JPH0695205B2 - Method for forming dye image with excellent rapid processability - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for forming a dye image, and more particularly to a method for forming a dye image which enables rapid processing and gives a dye image having a sufficiently small minimum density.

BACKGROUND OF THE INVENTION In recent years, a silver halide photographic light-sensitive material capable of rapid processing, high in image quality, excellent in processing stability, and low in cost has been demanded in the industry in recent years. There is a demand for a silver halide photographic light-sensitive material capable of rapid processing.

That is, the silver halide photographic light-sensitive material is usually processed continuously by an automatic processor provided at each developing station, but as part of improving the service to users, within the day when the development is accepted. It is required to process the image and return it to the user, and recently it is even required to return it within a few hours from the reception, and the need for rapid processing is increasing. Further, the shortening of the processing time leads to the improvement of the production efficiency and the cost reduction, so that the development of the rapid processing is urgently needed.

In order to achieve rapid processing, a light-sensitive material and a processing solution are approached from two sides. Regarding color development processing, attempts have been made to increase the temperature, increase the pH, increase the concentration of the color developing agent, and the like, and it is also known to add an additive such as a development accelerator. As the development accelerator, British Patent 811,18
1-phenyl-3-pyrazolidone described in No. 5, US Patent
Examples thereof include N-methyl-p-aminophenol described in 2,417,514 and N, N, N ', N'-tetramethyl-p-phenylenediamine described in JP-A-50-15554. However, these methods often do not achieve sufficient speediness and are often accompanied by performance deterioration such as increased fog.

On the other hand, it is known that the shape, size and composition of the silver halide grains of the silver halide emulsion used for the light-sensitive material have a great influence on the development speed and the like. It has been found that particularly high development rates are exhibited when silver is used.

However, when it is attempted to maintain the high developability of a high chloride silver halide emulsion, the increase of fog also becomes large.

Especially in the color development system compared to the black and white development system,
The fog density is more conspicuous than that of black and white because of the formation of a coloring dye, which is an important problem when the characteristics of rapid processability of the high chloride silver halide emulsion are sufficiently exhibited.

Generally, an antifoggant is used to reduce the fog density. One of the best known antifoggants is potassium bromide, which has been used in many developers in the past.
However, when a sample using a high chloride halogen emulsion is processed in a system of a color developing solution containing potassium bromide, rapid processability is significantly impaired. This means that potassium bromide acts as a very strong development inhibitor before fog prevention for high chloride silver halide emulsions,
For the purpose of rapid processability, it is necessary that the color developing solution used in the system of high chloride silver halide emulsion contains substantially no potassium bromide, and the fog becomes worse.

On the other hand, many other organic inhibitors are also known as antifoggants, for example, E. J. Beer, "Stabilization of Photographic Silver Halide Emulsions", Focal Press, Inc. (197
4) (EJBirr, “Stabilization of Photographic Silv
er Halide Emulsions "Focal Press). Among these antifoggants, heterocyclic mercapto compounds are often used because of their strong antifoggant effect. The amount of the heterocyclic mercapto compound used is limited because it is effective in preventing fog and at the same time has a considerably strong development inhibitory effect. When added in an amount that suppresses fogging, the rapid processability is impaired, though not as much as potassium bromide, and the features of using a high chloride silver halide emulsion are greatly reduced. If the addition amount is too large, fog which is a problem in practical use will occur. There is a strong demand for the development of technology that solves the dilemma of maintaining reason and controlling fog.

In general, a silver halide photographic light-sensitive material is continuously processed while replenishing a replenisher at various developing stations such as laboratories.In that case, the composition of the processing solution is changed at the start and the latter half of the continuous processing. It is impossible to keep it constant, and there is a problem that photographic characteristics are changed due to changes in the composition of the processing liquid. This problem is becoming more serious with the recent trend toward lower replenishment of processing solutions.

Above all, it is almost impossible to completely mix the bleach-fixing solution with the developing solution even if the strict setting of the replenishing rate of the replenishing solution, the prevention of evaporation, and the elimination of eluate from the photosensitive material are eliminated. The amount of bleach-fixing solution mixed in the developer remarkably differs depending on the processing amount and the squeeze method, especially in the roller transfer and automatic developing machine, and when the replenishment rate of the processing solution decreases, Since the rotation speed of the liquid is reduced, the mixing ratio is further different.

Further, although the color developing solution is maintained at a high pH, the pH of the color developing solution is unavoidable due to the influence of the replenishing amount of the replenishing solution and the air oxidation during continuous operation.

Fluctuations in photographic performance (in most cases, increase in fog and gradation change) due to mixing of the bleach-fixing solution into the color developing solution and fluctuations in the pH of the color developing solution are stable and good for color reproduction and gradation reproduction. Is a major obstacle. For the above reasons, it is extremely difficult to avoid mixing the bleach-fixing solution and the pH fluctuation itself.Therefore, even if the bleach-fixing solution is mixed, or if the pH fluctuation occurs, the photographic performance fluctuation is small. Development of a silver halide photographic light-sensitive material excellent in so-called BF contamination resistance and pH fluctuation resistance is desired.

The present inventors have conducted various studies on a technique for suppressing an increase in fog, which is a problem when using a silver halide grain having a high silver chloride content suitable for rapid processing, and as a result, a specific compound was identified. It has been found that the combined use of the two makes it possible to satisfactorily suppress fog while maintaining the rapid processability, and has reached the present invention. Furthermore, it is even more surprising to find that the BF
It has been found that it has an additional advantage that it is excellent in contamination resistance and pH fluctuation resistance.

[Object of the Invention] Accordingly, a first object of the present invention is to provide a method for forming a dye image, which is excellent in rapid processability and which can provide a dye image having a sufficiently suppressed minimum density. Second
It is an object of the present invention to provide a method for forming a dye image which is excellent in rapid processability, the minimum density is sufficiently suppressed, and is also excellent in BF contamination resistance and pH fluctuation resistance.

[Construction of the Invention] The above object of the present invention includes color development processing after imagewise exposure of a silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing a dye-forming coupler on a support. In the method of forming a dye image to be photographic processed,
At least one of the silver halide emulsion layers contains, as light-sensitive silver halide, silver halide grains having a silver chloride content of 90 mol% or more and a compound represented by the following general formula [S]. The color developer used in the developing treatment has a sulfite ion content of 2 × 10 ⁻⁴ to 1 × 10 ⁻² mol / l.
And was substantially free of bromide ions.

General formula [S] (In the formula, Q is 1,3,4-triazole ring, 1,3,4-oxadiazole ring, 1,3,4-thiadiazole ring, or 1,3,5-
It represents a group of atoms necessary for forming a triazine ring. M
Represents a hydrogen atom, an alkali metal atom, or an ammonium group. [Specific Structure of the Invention] The silver halide photographic light-sensitive material applied to the present invention contains a compound represented by the general formula [S] in at least one of the silver halide emulsion layers.

In the general formula [S], the 1,3,4-triazole ring, 1,3,4-oxadiazole ring, 1,3,4-thiadiazole ring, and 1,3,5-triazine ring formed by Q are , And those having any substitutable substituent. Examples of the substitutable group include an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, a mercapto group, an amino group, an acylamino group, a sulfonamide group, and a heterocyclic group. Examples of the alkali metal atom represented by M include sodium atom and potassium atom.

Among the compounds represented by the general formula [S] according to the present invention,
Preferred examples include compounds represented by the following general formula [SA].

General formula [SA] Where Z is Represents an oxygen atom or a sulfur atom. R _A is a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, —SR _A1 , -NHSO ₂ R _A5 or a heterocyclic group is represented, R _A1 represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, -COR _A4 , or -SO ₂ R _A5 , and R _A2 and R _A3 are It represents a hydrogen atom, an alkyl group, or an aryl group, and R _A4 and R _A5 represent an alkyl group or an aryl group. M represents a hydrogen atom, an alkali metal atom or an ammonium group.

Examples of the alkyl group represented by R _A , R _A1 , R _A2 , R _A3 , R _A4 and R _A5 in the general formula [SA] include a methyl group, a benzyl group, an ethyl group and a propyl group, and an aryl group is a phenyl group. , Naphthyl group and the like.

Examples of the alkenyl group represented by R _A and R _A1 include a propenyl group and the like, and examples of the cycloalkyl group include a cyclohexyl group and the like. Examples of the heterocyclic group represented by R _A include a furyl group and a pyridinyl group.

Examples of the alkali metal atom represented by M include potassium atom and sodium atom.

The above R _A , R _A1 , R _A2 , R _A3 , R _A4 and the alkyl group and aryl group represented by R _A5 , the alkenyl group and the cycloalkyl group represented by R _A and R _A1 , and the hetero ring represented by R _A The group further includes one having a substituent.

Other preferable examples of the compound represented by the general formula [S] according to the present invention include compounds represented by the following general formula [SB].

General formula [SB] In the formula, R _A and M each represent the same group as R _A and M in the general formula [SA]. R _B1 and R _B2 each represent a group having the same meaning as R _A1 and R _A2 in the general formula [SA].

Specific examples of the compound represented by the general formula [S] are shown below, but the invention is not limited thereto.

The compound represented by the above general formula [S] is, for example,
-28496, JP-A-50-89034, Journal of Chemical Society (J.Chem.Soc.) 49,1748 (1927), 42
37 (1952), Journal of Organic Chemistry (J.Org.Chem.) 39,2469 (1965), US Patent No. 2,
No. 824,001, Journal of Chemical Society,
1723 (1951), JP-A-56-111846, British Patent No. 1,275,7
The compounds described in No. 01, U.S. Pat. Nos. 3,266,897, 2,403,927, etc. are included, and the method of synthesis can also be performed according to the methods described in these documents.

The compound represented by the general formula [S] according to the present invention (hereinafter referred to as the compound [S]) is contained in the silver halide emulsion layer according to the present invention in water or an organic solvent which is optionally miscible with water. It may be added after being dissolved in (for example, methanol, ethanol, etc.). The compound [S] may be used alone, or may be used in combination with another compound represented by the general formula [S], or a stabilizer other than the compound represented by the general formula [S], or an antifoggant. You may use.

The compound [S] is added before the formation of silver halide grains, during the formation of silver halide grains, from the end of the formation of silver halide grains to the start of the chemical ripening, during the chemical ripening, at the end of the chemical ripening, It may be at any time from the end of chemical ripening to the coating. Preferably, it is added during chemical ripening, at the end of chemical ripening, or after the end of chemical ripening and before coating. The addition may be carried out all at once or may be added in a plurality of times.

The place of addition may be directly added to the silver halide emulsion or the silver halide emulsion coating liquid, or may be added to the coating liquid for the adjacent non-photosensitive hydrophilic colloid layer, and the present invention can be added by diffusion during multilayer coating. It may be contained in the silver halide emulsion layer related to the above.

The addition amount is not particularly limited, but is usually within the range of 1 × 10 ^-6 mol to 1 × 10 ^-1 mol, preferably 1 × 10 ^-5 mol to 1 × 10 ^-2 mol, per mol of silver halide. To be done.

The compound [S] according to the present invention is applied to the system of the present invention containing silver halide grains having a silver chloride content of 90 mol% or more, and the minimum dye image formed while maintaining rapid processability. It is not known that the concentration can be kept sufficiently low.

Furthermore, the system of the present invention has extremely stable and good reproducibility against fluctuations in photographic performance due to mixing of a bleach-fixing solution into a color developing solution and fluctuations in pH of the color developing solution, such as gradation change. It also had a completely unexpected additional effect of being excellent in so-called BF contamination resistance and pH fluctuation resistance. More specifically, the compound of the general formula [SA] has a great effect on the resistance to BF contamination, and the compound of the general formula [SB]
Greatly effective against pH fluctuation. In the compounds represented by the general formula [SA], Z is The compound having an oxygen atom showed a more preferable effect than the compound having a sulfur atom.

The silver halide emulsion layer containing the compound [S] according to the present invention contains silver halide grains having a silver chloride content of 90 mol% or more.

The silver halide grains of the present invention have a silver chloride content of 90 mol% or more, preferably a silver bromide content of 10 mol% or less and a silver iodide content of 0.5 mol% or less. . More preferred is silver chlorobromide having a silver bromide content of 0.5 to 5 mol%.

The silver halide grains of the present invention may be used alone,
It may be used by mixing with other silver halide grains having different compositions. Further, it may be used as a mixture with silver halide grains having a silver chloride content of less than 10 mol%.

Further, in a silver halide emulsion layer containing silver halide grains having a silver chloride content of 90 mol% or more of the present invention, the silver chloride content in all silver halide grains contained in the emulsion layer is The proportion of silver halide grains of 90 mol% or more is 60 wt% or more, preferably 80 wt% or more.

The composition of the silver halide grain of the present invention may be uniform from the inside to the outside of the grain, or the composition inside and outside the grain may be different. When the composition inside and outside the particle is different, the composition may continuously change or may be discontinuous.

The grain size of the silver halide grains of the present invention is not particularly limited, but in view of other photographic properties such as rapid processing property and sensitivity, it is preferably 0.2 to 1.6 μm, more preferably 0.25 to 1.2 μm. . The particle diameter can be measured by various methods generally used in the technical field. A typical method is Loveland's “Particle Size Analysis Method” (ASTM Symposium on
Wright Microscopy, 1955, pp. 94-122) or "The Theory of Photographic Processes" (Mies and James, 3rd edition, Chapter 2 published by Macmillan, Inc. (1966)).

This particle size can be measured using the projected area of the particle or a diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately expressed as a diameter or projected area.

The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse. Preferably, in the particle size distribution of silver halide grains, the coefficient of variation is 0.
The number of monodispersed silver halide grains is 22 or less, more preferably 0.15 or less. Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution and is defined by the following equation.

Here, ri represents the particle size of each particle, and ni represents the number. The term "particle size" used herein refers to the diameter of spherical silver halide grains, and the diameter of a cubic image or a grain having a shape other than spherical when the projected image is converted into a circular image of the same area. .

The silver halide grain used in the emulsion of the present invention is an acid method,
It may be obtained by either the neutral method or the ammonia method. The grains may be grown at one time, or may be grown after forming seed grains. The method of forming seed particles and the method of growing seed particles may be the same or different.

The method of reacting the soluble silver salt and the soluble halogen salt may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, and a combination thereof, but a method obtained by the simultaneous mixing method is preferable. Furthermore, as one type of simultaneous mixing method, Japanese Patent Laid-Open No.
It is also possible to use the pAg-controlled double jet method described in US Pat.

Further, if necessary, a silver halide solvent such as thioether may be used.

The silver halide grains according to the present invention may have any shape. One preferable example is a cube having a {100} plane as a crystal surface. In addition, US patent
4,183,756, 4,225,666, JP-A-55-26589, JP-B-55-42737 and the like, and the Journal of
Photographic Science (J.Photgr.Sci), 2
By the method described in the literature such as 1 , 39 (1973), particles having a shape of octahedron, tetrahedron, dodecahedron, etc. can be prepared and used. Further, grains having twin planes may be used.

The silver halide grain according to the present invention may be a grain having a single shape, or may be a mixture of grains having various shapes.

The silver halide grains used in the emulsion of the present invention include a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt, a rhodium salt or a complex salt, and an iron salt in the process of forming and / or growing the grain. Alternatively, a complex salt can be used to add a metal ion to the inside of the particle and / or to include it on the surface of the particle, and by placing in a suitable reducing atmosphere, a reduction sensitizing nucleus can be formed inside and / or on the surface of the particle. Can be given.

In the emulsion containing the silver halide grains of the present invention (hereinafter referred to as the emulsion of the present invention), unnecessary soluble salts may be removed after the completion of the growth of the silver halide grains, or may be kept contained. . The salts can be removed by the method described in Research Disclosure No. 17643.

The silver halide grain used in the emulsion of the present invention may be a grain in which a latent image is mainly formed on the surface, or may be a grain mainly formed inside the grain. Grains in which the latent image is mainly formed on the surface are preferable.

The emulsion of the present invention is chemically sensitized by a conventional method. That is, a sulfur-containing compound capable of reacting with silver ions, a sulfur sensitization method using active gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds. Sensing methods and the like can be used alone or in combination.

In the present invention, for example, a chalcogen sensitizer can be used as the chemical sensitizer. The chalcogen sensitizer is a general term for a sulfur sensitizer, a selenium sensitizer, and a tellurium sensitizer. For photographic use, the sulfur sensitizer and the selenium sensitizer are preferable. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbazide, thiourea, allylisothiocyanate,
Examples include cystine, p-toluenethiosulfonate, and rhodanine. Other U.S. Patents 1,574,944 and 2,41
0,689, 2,278,947, 2,728,668, 3,501,313
Issue 3,656,955, West German Application Publication (OLS) 1,422,869
The sulfur sensitizers described in JP-A Nos. 56-24937 and 55-45016 can also be used. The addition amount of the sulfur sensitizer varies over a considerable range depending on various conditions such as pH, temperature and size of silver halide grains, but as a guide, it is 10 ^-7 to 10 ^-1 mol per mol of silver halide. It is preferably about molar.

A selenium sensitizer can be used instead of the sulfur sensitization, and examples of the selenium sensitizer include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenamides, and selenocarboxylic acid. Salts and esters, selenophosphates, diethyl selenide, selenides such as diethyl diselenide can be used, and specific examples thereof are U.S. Pat.
No. 944, No. 1,602,592 and No. 1,623,499.

Further, reduction sensitization can be used together. The reducing agent is not particularly limited, but examples thereof include stannous chloride, thiourea dioxide, hydrazine, and polyamide.

Further, a noble metal compound other than gold, for example, a palladium compound or the like can be used together.

The silver halide grains according to the present invention preferably contain a gold compound. As the gold compound preferably used in the present invention, the oxidation number of gold may be +1 or +3, and various kinds of gold compounds are used. Representative examples include chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric azide, ammonium aurothiocyanate, pyridyl trichlorogold, gold sulfide, gold selenide and the like. To be

The gold compound may be used to sensitize the silver halide grains, or may be used so as not to substantially contribute to the sensitization.

The amount of the gold compound added varies depending on various conditions, but as a guide, it is 10 ^-8 mol to 10 ^-1 mol, and preferably 10 ^-7 mol to 10 ^-2 mol, per mol of silver halide. Further, these compounds may be added at any step of silver halide grain formation, physical ripening, chemical ripening and chemical ripening completion.

The emulsion of the present invention can be spectrally sensitized to a desired wavelength region by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more.

A dye that does not have a spectral sensitizing action by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, and that contains a supersensitizer that enhances the sensitizing action of the sensitizing dye in the emulsion. Is also good.

A dye-forming coupler is used in the silver halide emulsion layer of the silver halide photographic light-sensitive material used in the present invention.

It is desirable that these dye-forming couplers have a group called a ballast group, which has a carbon number of 8 or more, which makes the coupler non-diffusible.

As a yellow dye-forming coupler, an acylacetanilide type coupler can be preferably used. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous. A compound represented by the following general formula [Y] is preferred.

General formula [Y] In the formula, R _1Y represents a halogen atom or an alkoxy group. R
_2Y represents a hydrogen atom, a halogen atom or an alkoxy group. R _3Y is an acylamino group, an alkoxycarbonyl group,
Alkylsulfamoyl group, arylsulfamoyl group, arylsulfonamide group, alkylureido group,
It represents an arylureido group, a succinimide group, an alkoxy group or an aryloxy group. Z _1Y represents a group capable of splitting off upon coupling with an oxidized product of a color developing agent.

Specific examples of yellow couplers that can be used are described in British Patent No. 1,07.
7,874, Japanese Patent Publication No. 45-40757, JP-A No. 47-1031, 47-2
6133, 48-94432, 50-87650, 51-3631,
52-115219, 54-99433, 54-133329, 56-3
0127, U.S. Pat.Nos. 2,875,057, 3,253,924 and 3,
265,506, 3,408,194, 3,551,155, 3,551,1
No. 56, No. 3,664,841, No. 3,725,072, No. 3,730,722
No. 3, No. 3,891,445, No. 3,900,483, No. 3,929,484,
3,933,500, 3,973,968, 3,990,896, 4,0
12,259, 4,022,620, 4,029,508, 4,057,43
No. 2, No. 4,106,942, No. 4,133,958, No. 4,269,936,
4,286,053, 4,304,845, 4,314,023, 4,3
36,327, 4,356,258, 4,386,155, 4,401,75
It is described in No. 2 etc.

As the magenta dye-forming coupler, 5-pyrazolone-based couplers, pyrazoloazole-based couplers and the like can be preferably used. More preferred are couplers represented by the following general formula [P] or [a].

General formula [P] In the formula, Ar represents an aryl group, R _p1 represents a hydrogen atom or a substituent, and R _p2 represents a substituent. Y represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent, W represents -NH-, -NHCO- (N atom is bonded to carbon atom of pyrazolone nucleus) or -NHCONH-, and m Is an integer of 1 or 2.

General formula [a] In the formula, Za represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Za may have a substituent.

X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidant of a color developing agent.

Ra represents a hydrogen atom or a substituent.

As the substituent represented by Ra, for example, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group,
Acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, organic hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group , Carbamoyloxy group, amino group, acylamino group, sulfonamide group, imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group,
Examples thereof include an alkylthio group, an arylthio group and a heterocyclic thio group.

These are, for example, U.S. Patent Nos. 2,600,788 and 3,061,4.
No. 32, No. 3,062,653, No. 3,127,269, No. 3,311,
No. 476, No. 3,152,896, No. 3,419,391, No. 3,51
No. 9,429, No. 3,555,318, No. 3,684,514, No. 3,8
88,680, 3,907,571, 3,928,044, 3,
930,861, No. 3,930,866, No. 3,933,500, etc., JP-A-49-29639, 49-111631, 49-129538
No. 50, No. 50-13041, No. 52-58922, No. 55-62454, No. 55
-118034, 56-38043, 57-35858, 60-23855
Publications, British patent 1,247,493, Belgian patent 7
69,116, 792,525, West German Patent 2,156,111, Japanese Patent Publication No. 46-60479, JP-A-59-125732, 59-22
8252, 59-162548, 59-171956, 60-33552
No. 60-43659, West German Patent 1,070,030, and US Pat. No. 3,725,067.

As the cyan dye-forming coupler, a phenol-type or naphthol-type cyan dye-forming coupler is used. Of these, the following general formula [E] or [F] is preferable.
The coupler represented by is used.

General formula [E] In the formula, R _1E represents an aryl group, a cycloalkyl group or a heterocyclic group. R _2E represents an alkyl group or a phenyl group. R _3E represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Z _1E represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine type color developing agent.

General formula [F] In the formula, R _4F is an alkyl group (for example, a methyl group, an ethyl group,
Propyl group, butyl group, nonyl group, etc.). R _5F represents an alkyl group (eg, methyl group, ethyl group, etc.).
R _6F is a hydrogen atom, a halogen atom (for example, fluorine, chlorine,
Bromine etc.) or an alkyl group (eg methyl group, ethyl group etc.). Z _{2 F} represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine type color developing agent.

These cyan dye image-forming couplers are described in US Pat.
No. 306,410, No. 2,356,475, No. 2,362,598, No.
2,367,531, No. 2,369,929, No. 2,423,730, No. 2,474,293, No. 2,476,008, No. 2,498,466,
No. 2,545,687, No. 2,728,660, No. 2,772,162
No. 2, No. 2,895,826, No. 2,976,146, No. 3,002,83
No. 6, No. 3,419,390, No. 3,446,622, No. 3,476,5
No. 63, No. 3,737,316, No. 3,758,308, No. 3,839,
044, British Patent Nos. 478,991, 945,542, and 1,0
84,480, 1,377,233, 1,388,024 and
1,543,040, and JP-A-47-37425 and 5
0-10135, 50-25228, 50-112038, 50-11742
No. 2, No. 50-130441, No. 51-6551, No. 51-37647, No. 5
1-52828, 51-108841, 53-109630, 54-4823
No. 7, No. 54-66129, No. 54-131931, No. 55-32071, No.
59-146050, 59-31953 and 60-117249.

The dye-forming coupler used in the present invention is usually 1 × 10 ⁻³ per mol of silver halide in each silver halide emulsion layer.
Mol to 1 mol, preferably 1 × 10 ^-2 mol to 8 × 10 ^-1
It can be used in the molar range.

The above dye-forming coupler is usually dissolved in a high-boiling organic solvent having a boiling point of about 150 ° C. or higher, if necessary, in combination with a low-boiling point, and / or a water-soluble organic solvent, and is surface-active in a hydrophilic binder such as an aqueous gelatin solution. It may be added to the desired hydrophilic colloid layer after emulsifying and dispersing using the agent. A step of removing the low boiling point organic solvent may be added at the same time as the dispersion or dispersion.

Examples of the high boiling point organic solvent used in the present invention include esters such as phthalic acid ester and phosphoric acid ester, organic acid amides, ketones, hydrocarbon compounds and the like.

The silver halide photographic light-sensitive material used in the present invention can be, for example, a negative and a positive film of a color negative, a color photographic paper, and the like, and particularly when a color photographic paper used for direct viewing is used. The effect of the method of the present invention is effectively exhibited.

The silver halide photographic light-sensitive material of the present invention, including this color photographic paper, may be monochromatic or polychromatic. In the case of a multi-color silver halide photographic light-sensitive material, it is usually used as a photographic coupler in order to perform color reduction method color reproduction.
It has a structure in which a silver halide emulsion layer containing magenta, yellow, and cyan couplers and a non-photosensitive layer are laminated on a support in an appropriate number of layers and layer order. The order may be appropriately changed depending on the priority performance and purpose of use.

When the silver halide photographic light-sensitive material used in the present invention is a multicolor color light-sensitive material, the specific layer structure is as follows: on the support, from the support side, a yellow dye image forming layer, an intermediate layer, and a magenta dye. Those in which the image forming layer, the intermediate layer, the cyan dye image forming layer, the intermediate layer and the protective layer are arranged are particularly preferable.

As the binder (or protective colloid) used in the silver halide photographic light-sensitive material of the present invention, it is advantageous to use gelatin, but other than that, gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugars. Hydrophilic colloids such as derivatives, cellulose derivatives, and synthetic hydrophilic polymeric substances such as homopolymers or copolymers can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the silver halide photographic light-sensitive material are hardened by using a hardener which crosslinks the binder (or protective colloid) molecule and increases the film strength, either alone or in combination. The hardener is preferably added in an amount capable of hardening the photosensitive material to the extent that it is not necessary to add the hardener to the processing liquid, but it is also possible to add the hardener to the processing liquid.

In the present invention, in order to harden the silver halide emulsion layer, it is preferable to use a chlorotriazine type hardener represented by the following general formula [HDA] or [HDB].

General formula [HDA] In the formula, R _d1 is a chlorine atom, a hydroxy group, an alkyl group,
Alkoxy group, alkylthio group, -OM group (where M is a monovalent metal atom), -NR'R "group (here, R '.
And R ″ each represent a hydrogen atom, an alkyl group, an aryl group) or a —NHCOR group (wherein R represents a hydrogen atom, an alkyl group, an aryl group), and R _d2 represents the above R _d1 excluding a chlorine atom. Represents a synonymous group.

General formula [HDB] In the formula, R _d3 and R _d4 are each a chlorine atom, a hydroxy group,
It represents an alkyl group, an alkoxy group or an -OM group (where M is a monovalent metal atom). Q and Q'represent a linking group representing -O-, -S- or -NH-, respectively, and L represents an alkylene group or an arylene group. p
And q each represent 0 or 1.

Next, typical examples of preferred hardeners represented by the above general formulas [HDA] and [HDB] will be described.

To add the hardener represented by the general formula [HDA] or [HDB] to the silver halide emulsion layer and other constituent layers, dissolve it in water or a solvent miscible with water (eg, methanol, ethanol, etc.). It may be added to the coating liquid for the above-mentioned constituent layers. The addition method may be either a batch method or an in-line method. The addition timing is not particularly limited, but it is preferably added immediately before coating.

These hardeners are added in an amount of 0.5 to 100 mg, preferably 2.0 to 50 mg, per 1 g of coated gelatin.

The silver halide photographic light-sensitive material used in the present invention (hereinafter,
A plasticizer may be added for the purpose of increasing the flexibility of the silver halide emulsion layer and / or other hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention).

The photographic emulsion layer and other hydrophilic colloid layers of the silver halide photographic light-sensitive material of the present invention may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

An image stabilizer which prevents deterioration of a dye image can be used in the silver halide photographic light-sensitive material of the present invention.

In order to prevent fog due to discharge caused by charging of the hydrophilic colloid layer such as the protective layer and intermediate layer of the silver halide photographic light-sensitive material of the present invention due to friction and the like, and to prevent deterioration of the image by UV light. It may contain an ultraviolet absorber.

The silver halide photographic light-sensitive material of the present invention may be provided with auxiliary layers such as a filter layer, an antihalation layer, and / or an irradiation prevention layer. In these layers and / or emulsion layers, dyes which may be bleached or bleached from the color light-sensitive material during development processing may be incorporated.

A silver halide emulsion layer of the silver halide light-sensitive material of the present invention,
A matting agent can be added to the hydrophilic colloid layer for the purpose of reducing gloss of the light-sensitive material, enhancing writing property, and preventing sticking of the photosensitive materials to each other.

A lubricant may be added to the silver halide photographic light-sensitive material of the present invention to reduce sliding friction.

The silver halide photographic light-sensitive material of the present invention may contain an antistatic agent for the purpose of antistatic. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and may be used to protect the emulsion layer and / or the emulsion layer on the side of the support other than the emulsion layer. It may be used for the colloid layer.

The photographic emulsion layer of the silver halide photographic light-sensitive material of the present invention and /
Or, in other hydrophilic colloid layers, for the purpose of improving coating property, antistatic property, improving slipperiness, emulsifying dispersion, preventing adhesion, and improving photographic properties (such as acceleration of development, hardening, and sensitization),
Various surfactants are used.

The silver halide photographic light-sensitive material of the present invention is a photographic emulsion layer, and the other layers are baryta paper or paper laminated with α-olefin polymer or the like, flexible reflective support such as synthetic paper, cellulose acetate, cellulose nitrate, polystyrene, It can be applied to films made of semi-synthetic or synthetic polymers such as polyvinyl chloride, polyethylene terephthalate, polycarbonate and polyamide, and rigid bodies such as glass, metal and pottery.

The silver halide light-sensitive material of the present invention is directly or after (corresponding to the adhesiveness of the support surface, antistatic property, dimensional stability, after subjecting the support surface to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary. , One or more subbing layers) to improve abrasion resistance, hardness, antihalation, frictional properties, and / or other properties.

When coating a photographic light-sensitive material using the silver halide emulsion of the present invention, a thickener may be used in order to improve coatability. As the coating method, extrusion coating and curtain coating which can simultaneously coat two or more layers are particularly useful.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in the spectral region where the emulsion layer constituting the light-sensitive material of the present invention has sensitivity. As a light source, natural light (sunlight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, various laser light, light emitting diode light, electron beam,
Any known light source such as light emitted from a phosphor excited by X-rays, γ-rays or α-rays can be used.

The exposure time is usually 1 ms to 10 used in printers.
The exposure time of second is, of course, shorter than 1 millisecond, for example, a cathode ray tube or a xenon flash lamp can be used for 100 microsecond to 1 millisecond, or longer than 10 seconds.

The exposure may be performed continuously or intermittently.

The silver halide grains having a silver chloride content of 90 mol% or more and the compound [S] of the present invention represented by the general formula [S]
The silver halide photographic light-sensitive material used in the present invention having the above formula is processed with a color developer having a sulfite ion content of 2 × 10 ⁻⁴ to 1 × 10 ⁻² mol / l and containing substantially no bromide ion. It

The term "substantially free of bromide ion" as used herein means a treatment liquid containing bromide ion in an amount of 5 × 10 ^-4 mol / l or less. In the present invention, a high chloride silver halide having a silver chloride content of 90 mol% or more is used as the silver halide, and as the high chloride silver halide, a part of bromide other than silver chloride is used as described above. It may contain silver or silver iodide. Therefore, when silver bromide is contained, bromide ions are slightly eluted in the developing solution during development. This eluted bromide ion is partly replaced due to the difference in the solubility of chloride ion and silver in the high chloride silver halide which is not developed even in the area other than the image area, that is, in the high chloride silver halide, to several orders of magnitude. It is considered that they are held in the photographic light-sensitive material and taken out to the next step. However, as described above, it is possible to keep the bromide ion concentration in the developer completely zero as long as the bromide ion may be eluted in the developer although the amount is small by developing the high chloride silver halide. Can not. The term "substantially free of bromide ion" as used in the present invention means that only bromide ion inevitably mixed in, such as bromide ion eluted in a trace amount by development, is not contained, and 5 × 10 ^-4 mol / l means It shows the maximum allowable upper limit of the concentration of bromide ions inevitably mixed.

Further, the color developer used in the present invention does not substantially contain bromide ion, but it is preferable that a certain amount of chloride ion be present. That is, 1 per 1 color developing solution
It is preferable to contain x10 ^{-3 to} 0.5 mol, and more preferably 2 x 10 ^{-3 to} 0.2 mol of chloride ion.

Further, the color developer according to the present invention has a sulfite ion content of 2 × 10 ⁻⁴ to 1 × 10 ⁻² mol / l.

In the color development step, generally, an aromatic primary amine developing agent dissolved in an alkaline aqueous solution is used. Alkaline developers are usually unstable to oxidation, and sulfite ion is added as a storage stabilizer (preservative) to prevent oxidation. However, it is known that the sulfite ion reacts with the oxidized product of the color developing agent, and thus reduces the color developing efficiency. Therefore, for example, JP-A-61-73955
JP-A No. 2003-242242 and the like disclose a technique for improving the color developability by setting the sulfite ion concentration to a specific amount or less. However, the present inventors have found that the compound [S] and a high chloride silver halide emulsion are used. When the light-sensitive material used is processed with a color developing solution containing substantially no bromide ion, the effect of improving color developability is particularly remarkable when sulfite ion is reduced, and in the specific low sulfite ion concentration range. It has been found that the most favorable results are obtained. In other words, when the sulfite ion concentration exceeds 1 × 10 ⁻² mol / l, rapid color development cannot be achieved, and when it is less than 2 × 10 ⁻⁴ mol / l, the color development speed is improved even if it is further reduced. Is not allowed,
Even if the compound [S], which is a development inhibitor, is present, the minimum density (D _min ) increases and the quality of photographic images is significantly impaired. In this way, when a light-sensitive material containing a high chloride silver halide emulsion is used and a color developing solution containing substantially no bromide ion is used, in a system having an extremely high color developing speed, the sulfite ion concentration is simply reduced. It cannot be said that it is good, and it has been found that the minimum concentration can be sufficiently suppressed only in the above-mentioned specific range and both of the rapid processability can be satisfied at the same time.

Further, surprisingly, the system of the present invention, that is, a silver halide photographic light-sensitive material containing the silver halide grains having a silver chloride content of 90 mol% or more and the compound [S] according to the present invention was prepared by using a bromide ion. Bleach-fixing in a color developing solution in a system in which a color developing solution containing substantially no sulfite ion in a specific range of 2 × 10 ^-4 to 1 × 10 ^-2 mol / l is used. It has been found that there is a great advantage in quality stability that the fluctuation of photographic performance such as the gradation fluctuation of the dye image obtained by the mixing of the solution and the difference of the pH fluctuation of the color developing solution is extremely small.

The sulfite ion concentration in the above color developing solution is 2 × 10 ⁻⁴ to 1 ×
The purpose of the present invention can be achieved with 10 ^-2 mol / l, but it is preferably in the range of 3 x 10 ^{-4 to} 6 x 10 ^-3 mol / l, more preferably 3 x 10 ^{-4 to} 3 × 10 ⁻³ mol / l.

Sulfite ions can be used, for example, in the form of alkali metal sulfites, alkali metal bisulfites or ammonium sulfites or bisulfites. In the color developer used in the present invention, in order to maintain the sulfite ion at the above specific low concentration and to stabilize the color developer,
Dihydroxyacetones described in U.S. Pat.No. 3,615,503, hydroxyureas described in JP-A-52-27638, monosaccharides such as pentose described in JP-A-52-102727, JP-A-5
Aromatic secondary alcohols described in 2-7729 may be used, and a method of replenishing the color developing solution in a large amount, a method of keeping the developing solution close to a sealed system and avoiding contact with air as much as possible, sulfurous acid The color developing solution may be kept stable and at a low sulfite concentration by using a method of adding to the developer a compound that keeps the ion concentration low and forms a stable sulfite ion adduct in an equilibrium state.

Examples of the compound that forms a stable sulfite ion adduct with sulfite ion include a compound having an aldehyde group,
Examples thereof include compounds containing a cyclic hemiacetal, compounds having an α-dicarbonyl group, compounds having a nitrile group, and the like.

The color developing agent used in the color developing solution in the present invention includes known ones widely used in various color photographic processes. These developers include aminophenol-based and p-phenylenediamine-based derivatives. Since these compounds are more stable than the free state, they are generally used in the form of salts, for example, hydrochlorides or sulfates. Also, these compounds generally have a concentration of about 0.1 g to about 30 g, preferably Color Developer 1 for Color Developer 1.
Is used at a concentration of about 1 g to about 15 g.

Examples of the aminophenol-based developer include o-aminophenol, p-aminophenol, 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-Oxy-3-amino-1,4-dimethylbenzene and the like are included.

Particularly useful primary aromatic amine color developing agents are N, N'-
A dialkyl-p-phenylenediamine compound,
The alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include
N, N'-diethyl-p-phenylenediamine hydrochloride, N
-Methyl-p-phenylenediamine hydrochloride, N, N'-dimethyl-p-phenylenediamine hydrochloride, 2-amino-
5- (N-ethyl-N-dodecylamino) -toluene,
N-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline sulfate, N-ethyl-N
-Β-hydroxyethylaminoaniline, 4-amino-
3-methyl-N, N'-diethylaniline, 4-amino-
Examples thereof include N- (2-methoxyethyl) -N-ethyl-3-methylaniline-p-toluenesulfonate.

A known developer component compound can be added to the color developing solution applied to the present invention in addition to the above-mentioned primary aromatic amine color developing agent. For example sodium hydroxide,
It may optionally contain an alkali agent such as sodium carbonate or potassium carbonate, an alkali metal sulfite, an alkali metal bisulfite, an alkali metal thiocyanate, an alkali metal halide, benzyl alcohol, a water softener and a thickener. it can.

The pH value of the color developer is usually 7 or higher, most commonly about
10 to about 13.

Color development temperature is usually 15 ℃ or higher, generally 20 ℃ ~
It is in the range of 50 ° C. For rapid development, it is preferably carried out at 30 ° C or higher. Also, the color development time is generally 20
The time is preferably in the range of seconds to 60 seconds, more preferably 30 seconds to 50 seconds.

The silver halide photographic light-sensitive material according to the present invention can contain these color developing agents as the color developing agent itself or as a precursor thereof in the hydrophilic colloid layer, and can be processed with an alkaline activating bath. Color developing agent precursor is a compound capable of producing a color developing agent under alkaline conditions, a shift base type precursor with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a phthalic acid imide derivative precursor, a phosphoric acid amide derivative precursor, Examples include sugar amine reactant precursors and urethane type precursors. Precursors for these aromatic primary amine color developing agents are disclosed, for example, in U.S. Pat. Nos. 3,342,599 and 2,507,114,
No. 2,695,234, No. 3,719,492, British Patent No. 803,78
No. 3, each specification, JP-A Nos. 53-185628 and 54-79035, Research Disclosure 15159, 121
No. 46 and No. 13924, it is necessary to add these aromatic primary amine color developing agents or their precursors so that sufficient amount can be obtained by the amount when activated. is there. This amount varies greatly depending on the kind of the light-sensitive material, but it is generally between 0.1 and 5 mol, preferably 1 mol, per mol of silver halide.
It is used in the range of 0.5 mol to 3 mol. These color developing agents or their precursors can be used alone or in combination. Water to incorporate in the photosensitive material,
It can also be added by dissolving it in an appropriate solvent such as methanol, ethanol or acetone, or it can be added as an emulsion dispersion using a high boiling organic solvent such as dibutyl phthalate, dioctyl phthalate or tricresyl phosphate. It can also be added by impregnating a latex polymer as described in Disclosure No. 14850.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching treatment and fixing treatment after color development. The bleaching process may be performed simultaneously with the fixing process. Many compounds are used as bleaching agents, among which iron (III), cobalt (III), copper (II)
Polyvalent metal compounds, especially complex salts of these polyvalent metal cations with organic acids, for example aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, N-hydroxyethylethylenediaminediacetic acid, malonic acid, tartaric acid, malic acid. , Metal complex salts such as diglycolic acid and dithioglycolic acid, ferricyanates, dichromates, etc., alone or in an appropriate combination.

As the fixing agent, a soluble complexing agent that solubilizes silver halide as a complex salt is used. Examples of the soluble complexing agent include sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, thiourea and thioether.

After the fixing process, a washing process is usually performed. Further, as a substitute for the water washing treatment, a stabilizing treatment may be performed, or both may be used in combination. The stabilizing solution used for the stabilizing treatment may contain a pH adjusting agent, a chelating agent, a fungicide, and the like. For these specific conditions, reference can be made to JP-A-58-134636.

[Specific effects of the invention] According to the dye image forming method of the present invention having the structure as described above, the minimum density of the dye image to be formed can be suppressed to a sufficiently low level, the rapid processing property is excellent, and BF is mixed. It was also excellent in tolerance and pH fluctuation tolerance.

Specific Examples of the Invention Hereinafter, the present invention will be specifically described with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example-1 Preparation of silver halide emulsion EMP-1 An aqueous solution of silver nitrate and an aqueous solution of sodium chloride were added to an aqueous solution of inert gelatin by stirring by a double jet method and mixed. At this time, the temperature is 60 ° C, pH = 3.0, pAg = 7.
It was controlled to be kept at 8. Then, desalting was carried out by a conventional method to obtain EMP-1. EMP-1 has an average particle size of 0.7
It was a cubic monodisperse silver chloride emulsion of μm.

EMP-2 Aqueous silver nitrate solution and aqueous halide solution (mixed aqueous solution of potassium bromide and sodium chloride) were added and mixed into the aqueous solution of inert gelatin by the double jet method. At this time, the temperature was maintained at 60 ° C., pH = 3.0 and pAg = 7.8.
Control was performed according to the method described in No. 437. Then, desalting was performed by a conventional method to obtain EMP-2. EMP-2 was a monodisperse emulsion composed of tetradecahedral silver chlorobromide grains having an average grain size of 0.7 μm and containing 90 mol% of silver bromide.

Next, EMP-1 and EMP-2 were chemically sensitized under the following conditions to prepare EMB-1 and EMB-2, respectively. However, the compound [S] was added at the end of the chemical sensitization.

Sulfur sensitizer: Sodium thiosulfate 2.5 mg / mol AgX sensitizing dye: D-1 100 mg / mol AgX Compound [S]: S-6 1.5 × 10 ^-3 mol / mol Temperature: 60 ° C Time: 60 minutes Sensitizing dye (D-1) Next, a yellow coupler dispersion was prepared by the following method.

[Dispersion method of yellow coupler] 40 g of yellow coupler (YC-1) was added to dibutyl phthalate 1
It was dissolved in a mixed solvent of 0 ml and ethyl acetate, this solution was added to a gelatin aqueous solution containing sodium dodecylbenzenesulfonate, and then dispersed using an ultrasonic homogenizer.

Next, the above emulsions EMB-1 and EMB-2 were used to prepare light-sensitive materials [A] and [B] with the following constitutions.

However, the yellow coupler was added in the form of the coupler dispersion.

Photosensitive material [A] and photosensitive material [B] thus obtained
Was used to evaluate the rapid processability by the following method.

[Evaluation of rapid processability] A KS-7 type sensitometer (manufactured by Konishi Rokusha Kogyo Co., Ltd.) was used to perform exposure through an optical wedge, and then the following processes were performed. However, regarding the color developing step, the processing time is set to three types of 20 seconds, 45 seconds and 90 seconds, and the following color developing composition is four types of (A), (B), (C) and (D). did.

[Processing process] Temperature Time Color development 34.7 ± 0.3 ℃ 20 seconds, 45 seconds, 90 seconds Bleach fixing 34.7 ± 0.5 ℃ 45 seconds Stabilization 30-34 ℃ 90 seconds Dry 60-80 ℃ 60 seconds [Bleaching fixer] Ethylenediaminetetraacetic acid ferric ammonium dihydrate
60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% solution) 100 ml Ammonium sulfite (40% solution) 27.5 ml Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid and add water to bring the total volume to 1.

[Stabilizing liquid] 5-chloro-2-methyl-4-isothiazolin-3-one 1g 1-hydroxyethylidene-1,1-disphosphinic acid 2g Water was added to 1 to adjust pH with sulfuric acid or potassium hydroxide.
Adjust to 7.0.

The reflection density of the obtained sample was measured with a densitometer (PDA-65; Konishi Roku Photo Industry Co., Ltd.) to obtain the characteristic values defined below.

Gradation (γ): slope of a straight line connecting the points of density 0.5 and 1.5 of the characteristic curve Minimum density (D _min ): density of unexposed area The results are shown in Table-1. In Table 1, it is judged that the faster the processability is, the lower the D _min is, the sufficient γ value is, and the smaller the change in the characteristic value between the time steps of color development is.

As is clear from Table 1, for Comparative Experiments 1-5 to 1-8 using silver chlorobromide grains having a low silver chloride content,
Basically, rapid processability is not satisfactory. Further, in the sample having a high silver chloride content, the rapid processability was unsatisfactory when the bromide ion was treated with the color developer containing the bromide ion in an amount exceeding the amount specified in the present invention (Comparative Experiment 1-4). Further, in the case of processing with a color developer containing the sulfite ion in an amount exceeding the amount specified in the present invention (Comparative Experiment 1-1), the rapid processability was also unsatisfactory, while the sulfite ion was completely absent. In the case of processing with a color developing solution that does not contain it (Comparative Experiment 1-3), the rapid processing property is satisfactory but an increase in the minimum density is observed, and any sample has a problem. On the other hand, Experiment 1-2 of the present invention satisfies both the rapid processability and the minimum concentration level.

Example-2 The EMP-1 prepared in Example-1 was chemically sensitized under the following conditions to give red-sensitive emulsions EMR-1 to EMR-7.
Got

Sulfur sensitizer: sodium thiosulfate 2.5 mg / mol AgX sensitizing dye: D-2 40 mg / mol AgX chloroauric acid: (conditions shown in Table 2) Compound [S]: (〃) Temperature: 55 ° C , 5 minutes after adding sodium thiosulfate for sensitizing dye, 60 minutes after adding sodium thiosulfate for chloroauric acid, compound [S]
Was added 70 minutes after the addition of sodium thiosulfate, and the chemical sensitization was completed by adding the compound [S].

Next, the average particle size was measured in the same manner as in EMP-2 of Example-1.
A monodisperse emulsion EMP-3 consisting of cubic silver chlorobromide grains having a size of 0.5 μm and containing 2.0 mol% of silver bromide was prepared.

This EMP-3 was chemically sensitized under the same conditions as in EMR-1 to EMR-7 to obtain EMR-8 to EMR-28.

Next, a cyan coupler dispersion was prepared by the following method.

[Cyan coupler dispersion method] Cyan coupler (CC-1) 40 g was added to dibutyl phthalate 10 m
It was dissolved in a mixed solvent of 1 and ethyl acetate, and this solution was added to an aqueous gelatin solution containing sodium dodecylbenzenesulfonate, and then dispersed using an ultrasonic homogenizer.

Next, using the above coupler dispersion and the above emulsions EMR-1 to EMR-28, samples 2-1 to 2-28 having the following constitution were prepared.
It was created.

The samples 2-1 to 2-28 were evaluated for rapid processability in the same manner as in Example-1. However, for the color developing solution, only the composition of [B] was used.

The results are shown in Table-2.

Furthermore, the BF contamination resistance and pH fluctuation resistance were evaluated by the methods described below.

[BF mixing resistance test] Each of the color developing solutions [B] is mixed with the bleach-fixing solution.
Color developing solutions [E] and [F] containing 0.5 ml and 1.0 ml were prepared.

Using these color developing solutions, processing was carried out in accordance with the color developing processing step similar to the evaluation of rapid processing property, and sensitometric measurement was carried out. However, the color development time was only 45 seconds.

The results are shown in Table-2. In the table, Δγ is a value that indicates the fluctuation range when processing with a color developing solution containing a bleach-fixing solution based on the gradation (γ) when processing with a color developing solution without a bleach-fixing solution. The smaller this value, the better the BF contamination resistance.

[PH fluctuation resistance test] With the same composition as the color developer [B], pH = 9.8, and 10.
A color developer adjusted to 6 was prepared.

Using these color developing solutions, processing was performed according to the same color development processing step as in the evaluation of rapid processing property, and sensitometric measurement was performed. However, the color development time was only 45 seconds.

The results are shown in Table-2. In the table, Δγ is a value indicating the range of fluctuation when processed with color developing solutions having different pHs based on the gradation (γ) when processed with the color developing solution with pH = 9.8.

The structural formulas of comparative compounds (SC-1) and (SC-2) of the compound [S] used in Table-2 are as follows.

As is apparent from Table-2, even when the color developing solution according to the present invention was used, Samples 2-1, 2-2, 2-8 and 2 using the comparative compound of the compound [S] according to the present invention were used. At -9, the increase in the minimum concentration was remarkable, and the BF
Contamination resistance and pH fluctuation resistance are also problematic levels.
On the other hand, Sample 2 using the compound [S] according to the present invention
In all of -3 to 2-7 and 2-10 to 2-28, the minimum concentration was suppressed to be sufficiently low, rapid processability was satisfied, and BF contamination resistance and pH fluctuation resistance were also extremely excellent. More specifically, by adding a gold compound, the effects of the present invention of minimum concentration reduction, rapid processability, BF contamination resistance and pH fluctuation resistance were efficiently achieved, and a trace amount of silver bromide was contained. By using silver halide grains having a high silver chloride content, the minimum concentration is further reduced and the BF contamination resistance and pH fluctuation resistance are improved.

Example-3 Emulsions EMP-1 to EMP-3 prepared in Examples-1 and 2
Was chemically sensitized under the following conditions, and EM-1 to EM-12
Got In addition, a sensitizing dye, chloroauric acid and compound [S]
The addition conditions of were the same as in Example-2.

Next, using the above EM-1 to EM-12, Samples 3-1 to 3-8 were prepared under the conditions shown in Table 4 with the configuration shown in Table 3. However, the hardeners shown in Table 4 were added to the seventh layer.

UV absorber (UV-1) Magenta coupler (MC-1) Sensitizing dye (D-3) Samples 3-1 to 3-8 were evaluated for rapid processability, BF contamination resistance, and pH fluctuation resistance in the same manner as in Example-2. The results are shown in Table-4.

As is clear from Table 4, in Samples 3-1 and 3-5 having a silver chloride content other than the present invention, both the rapid processability and the minimum concentration were unsatisfactory, and the BF contamination resistance and pH fluctuation resistance Was also at the level of the problem. In addition, samples 3-2 and 3-6 using a comparative compound of compound [S]
Although the rapid processability is satisfactory, the minimum concentration and BF
Contamination resistance and pH fluctuation resistance are significantly deteriorated. In contrast, samples 3-3, 3-4, 3-7 and 3 of the present invention
In -8, excellent properties are exhibited in both rapid processability and minimum concentration, and BF contamination resistance and pH fluctuation resistance are also greatly improved. More specifically, it can be seen that the effect of the present invention can be achieved more efficiently by using a chlorotriazine compound as the hardener.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Eiichi Sakamoto 1 Sakura-cho, Hino-shi, Tokyo Konishi Roku Photo Industry Co., Ltd. (56) References Special Table Sho 63-502222 (JP, A)

Claims (1)

[Claims] 1. A dye image which is subjected to photographic processing including color development processing after imagewise exposing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing a dye-forming coupler on a support. In the forming method, at least one layer of the silver halide emulsion layer contains silver halide grains having a silver chloride content of 90 mol% or more and a compound represented by the following general formula [S] as a photosensitive silver halide. And the color developer used for the color developing treatment has a sulfite ion content of 2 × 10 ⁻⁴ to 1 × 10 ⁻² mol / l,
And a method of forming a dye image, which is substantially free of bromide ion. General formula [S] (In the formula, Q is 1,3,4-triazole ring, 1,3,4-oxadiazole ring, 1,3,4-thiadiazole ring, or 1,3,5-
It represents a group of atoms necessary for forming a triazine ring. M
Represents a hydrogen atom, an alkali metal atom, or an ammonium group. )