide color photographic light-sensitive material comprises a cyan dye image-forming unit comprising at least one red-sensitive silver halide emulsion layer containing at least one cyan dye-forming coupler, at least one magenta dye-forming unit. Contains a coupler,
A magenta dye image-forming structural unit comprising at least one green-sensitive silver halide emulsion layer and a yellow dye-image forming structural unit comprising at least one blue-sensitive silver halide emulsion layer containing at least one yellow dye-forming coupler. It is made to be carried on a support. In this case, there are layers other than the layer of the image forming constituent unit, for example, a non-photosensitive layer such as a filter layer, an intermediate layer, a protective layer, an antihalation layer and an undercoat layer.

More specifically, the multicolor silver halide color photographic light-sensitive material of the present invention comprises a blue-sensitive layer, a non-photosensitive layer (first intermediate layer), a green-sensitive layer and a non-photosensitive layer (second An intermediate layer), a red-sensitive layer, a non-photosensitive layer containing an ultraviolet absorber (third intermediate layer) and a protective layer may be used.

Examples of the support according to the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper; a transparent support provided with a reflective layer or combined with a reflector; a glass plate;
Examples thereof include polyester films such as cellulose acetate, cellulose nitrate, and polyethylene terephthalate; polyamide films; polycarbonate films; polystyrene films. Each of these supports is appropriately selected according to the purpose of use of the silver halide photographic light-sensitive material of the present invention.

For coating the silver halide emulsion layer and the non-photosensitive layer used in the present invention, various coating methods such as dipping coating, air doctor coating, curtain coating and hopper coating are used.

The silver halide used in the silver halide emulsion according to the present invention includes silver bromide, silver chloride, silver iodobromide, silver chlorobromide,
It includes any of those used in ordinary silver halide emulsions such as silver chloroiodobromide. These silver halide grains may be coarse grains or fine grains, and the grain size distribution may be narrow or wide. A monodisperse emulsion having a narrow particle size distribution is preferably used.

The crystals of these silver halide grains are normal crystals,
Twins may be used, and any ratio of {100} faces to {111} faces can be used.

Preferable are cubic and tetradecahedral grains, and more preferable are tetradecahedral grains.

The tetrahedral grain is measured by the X-ray diffraction analysis method described in JP-A-59-29243, Is a monodisperse silver halide grain satisfying 5 ≦ K ≦ 500.

Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may be a layered structure having different inside and outside. Further, these silver halides may be of a type that forms a latent image mainly on the surface or may be of a type that is formed inside the grain. Furthermore,
These silver halides may be produced by any of the neutral method, the ammonia method and the acidic method, and may be produced by any of the simultaneous mixing method, the forward mixing method, the back mixing method and the conversion method. Also applicable are silver halide grains.

The silver halide emulsion of the present invention comprises, in addition to the sensitizing dye of the present invention, sulfur sensitizers such as arylthiocarbamide, thiourea and cystine, active or inactive selenium sensitizers, and reduction sensitizers. Sensitizers such as stannous salt,
Sensitizers of noble metal sensitizers such as polyamines, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurosulfobenzthiazole methyl chlorite, or water-soluble salts such as ruthenium and iridium. Sensitizers, specifically, ammonium chloroparadate, potassium chloroplatinate, sodium chloroparadide and the like can be chemically sensitized alone or in combination.

The silver halide emulsion according to the present invention can contain various known photographic additives. For example, it is a photographic additive as described in "Research Disclosure", December 1978, No. 17643.

The silver halide emulsion layer and the non-photosensitive layer of the silver halide color photographic light-sensitive material of the present invention may contain various other photographic additives. For example, antifoggant, white stain inhibitor, fluorescent whitening agent, antistatic agent, hardener, which are described in Research Disclosure Magazine 17643.
A plasticizer, a wetting agent, an antioxidant, an ultraviolet absorber and the like can be appropriately used.

When the color light-sensitive material of the present invention is subjected to color development processing, an aromatic primary amine compound is used as a color developing agent used in a color developing solution. The following compounds can be mentioned as such an example.

4-amino-N, N-diethylaniline, 3-methyl-
4-amino-N, N-diethylaniline, 4-amino-N
-Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-
N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethyl-4-amino-N, N-diethylaniline, 3-methoxy-4-amino-N- Ethyl-N-β-hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-
N-β-methoxyethylaniline, 3-acetamido-
4-amino-N, N-diethylaniline, 4-amino-N, N
-Dimethylaniline, N-ethyl-N-β- [β- (β
-Methoxyethoxy) ethoxy] ethyl-3-methyl-
4-aminoaniline, N-ethyl-N-β- (β-methoxyethoxy) ethyl-3-methyl-4-aminoaniline and salts thereof such as sulfate, hydrochloride, sulfite, p
-Toluene sulfonate and the like. Especially 3-methyl-
Most preferred is 4-amino-N-ethyl-N-β-methanesulfonamide ethylaniline sulfate.

It is necessary to add 0.02 mol or more, preferably 0.025 mol or more, of these aromatic primary amine type color developing agents to one color developing solution in order to obtain the effects of the present invention.

Further, various additives can be added to these color developing solutions as needed.

Typical examples are alkaline agents (eg, alkali metal or ammonium hydroxides, carbonates, phosphates, etc.), pH adjusting or buffering agents (eg, weak acids such as acetic acid and boric acid, weak bases, salts thereof, etc.). ), Development accelerators (for example, pyridinium compounds, cationic compounds, potassium nitrate and sodium nitrate, polyethylene glycol condensates and their derivatives, nonionic compounds such as polythioethers, polymer compounds having sulfite ester, etc. Pyridine, ethanolamine, etc., organic amines, hydrazines, etc., antifoggants (eg alkali bromide, alkali iodide and nitrobenzimidazoles,
Mercaptobenzimidazole, 5-methylbenzotriazole, 1-phenyl-5-mercaptotetrazole, compounds for rapid processing liquids, thiosulfonyl compounds, phenazine N oxides, benzothiazolium nitrobenzoate derivatives, etc.), stain or sludge prevention Agent, layering effect accelerator, preservative (for example, sulfite, acidic sulfite,
Hydroxylamine hydrochloride, form sulfite, alkanolamine sulfite adduct, etc.) and the like.

The silver halide color photographic light-sensitive material according to the present invention can be bleached by a conventional method after color development processing. This process may be simultaneous with fixing or may be separate. This processing solution can be used as a bleach-fix bath by adding a fixing agent as needed.

In the present invention, it is preferable to use a bleach-fixing bath suitable for rapid processing.

A metal complex salt of an organic acid as a bleaching agent used in a bleach-fixing solution used in a bleach-fixing treatment step is an aminopolycarboxylic acid or an acid, an organic acid such as citric acid, and coordinates metal ions such as iron, cobalt and copper. It was done. The most preferable organic acid used for forming such a metal complex salt of an organic acid includes a polycarboxylic acid. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific examples of these include the following.

These bleaching agents are 5-450 g / l, more preferably 20-25
Use at 0g / l. As the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the above-mentioned bleaching agent and, if necessary, a sulfite as a preservative is applied. Also,
A bleach-fixing solution having a composition in which a small amount of an ethylenediaminetetraacetate iron (III) complex salt bleaching agent and another halide such as ammonium bromide of the above silver halide fixing agent are added, or conversely, a halide such as ammonium bromide is added. It is also possible to use a bleach-fixing solution having a composition added in a large amount, or a special bleach-fixing solution having a composition comprising a combination of an ethylenediaminetetraacetic acid iron (III) complex salt bleaching agent and a large amount of a halide such as ammonium bromide. it can. As the halide, hydrochloric acid other than ammonium bromide,
Hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide and the like can also be used.

The silver halide fixing agent contained in the bleach-fixing solution is a compound which reacts with silver halide as used in ordinary fixing processing to form a water-soluble complex salt, for example, potassium thiosulfate, sodium thiosulfate, thiol. Typical examples thereof include thiosulfates such as ammonium sulfate, potassium thiocyanate, sodium thiocyanate, thiocyanates such as ammonium thiocyanate, thiourea and thioether. These fixing agents are used in an amount in the range of 5 g / l or more so that they can be dissolved, but generally 70 g to 250 g / l are used.

The bleach-fixing solution contains boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Various pH buffering agents such as sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide can be contained alone or in combination of two or more kinds.
Furthermore, various fluorescent whitening agents, antifoaming agents or surfactants may be contained. In addition, preservatives such as bisulfite adducts of hydroxylamine, hydrazine, and aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohol and nitrates, organic agents such as methanol, dimethylsulfamide, dimethylsulfoxide, etc. A solvent and the like can be contained as appropriate.

For the bleach-fixing solution, JP-A-46-280 and JP-B-45-8506
No. 46-556, Belgian Patent No. 770,910, Japanese Patent Publication No. 45-
8836, 53-9854, JP-A-54-71634 and 49-4234
Various bleaching accelerators described in No. 9 and the like can be added.

The pH of the color developing solution of the present invention is preferably 10 or more,
Particularly, when benzyl alcohol is removed from the color developing solution in the case of 10.4 or more and 12.0 or less, good photographic performance can be quickly obtained. Also, the temperature of the color developing solution is 30 ℃ or higher, 45
C. or less is preferable, and 32.degree. C. or more and 42.degree. C. or less are most preferable.

The pH of the bleach-fix solution is about 4.0 or more and 9.0 or less, preferably about 5.0 to 8.0. The temperature of the bleach-fix solution is 20
The temperature is not lower than 50 ° C and not higher than 50 ° C, preferably not lower than 25 ° C and not higher than 40 ° C.

The color light-sensitive material of the present invention is subjected to bleach-fixing treatment,
It is necessary to remove unnecessary treatment chemicals by washing with water, but instead of washing with water, JP-A-58-14834, 58-105145, 58-
You may perform water washing alternative stabilization treatment as shown in 134634 and 58-18631, and Japanese Patent Application No. 58-2709 and 59-89288.

The processing time of the color light-sensitive material of the present invention varies depending on the kind of the light-sensitive material, the temperature of each processing solution, pH and the like, but the color development processing is generally within 2 minutes, preferably within 1 minute 30 seconds, and most preferably. Is done within a minute. The bleach-fixing treatment is preferably carried out within 60 seconds, particularly preferably within 50 seconds. Furthermore, washing or stabilizing treatment within 2 minutes,
It is preferably performed within 1 minute and 30 seconds.

When the color light-sensitive material of the present invention is processed while continuously replenishing the replenishing solution, it is preferable to use a color developing replenishing solution having a treatment chemical concentration of about 10% to 50% more concentrated than that of the color developing solution. Further, it is preferable that bromide ion is not contained.

The pH of the color developing replenisher is about 0.1 than the pH of the color developing solution.
The pH of the bleach-fix replenisher is preferably about 0.3 to 1.5 lower than the pH of the continuously processed bleach-fix.

When processing is carried out while continuously replenishing each color developing, bleach-fixing and stabilizing solution of the present invention, the replenishment rate of each replenishing solution is 100 to 1,000 ml, preferably 150 to 1,000 per 1 m ² of color light-sensitive material. It is 500 ml.

Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 A polyethylene support was laminated on one side of a 170 g / m ² paper support with polyethylene on one side and polyethylene containing 11% by weight of anatase titanium dioxide on the other side. The silver halide color photographic light-sensitive materials Nos. 1 to 14 were prepared by sequentially coating. still,
Unless otherwise specified, the addition amount is shown as an amount per 1 m ² .

Layer 1: 1.2 g of gelatin, 0.32 g (in terms of silver, the same applies hereinafter) of a blue-sensitive silver chlorobromide emulsion (Note-1, AgBr 90 mol%, average particle size 0.50 μm), 0.50 g of di-2-ethylhexyl A layer containing 0.70 g of a yellow coupler (Y-1) dissolved in phthalate (hereinafter abbreviated as DOP) and 0.04 g of a color stain inhibitor HQ-1.

Layer 2 ... an interlayer containing 0.7 g gelatin, 15 mg anti-irradiation dye (AI-1), 10 mg (AI-2) and 0.05 g DOP in which 0.05 g HQ-1 was dissolved.

Layer 3: 1.25 g of gelatin, 0.22 g of green-sensitive silver chlorobromide emulsion (Note-2, AgBr60 mol%, average particle size 0.40 μm) 0.30 g of D
0.45g magenta coupler (M-1) dissolved in OP and
Layer containing 0.01 g of HQ-1.

Layer 4--An intermediate layer containing 1.2 g gelatine, 0.08 g HQ-1 and 0.35 g DOP with 0.5 g UV absorber (UV-1) dissolved.

Layer 5: 1.4 g of gelatin, 0.20 g of red-sensitive silver chlorobromide emulsion (Note-3, AgBr60 mol%, average particle size 0.65 μm), 0.20 g
A layer containing the cyan coupler shown in Table 1 and 0.01 g of HQ-1 dissolved in di-butyl phthalate.

Layer 6 ... 0.30 g dissolved in 1.0 g gelatin and 0.20 g DOP
UV-1 containing layer.

Layer 7: Layer containing 0.5 g of gelatin.

As a hardener, 0.04 g of 2,4-dichloro-6-hydroxy-s-triazine sodium was added to each of the layers 4 and 7 immediately before coating.

Further, in Layer 5, instead of di-butyl phthalate
0.20 g of phosphoric acid ester organic solvent, S-1 and S-2
Sample Nos. 15 and 16 were prepared in the same manner as Sample Nos. 1 to 14 except that the cyan coupler was dissolved in.

(Note-1) Blue-sensitive silver chlorobromide emulsion 2.8 × 1 sodium thiosulfate per mol of silver halide
It was chemically sensitized by adding 0 ^-5 mol and optically sensitized with a blue sensitizing dye. As a stabilizer, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene compound was added in an amount of 4.5 × 10 ⁻³ mol per mol of silver halide.

(Note-2) Green-sensitive silver chlorobromide emulsion Sodium thiosulfate 3.5 × 1 per mol of silver halide
It was chemically sensitized by adding 0 ^-5 mol, and optically sensitized with a green sensitizing dye. As a stabilizer, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene compound was added to silver halide 1
4.5 × 10 ⁻³ mol was added per mol.

(Note-3) Red-sensitive silver chlorobromide emulsion sodium thiosulfate 3.5 × 1 per mol of silver halide
Chemical sensitization was performed by adding 0 ^-3 mol, and optical sensitization was performed using a red sensitizing dye. As a stabilizer, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene compound was added in an amount of 4.5 × 10 ⁻³ mol per mol of silver halide.

After exposing each of the above light-sensitive materials to white light through an optical wedge,
It processed in the following processes.

[Processing Step I] Color development (38 ° C) 50 seconds, 60 seconds, 70 seconds Bleach-fixing (38 ° C) 60 seconds Water washing (30-34 ° C) 60 seconds Drying 80-90 ° C, 45 seconds The composition of each processing solution is It is as follows.

[Color developer A] Pure water 800 ml Hydroxylamine sulfate 2.4 g Potassium bromide 1.35 g Sodium chloride 1.0 g Potassium sulfite 2.5 g N-ethyl-N-β-methanesulfonamidoethyl-3
- methyl-4-amino-aniline 3/2 sulfate · 1 · H ₂ O9.2
g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g Anhydrous potassium carbonate 35 g Kaykoll PK-conc 2.0 g (Fluorescent brightener, manufactured by Shin Nisso Co., Ltd.) Add pure water to 1 to make 20% hydroxylation Adjust the pH to 10.7 with potassium or 10% dilute sulfuric acid.

[Bleach-fixing solution] Pure water 600 ml Ethylenediaminetetraacetic acid iron (III) ammonium 65 g Ethylenediaminetetraacetic acid 2-sodium salt 5 g Ammonium thiosulfate 85 g Sodium hydrogen sulfite 10 g Sodium metabisulfite 2 g Ethylenediaminetetraacetic acid-2 sodium 20 g Sodium bromide 10 g Color developer 200 ml Pure water is added to adjust to 1 and pH is adjusted to 7.0 with dilute sulfuric acid.

The reflection density of the obtained sample is measured with monochromatic red light,
The sensitivity, gradation and maximum density as a cyan dye image were determined. The results are shown in Table 1. In the table, the sensitivity indicates the relative sensitivity when the sensitivity is 100 when the color development processing of Sample 1 is performed for 60 seconds. Further, the gradation represents the slope of the reflection density of 0.5 to 1.8.

On the other hand, 0.3% of the sample obtained by the development process for 60 seconds
The value obtained by subjecting the sample to immersion treatment in an aqueous solution of red blood salt for 60 seconds and measuring the maximum red concentration again is shown in Table 1.

Further, for each of the samples subjected to the processing step (I) (color development for 60 seconds) and the following processing step (II),
Xenon fade meter (Suga Test Instruments Co., Ltd.)
For 240 hours at 80 ° C and 60% relative humidity for 1 week, the density of the cyan dye image was measured by measuring the density with red light, and the residual dye ratio of the cyan dye image was examined. It was

 The results are shown in Table 1.

[Processing step II] Color development B (38 ° C) 3 minutes Bleach-fixing (38 ° C) 1 minute Washing with water (30-34 ° C) 1 minute Drying 80-90 ° C, 45 seconds Color developing solution B becomes color developing solution A. On the other hand, the color developing agent was reduced from 9.2 g to 4.5 g, and diethylene glycol 15 ml / l and benzyl alcohol 15 ml / l were added. (PH
= Adjusted to 10.1) From the results shown in Table-1, it can be seen that Samples 3 to 14 of the present invention have good sensitivity, gradation and maximum density even when treated with a color developing solution containing no benzyl alcohol. On the other hand, Samples 1 and 2 using cyan couplers other than the present invention had a low maximum density, and it was found from the results after bleaching with red blood salt that the treatment (I) formed a cyan leuco dye.

Further, it can be seen that in Samples 15 and 16 in which the cyan coupler is dissolved in a phosphate ester-based high boiling point organic solvent, the gradation is soft and the photofading and dark fading properties are poor.

On the other hand, the photofading and the dark fading were treated by Comparative Samples 1 and 2 (I
It can be seen that, by changing from I) to processing (I), all of the samples 3 to 14 of the present invention show almost no deterioration in the fastness of the dye image due to the difference in processing. .

Example-2 For the sample used in Example-1, processing steps I and II
For each of the, bleach-fixing time 45 seconds, 60 seconds,
After changing to 90 seconds, the photobleaching property and the dark fading property of the cyan dye image were examined in the same manner as in Example-1. However, the color development time is 60 seconds in the processing step (I), 3 minutes in the processing step (II), and the washing time is 1 minute in each case. The obtained results are shown in Table-2.

From the results shown in Table 2, Comparative Samples 1 and 2 show a decrease in the fastness of the dye image in the processing step (I) as the bleach-fixing time is shortened, while Samples 3 to 14 related to the present invention. It can be seen that each of these shows good dye image fastness.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having a silver halide emulsion layer containing at least one diffusion-resistant hydrophobic coupler on a support, and after exposure to an image, benzyl alcohol is substantially added thereto. In a method of forming a dye image by performing color development processing with a color developing solution not containing it, and then performing bleach-fixing processing within 60 seconds, the color developing solution contains 0.02 mol / l or more color developing agent, and At least one of the diffusion-resistant hydrophobic couplers is represented by the following general formula [I] or [II], and the hydrophobic couplers are dissolved in a phthalate ester high boiling point organic solvent and dispersed in the silver halide emulsion layer. And a method for forming a dye image. General formula [I] [In the formula, R ₁ represents an alkyl group having 1 to 6 carbon atoms, and R ₂
Represents a ballast group having 10 or more carbon atoms. Z represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. ] General formula [II] [In the formula, R ₃ represents a hydrogen atom, a halogen atom, an alkoxy group or an alkyl group. R ₄ represents an alkyl group or an aryl group. R ₄ may combine with R ₃ to form a ring.
R ₅ represents an alkyl group, a cycloalkyl group, an aryl group, an alkylamino group, an arylamino group or a heterocyclic group. Z'is synonymous with Z. ]