JPS6337348A - Dye image forming method superior in rapid processability - Google Patents

Abstract

PURPOSE:To enhance rapid processability and to form a dye image sufficiently lowered in minimum density by incorporating photosensitive silver halide grains containing silver chloride in an amount of >=90mol%, and a specified compound in at least one of silver halide emulsion layers. CONSTITUTION:At least one of the silver halide emulsion layers contains the photosensitive silver halide grains having the silver chloride content of >=90mol% and the compounds represented by formula I, and, preferably, formulae II and III in which Z is an atomic group necessary to form a benzotriazole ring or 1,2,3,4-thiatriazole ring; each of RA and RB is H, halogen, nitro, alkyl, alkenyl, or the like; and RC is H, halogen, nitro, cyano, amino, or the like. The color developing solution to be used for color development processing contains sulfite ions in an amount of 2X10<-4>-1X10<-2>mol/l, and substantially no bromide ions.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for forming a dye image, and more particularly to a method for forming a dye image that can be processed quickly and has a sufficiently low minimum density.

[Background of the Invention] In recent years, there has been a demand in the industry for silver halide photographic materials that can be processed rapidly, have high image quality, excellent processing stability, and are low cost. A silver halide photographic material that can be rapidly processed is desired.

In other words, silver halide photographic light-sensitive materials are normally processed continuously in automatic processing machines installed at each processing laboratory, but as part of an effort to improve service to users, processing is carried out on the same day when processing is received. It is now required to develop the product and return it to the user, and in recent years it has even become necessary to return the product within a few hours of receiving it, and the need for rapid processing is increasing. Furthermore, since shortening processing time improves production efficiency and reduces costs, there is an urgent need to develop rapid processing.

In order to achieve rapid processing, approaches have been taken from two aspects: photosensitive materials and processing solutions. Regarding color development processing, attempts have been made to increase the temperature, pH, and concentration of the color developing agent, and it is also known to add additives such as development accelerators. As the development accelerator mentioned above, British Patent No. 8
1-phenyl-3-pyrazolidone described in No. 11,185, N-methyl-〇-aminophenol described in U.S. Pat. '-tetramethyl-p-phenylenediamine and the like. However, these methods often fail to achieve sufficient speed and are accompanied by performance deterioration such as increased fog.

On the other hand, it is known that the shape, size, and composition of silver halide grains in silver halide emulsions used in photosensitive materials have a large effect on development speed, etc., and the halogen composition has a particularly large effect on high chloride halogenated materials. It has been found that especially when silver is used, extremely high development rates are exhibited.

However, when trying to maintain the high developability of chloride silver halide emulsions, fog generally increases.

Especially in color development systems compared to black and white development systems,
Because a colored dye is produced, the fog density is also more noticeable than in black and white, which is an important problem in making full use of the rapid processing characteristics of high chloride silver halide emulsions.

Antifoggants are generally used to reduce fog density. One of the most well-known antifoggants is potassium bromide, which has traditionally been used in many developer solutions.

However, when a sample containing a high chloride halogen emulsion is processed with a color developing solution containing potassium bromide, rapid processability is significantly impaired. This means that potassium bromide acts as an extremely strong development inhibitor for high chloride silver halide emulsions before preventing fogging.
When rapid processability is aimed at, it is necessary that the color developing solution used in the high chloride silver halide emulsion system contain substantially no potassium bromide, resulting in even worse conditions regarding fog.

On the other hand, many organic inhibitors are also known as other antifoggants, such as "Stabilization of Photographic Silver Halide Emulsions" by E.G. Beer, Focal Press (19
74) (E, J, Birr.

” S tabilization of P hot
graphic 31lver Halide Emu
lsions' Focal press). Among these antifoggants, many heterocyclic mercapto compounds have a strong antifogging effect and have been commonly used. However, since the heterocyclic mercapto compound is effective in preventing fog and at the same time has a fairly strong effect of inhibiting development, there is a limit to the amount of the compound to be used. Heterocyclic mercapto compounds also exhibit effective fog suppressing effects on high chloride silver halide emulsions, but when added to sufficiently suppress fog, rapid processability is inhibited, although not as much as potassium bromide. , the advantages of using a high chloride silver halide emulsion are greatly reduced.

Furthermore, if the amount added satisfies rapid processing performance, fogging will occur, which is a practical problem. Thus, there is a strong desire to develop a technique that solves the dilemma of maintaining rapid processability and suppressing fog in high chloride silver halide emulsions that basically have high developability.

In general, silver halide photographic materials are continuously processed while replenishing a replenisher in various processing laboratories such as laboratories. It is impossible to keep it constant, and there is a problem in that changes in the composition of the processing solution cause variations in photographic properties. This problem has become even more serious as processing liquids have become less replenishable in recent years.

In particular, it is almost impossible to completely eliminate contamination of the bleach-fixer with the developer, even if you set a strict replenishment rate, prevent evaporation, and eliminate substances eluted from the photosensitive material. However, especially in roller conveyance and automatic processing machines, the amount of bleach-fix solution mixed into the developer solution varies significantly depending on the throughput and squeezing method, and if the processing solution replenishment rate decreases, The actual situation is that since the rotation speed of the processing liquid decreases, there is a further difference in the mixing rate.

Generally speaking, although the color developer is maintained at a high DH, pH fluctuations in the color developer are unavoidable due to the amount of replenisher replenishment during continuous operation, the influence of air oxidation, etc.

Changes in photographic performance (in most cases, increased fog and gradation changes) due to contamination of the bleach-fix solution into the color developer and pH fluctuations in the color developer are important for achieving stable and good color and gradation reproduction. has become a major obstacle. For the reasons mentioned above, it is extremely difficult to avoid contamination with bleach-fix solution and pH fluctuations. is small, so-called BF contamination resistance and pH
It is desired to develop a silver halide photographic material with excellent fluctuation resistance.

The present inventors have conducted various studies on techniques for suppressing an increase in fog, which is a problem when using silver halide grains with a high silver chloride content suitable for rapid processing and a stain inhibitor. The inventors have discovered that by using a specific compound in combination, fogging can be effectively suppressed while maintaining rapid processability, and the present invention has been completed. Furthermore, it has been surprisingly discovered that a silver halide photographic material containing a specific compound has the additional advantage of being excellent in resistance to BF contamination and resistance to pH fluctuation.

[Object of the Invention] Therefore, an object of the present invention is to provide a method for forming a dye image that is excellent in rapid processing properties and further has a sufficiently suppressed minimum density. It is an object of the present invention to provide a method for forming a dye image having excellent processability, sufficiently suppressing the minimum density, and having excellent resistance to BF contamination and pH fluctuation.

[Structure of the Invention] The above-mentioned object of the present invention includes a color development treatment after imagewise exposure of a silver halide photographic material having at least one silver halide emulsion layer containing a dye-forming coupler on a support. In a method for forming a dye image using photographic processing,
At least one of the silver halide emulsion layers 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 photosensitive silver halide, and the color forming The color developing solution used for development processing has a sulfite ion content of 2X10' to 1X10'
mol/l and was achieved by a method of forming a dye image that is substantially free of bromide ions.

General formula [S] (wherein 2 is a benzenetriazole ring, or 1°2.
3. Represents the atomic group necessary to complete the 4-thiatriazole ring. ] [Specific structure of the invention] In the silver halide photographic material applied to the present invention, at least one of the silver halide emulsion layers has the general formula [S
] Contains the compound shown.

The benzotriazole ring or 1.2.3°4-thiatriazole ring of the compound represented by the general formula [31 according to the present invention] can have any substitutable substituent. Examples of substitutable groups include silver halide, nitro group, cyam L-amino group, mercapto group, acyl group, alkyl group, cycloalkyl group, alkenyl group, aryl group, and heterocyclic group.

Among the compounds represented by the general formula [S], particularly preferred compounds can be represented by the following general formula [SA] or [S, B].

General formula [SA] (wherein RA and RB are each a hydrogen atom,
It represents a halogen atom, nitro group, alkyl group, cycloalkyl group, alkenyl group or aryl group, and RA and R3 may be the same or different.

General Formula [SB] In the formula, Ro represents a hydrogen atom, a halogen atom, a nitro group, a sialyl group, an amino group, a mercapto group, an acyl group, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group.

In the general formulas [SA and [SB], examples of the halogen atoms represented by R, 4 and R6 include chlorine atom and bromine atom. The amino group represented by Rc includes those having a substituent, such as an amine group, a methylamine group, a methylethylamino group, a phenyl-naphthylamino group, an acetamido group, a benzamide group, and the like. The mercapto group represented by R includes those having a substituent, such as -8M (M represents a hydrogen atom, an alkali metal atom such as sodium, or an ammonium group), an alkylthio group such as a methylthio group or a hexylthio group, Examples include alkenylthio groups such as propenylthio groups, and arylthio groups such as phenylthio groups. Examples of the acyl group represented by Ro include an acetyl group, an alkylcarbonyl group such as an ethylcarbonyl group, and an arylcarbonyl group such as a phenylcarbonyl group, and examples of the heterocyclic group represented by Rc include a thietriyl group, Imidazolyl group, thiazolyl group, etc. are mentioned, and the alkyl group represented by RA, R8 and SERO is preferably a straight or branched alkyl group having 1 to 8 carbon atoms (more preferably 1 to 6 carbon atoms), such as a methyl group. , ethyl group, propyl group, (-butyl group, hexyl group, etc.).

The alkenyl group is preferably an alkenyl group having 3 to 8 carbon atoms (more preferably 3 to 6 carbon atoms), such as an allyl group,
Examples include a pevenyl group, a butenyl group, a hexenyl group, and the like. The cycloalkyl group is preferably 3- to 8-membered (
More preferably 3- to 6-membered) cycloal:1-nyl group,
For example, cyclopropyl group, cyclobenpur group, Schiff "1"
Examples include hexyl group. t, t as an aryl group
Examples of IA include phenyl group and naphthyl group.

The alkyl group, Schifflcore group, alkenyl group, aryl group, heterocyclic group, etc. represented above also include those having a substituent.

Typical specific examples of the compound represented by the general formula [3] are shown below, but the present invention is not limited thereto.

The compound represented by the above general formula [S] can be found, for example, in
Hemy (B eilsteins Handbackd)
er 0raanischen Shemie)
26.41, 43°58, etc.,
The synthesis method can also be carried out in accordance with the methods described in these documents.

In order to contain the compound represented by the general formula [S] according to the present invention (hereinafter referred to as compound [S]) in the silver halide emulsion layer according to the present invention, water or an organic solvent optionally miscible with water can be used. It may be added after being dissolved in (for example, methanol, ethanol, etc.). Compound [S] may be used alone or in combination with other compounds represented by general formula [S], other stabilizers other than those represented by general formula [81], or fog suppressants. Good too.

The timing of adding the compound [S] is before the formation of silver halide grains, during the formation of silver halide grains, from after the completion of silver halide grain formation to before the start of chemical ripening, during chemical ripening, at the end of chemical ripening, It may be applied at any time from the end of chemical ripening to the time of application. Preferably, it is added during chemical ripening, at the end of chemical ripening, or after the end of chemical ripening and before the time of coating. The entire amount may be added at one time, or may be added in multiple portions.

The addition site may be directly added to the silver halide emulsion or silver halide emulsion coating solution, or it may be added to the coating solution 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.

The amount added is not particularly limited, but it is usually added in the range of 1.times.10@-6 mol to 1.times.10@-1 mol, preferably 1.times.10@-5 mol to 1.times.10@-2 mol, per 1 mol of silver halide.

When 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, rapid processability is maintained, and the dye image formed is It is not known that the minimum concentration can be kept sufficiently low.

Furthermore, the system of the present invention is extremely stable and has good reproducibility against fluctuations in photographic performance due to mixing of the bleach-fixing solution into the color developer and pH fluctuations in the color developer, such as an increase in fog. , so-called BF contamination resistance and l)
It also had the completely unexpected additional effect of being excellent in H fluctuation resistance. Looking more closely, we can see that - the following equation [SA
] has a great effect on resistance to BF contamination, and the compound with the following formula [S
B]k compounds have a large effect on pH fluctuation tolerance.

1 White J6. 2i The silver halide emulsion layer containing the compound [8] 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, a silver bromide content of 10 mol% or less,
The silver iodide content is preferably 0.5 mol% or less. More preferably, the silver bromide content is 0.5 to 5 mol%.
silver chlorobromide.

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

In addition, in the silver halide emulsion layer containing silver halide grains having a silver chloride content of 90 mol% or more according to the present invention, the silver chloride content in the total silver halide grains contained in the emulsion layer is The proportion of silver halide grains of 90 mol% or more is 60% by weight or more, preferably 80% by weight or more.

The composition of the silver halide grains 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. Further, when the composition inside and outside the particle is different, the composition may change continuously or discontinuously.

The grain size of the silver halide grains of the present invention is not particularly limited, but in consideration of other photographic performance such as rapid processing and sensitivity, it is preferably 0.2 to 1.6 μm, more preferably 0.
．． It is a cylindrical vessel with a diameter of 25 to 1.2 μm.

Note that the particle size can be measured by various methods commonly used in the technical field. A typical method is Loveland's "Particle Size Analysis Method J.
(A, S, T, M, Symposium on Light Microscopy, 1955.

(pp. 94-122) or The Theory of the Photographic Process (by Mies and James, 3rd edition, published by Macmillan)
1966), Chapter 2).

The particle size can be measured using the particle's projected area or diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be described fairly accurately as diameter or projected area.

The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse.

Preferably, the silver halide grains are monodisperse silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less in the grain size distribution. The coefficient of variation here is a coefficient indicating the breadth of the particle size distribution, and is defined by the following equation.

Here, rl represents the particle size on each side of the particle, and nl represents the number thereof.

The grain size here refers to the diameter in the case of spherical silver halide grains, and in the case of grains with shapes other than cubic or spherical, the diameter when the projected image is converted to a circular image of the same area. .

The silver halide grains used in the emulsion of the present invention can be prepared by acidic method.
It may be obtained by either the neutral method or the ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced.

The method of creating and growing the seed particles may be the same or different.

Further, the soluble silver salt and the soluble halogen salt may be reacted by any method such as a forward mixing method, a back mixing method, a simultaneous mixing method, or a combination thereof, but those obtained by a simultaneous mixing method are preferable. Furthermore, as a form of simultaneous mixing method,
It is also possible to use the I) AC+-chondrold-double jet method described in No. 4-48521 and the like.

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

Any shape of the silver halide grains according to the present invention can be used. One preferred example is a cube having a (100) plane as a crystal surface.

Also, U.S. Patent Nos. 4,183,756 and 4,22
No. 5,666, JP-A No. 55-26589, Special Publication No. 55-Sho.
Specifications such as -42737, The Journal of
Photographic Science LJ, Photo
r, 5ci), 21.

39 (1973), etc., by the method described in the literature such as
Particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons can also be prepared and used. Furthermore, particles having twin planes may be used.

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

The silver halide grains used in the emulsion of the present invention are formed by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts, etc. Alternatively, metal ions can be added using complex salts and included inside the particles and/or on the particle surface, and by placing them in an appropriate reducing atmosphere.
Reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

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 growth of the silver halide grains, or they may be left in the emulsion. . In the case of removing the salts, it can be carried out based on the method described in Research Disclosure 17643m.

The silver halide grains used in the emulsion of the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains. Preferably, the particles are particles on which latent images are mainly formed.

The emulsion of the present invention is chemically sensitized by conventional methods.

That is, compounds or substances containing sulfur that can react with silver ions, sulfur sensitization using active gelatin, selenium sensitization using selenium compounds, reduction sensitization using reducing substances, gold or other noble metal compounds are used. Noble metal sensitization methods can be used alone or in combination.

In the present invention, for example, a chalcogen sensitizer can be used as a chemical sensitizer. Chalcogen sensitizer is a general term for sulfur sensitizers, selenium sensitizers, and tellurium sensitizers, and for photography, sulfur sensitizers and selenium sensitizers are preferred. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbazide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, and rhodanine. Others: U.S. Patent No. 1,574,944;
No. 2.410,689, No. 2,278,947,
No. 2,728,668, No. 3,501,313,
No. 3,656,955, West German Publication (OLS)
Sulfur sensitizers described in JP-A No. 1,422,869, JP-A No. 56-24937, JP-A No. 55-45016, etc. can also be used. The addition port for sulfur sensitizer is pH
It varies over a considerable range depending on various conditions such as temperature and size of silver halide grains, but as a rough guide, it is preferably about 10 -7 mol to 10 -1 mol per mol of silver halide.

Selenium sensitizers can be used instead of sulfur sensitizers, but examples of selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas,
Selenides such as selenoketones, selenoamides, selenocarboxylic acid salts and esters, selenophosphates, diethylselenide, and diethyl diselenide can be used, and specific examples thereof are described in U.S. Pat. No. 1,577.
No. 4,944, No. 1.602.592, No. 1,623
, No. 499.

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

Further, a noble compound other than gold, such as a palladium compound, can also be used in combination.

The silver halide grains according to the 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 types of gold compounds are used.

Representative examples include chlorauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyano auric azide, ammonium aurothiocyanate, pyridyl trichlorogold, gold sulfide,
Examples include gold selenide.

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

The amount of addition (1) of the gold compound varies depending on various conditions, but as a guide, it is from 10@-8 mol to 10@-1 mol, preferably from 10@-7 mol to 10@-2 mol, per mol of silver halide. These compounds may be added at any time during silver halide grain formation, during physical ripening, during chemical ripening, or after completion of chemical ripening.

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

Along with the sensitizing dye, the emulsion contains a dye that does not itself have a spectral sensitizing effect, or a super sensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. It's okay.

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

It is desirable that these dye-forming couplers have in the molecule a group called a baras group having 8 or more carbon atoms which makes the coupler non-diffusive.

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

General Formula [Y] In the formula, R1 represents a halogen atom or an alkoxy group. R2Y represents a hydrogen atom, a halogen atom or an alkoxy group. R3 represents an acylamino group, an alkoxycarbonylarylsulfamoyl group, an arylsulfonamide group, an alkylureido group, an arylureido group, a succinimide group, an alkoxy group, or an aryloxy group. ZIY represents a group that can be separated upon coupling with an oxidized color developing agent.

Specific examples of yellow couplers that can be used include British Patent Nos.
077, 874, JP 45-40757, JP 47-1031, JP 47-26133, JP 48-9
No. 4432, No. 50-87650, No. 51-363
No. 1, No. 52-115219, No. 54-99433, No. 54-133329, No. 5G-30127, U.S. Patent No. 2,875,057, No. 3,253,924
No. 3,265.

No. 506, No. 3,408,194, No. 3,551,1
No. 55, No. 3, No. 551,156, No. 3,664,8
No. 41, No. 3,725,072, No. 3,730,
No. 722, No. 3,891,445, No. 3,900,4
No. 83, No. 3,929,484, No. 3,933,50
No. 0, No. 3,973, 968, No. 3,990,8
No. 96, No. 4, 012, No. 259, No. 4, 022
, No. 620, No. 4,029,508, No. 4,05
No. 7,432, No. 4,106,942, No. 4,133
, No. 958, No. 4,269,936, No. 4,286,
No. 053, No. 4, 304, 845, No. 4,314
.

No. 023, No. 4,336,327, No. 4, 356,
No. 258, No. 4, No. 386,155, No. 4,401,
This is described in No. 752, etc.

As the magenta dye-forming coupler, 5-pyrazolone couplers, birazo-O azole couplers, etc. can be preferably used. More preferred are couplers represented by the following formula [Pl or [a].

General formula [Pl'' Ar In the formula, Ar represents an aryl group, Rp+ represents a hydrogen atom or a substituent, and RD2 represents a substituent. Y is ml due to reaction with a hydrogen atom or an oxidized product of a color developing agent.
A group capable of JIQ, W is -NH-1-Nl-IGO-
(N atom is bonded to the carbon atom of the pyrazolone nucleus) or -N
It represents HCONH-, and m is an integer of 1 or 2.

General Formula [11] In the formula, Za represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Za may have an M substituent.

X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent; Ra represents a hydrogen atom or an exchange group; ,
Substituents for a include, for example, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a hetero rM group, an acyl group, a sulfonyl group, a sulfinyl group, a phosphonyl group, and a carbamoyl group. group, sulfamoyl group, cyan group, spiro compound residue, organic hydrocarbon compound residue, alkoxy group, aryloxy group, hederocyclic oxy group, siloxy group,
Acyloxy group, carbamoyloxy group, amine L acylamino group, sulfonamide group, imide group, ureido group, sulf7moyl amine L alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, and a heterocyclic thio group.

These include, for example, U.S. Patent Nos. 2.600.788, 3.061.432, 3.062.653,
3.127゜269, 3,311,476, 3,152,896, 3,419,391
No. 3,519,429@, No. 3,555.31
No. 8, No. 3,684,514, No. 3,888,6
No. 80, No. 3.907.571, No. 3,928,
No. 044, No. 3.930.861, No. 3,930
, No. 866, specifications such as No. 3,933,500, JP-A No. 49-29639, No. 49-111631, No. 49-129538, No. 50-13041, No. 5
No. 2-58922, No. 55-62454, No. 55-
No. 118034, No. 56-38043, No. 57-35
Publications No. 858 and No. 60-23855, British Patent No. 1.247.493, Belgian Patent No. 769,116
No. 792.525, West German Patent No. 2,156,11
Specifications of No. 1, Japanese Patent Publication No. 46-60479, Japanese Patent Publication No. 1973
No. 9-125732, No. 59-228252@, No. 59
-162548%, 59-17195 (No. 3, 60
-33552, 60-43659, West German Patent No. 1, 070.030, and U.S. Patent No. 13,725,
It is described in each specification etc. of No. 067.

As the cyan dye-forming coupler, a phenol-based or naphthol-based cyan dye-forming coupler is used. Among these, preferably the following - Clothing charges [E] or [F]
A coupler shown in is used.

General formula [U:1 In the formula, R+a represents an aryl group, a cycloalkyl group, or a heterocyclic group. R2E represents an alkyl group or a phenyl group. R3E represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.

zl represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent. , methyl group, nonyl group, etc.). R5
F represents an alkyl group (eg, methyl group, ethyl group, etc.). R6F' is a hydrogen atom, a halogen atom (e.g. fluorine, chlorine, bromine, etc.) or an alkyl group (e.g. methyl group,
(ethyl group, etc.).

Z21- reacts with a hydrogen atom or an oxidized product of an aromatic primary amine color developing agent! ! lIt represents a group that can be eliminated.

These cyan dye image-forming couplers are described in U.S. Pat.
, No. 306,410, No. 2,356,475, No. 2.362,598, No. 2.367, 531, No. 2.369.929, No. 2.423.730 @ ,
2,474.2'93, 2,476.008
No. 2,498.466@, No. 2.545゜68
No. 7, No. 2,728,660, No. 2.772.1
No. 62, No. 2,895,826, No. 2,976,
No. 146, No. 3.002, No. 836, No. 3.41
No. 9,390, No. 3.446.622, No. 3.4
76, 563, 3.737.316, 3.
758.308, British Patent No. 3,839,044, British Patent No. 478,991, British Patent No. 945.542, British Patent No. 1
, 084,480, 1.377.233, 1,388,024, and 1,543°040, as well as JP-A-47-37425 and JP-A-50-
No. 10135, No. 50-25228, No. 50-11
No. 2038, No. 50-117422, No. 50-13
No. 0441, No. 51-6551, No. 51-3764
No. 7, No. 51-52828, No. 51-108841
No. 53-109630, No. 54-48237, No. 54-66129, No. 54-131931, No. 55-32071, No. 59-146050, No. 59
It is described in various publications such as No. 31953 and No. 60-117249.

The dye-forming couplers used in this invention are typically present in each silver halide emulsion layer at a concentration of 1X per mole of silver halide.
It can be used in a range of 10-3 mol to 1 mol, preferably 1X10-2 mol to 8X10-1 mol.

The above dye-forming couplers are usually dissolved in a high-boiling organic solvent with a boiling point of about 150°C or higher, if necessary in combination with a low-boiling point and/or water-soluble organic solvent, and then added to a hydrophilic binder such as an aqueous gelatin solution to form a surfactant. After emulsifying and dispersing using an agent,
It may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

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

The silver halide photographic light-sensitive material used in the present invention can be, for example, a color negative film, a positive film, or a color photographic paper, but in particular, when a color photographic paper directly used for the W Prize is used. The effects of the method of the present invention are effectively exhibited.

The silver halide photographic material of the present invention, including this color photographic paper, may be one for monochrome use or one for multicolor use. In the case of multicolor silver halide photographic materials, in order to perform subtractive color reproduction, a photographic coupler is usually used.
It has a structure in which a silver halide emulsion layer containing magenta, yellow, and cyan couplers and a non-light-sensitive layer are laminated on a support in an appropriate number and order of layers. The order may be changed as appropriate depending on the important performance and purpose of use.

When the silver halide photographic light-sensitive material used in the present invention is a multicolor light-sensitive material, the specific layer structure includes a yellow dye image-forming layer, an intermediate layer, a magenta dye image-forming layer, an intermediate layer, and a magenta dye image-forming layer on the support. Particularly preferred is an arrangement consisting of an image forming layer, an intermediate layer, a cyan dye image forming layer, an intermediate layer, and a protective layer II.

As the binder (or protective colloid) used in the silver halide photographic material of the present invention, gelatin is advantageously used, but gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugars, etc. Hydrophilic colloids such as derivatives, cellulose derivatives, synthetic hydrophilic polymeric substances such as single or copolymers can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the silver halide photographic light-sensitive material of the present invention can be hardened by crosslinking binder (or protective colloid) molecules and using a hardening agent alone or in combination to increase film strength. be done. It is desirable that the hardening agent be added to the processing solution to the extent that it can harden the photosensitive material, but it is also possible to add the hardening agent to the processing solution.

In the present invention, the silver halide emulsion layer is vI! In order to form a film, it is preferable to use a chlorotriazine-based hardener represented by [HDAI or [HOB] below.

General formula [11DΔ] In the formula, R and J+ are ml atom, hydroxy group, alkyl group, alkoxy group, alkylthio group, -0M group (here, M is a monovalent metal atom), -NR' R” group (
Here, R' and R'' represent a hydrogen atom, an alkyl group, or an aryl group, respectively) or a -NHCOR group (where Rn is a hydrogen atom, an alkyl group, or an aryl group), and Rclλ represents a chlorine atom. Kai general formula [+-11') 13] In the formula, RJ3 and fld4 each represent a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group or a 1○M group (here, M is a monovalent metal atom).QOJ:
and Q' represent a linking group representing 10-, -S- or -NH-, respectively, and q represents an alkylene group or an arylene group. O and q each represent O or 1.

Next, the above-mentioned clothes cost [HD A] 63 and [+-I D
Typical specific examples of preferred hardeners represented by B] will be described below.

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

These hardeners are used in an amount of 0.5 to 10 per gram of coated gelatin.
(1 mg, preferably 2.0 to 5011 (+ added).

Silver halide photographic material used in the present invention (hereinafter referred to as
A plasticizer can 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.

The silver halide photographic material of the present invention can contain an image stabilizer that prevents deterioration of the dye image.

To prevent fogging caused by discharge caused by friction of the photosensitive material in the hydrophilic colloid layers such as the protective layer and intermediate layer of the silver halide photographic light-sensitive material of the present invention, and to prevent image deterioration due to U light. may contain an ultraviolet absorber.

The silver halide photographic material of the present invention may be provided with auxiliary layers such as a filter layer, an antihalation layer, and/or an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development.

The silver halide emulsion layer of the silver halide photosensitive material of the present invention,
And/or a matting agent can be added to other hydrophilic colloid layers for the purpose of reducing the gloss of the photosensitive material, increasing the ease of writing, and preventing mutual poking of the photosensitive materials.

A lubricant can be added to the silver halide photographic material of the present invention in order to reduce sliding friction.

The silver halide photographic light-sensitive material of the present invention may contain an antistatic agent for the purpose of preventing static electricity. Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used in a colloid layer.

The photographic emulsion layer and/or the silver halide photographic light-sensitive material of the present invention
Other hydrophilic colloid layers may contain various additives for the purpose of improving coating properties, preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (such as accelerating development, increasing contrast, and sensitizing). Surfactants are used.

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

The silver halide photosensitive material of the present invention can be produced directly or (adhesiveness, antistatic property, dimensional stability of the support surface) after subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary. The coating may be coated via one or more subbing layers (to improve properties such as hardness, abrasion resistance, hardness, antihalation properties, 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 to improve coating properties. Particularly useful coating methods are extrusion coating and curtain coating, which allow two or more layers to be applied simultaneously.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams,
Any known light source can be used, such as light emitted from a phosphor excited by X-rays, T-rays, α-rays, or the like.

The exposure time is 1 millisecond to 1 millisecond, which is normally used in printers.
Not only can exposure times be 0 seconds, but also exposures shorter than 1 millisecond, such as 100 microseconds or more using a cathode ray tube or xenon flash lamp.
Exposures of 1 millisecond can be used, or exposures longer than 10 seconds are possible.

The exposure may be performed continuously or intermittently.

Yu/Two, two.

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

Here, the term "substantially free of bromide ions" refers to a processing solution containing no more than 5 x 10' mol/l of bromide ions. In the present invention, high chloride silver halide having a silver chloride content of 90 mol% or more is used as the silver halide. It may contain silver oxide or silver iodide. Therefore, when silver bromide is contained, a small amount of bromide ions are eluted into the developer during development. This eluted bromide ion partially replaces the silver halide due to the difference in solubility of several orders of magnitude between the chloride ion in the high chloride silver halide, which is not developed even in the developer, and the part other than the image area, that is, the silver halide which is not developed even in the developer. It is also conceivable that the photosensitive material is retained in the photographic material and taken out to the next process. However, as long as bromide ions may be eluted into the developing solution by developing high chloride silver halide as described above, the bromide ion concentration in the developing solution can be completely reduced to O.
cannot be maintained. In the present invention, "substantially no bromide ions are contained" means that no bromide ions are contained other than unavoidably mixed bromide ions such as trace amounts of bromide ions eluted during development, and 5 x 10' mol/l is unavoidable. This indicates the maximum allowable concentration of bromide ions.

Further, the color developing solution used in the present invention does not substantially contain bromide ions, but it is preferable that a certain amount of chloride ions be present. That is, I per 12 color developing solutions.
X 10-3 to 0.5 mol, more preferably 2X10
It is preferred to contain -3 to 0.2 moles of chloride ions.

Further, the color developing solution according to the present invention has a sulfite ion content of 2×10 −2 to I×10 −2 mol/l.

In the color development step, an aromatic primary amine developing agent dissolved in an alkaline aqueous solution is generally used. Normally, alkaline developers are unstable to oxidation, and sulfite ions are added as a storage stabilizer (preservative) to prevent oxidation. However, it is known that this sulfite ion reacts with the oxidized color developing agent and thus reduces the color development efficiency. For this reason, for example, JP-A-61-7
No. 3955, etc., discloses a technique for improving color development by setting the sulfite ion concentration to a specific m or less. When a photographic material using an emulsion is processed with a color developing solution that does not substantially contain bromide ions, the effect of improving color development properties is particularly remarkable when sulfite ions are reduced, and the above-mentioned specific low sulfite ion concentration range It was found that the most favorable results were obtained. In other words, if the sulfite ion concentration exceeds 1 X 10-2 mol/l, rapid color development cannot be achieved, and if it is less than 2 Compound [S] which is not only a development inhibitor but also a development inhibitor.
Even in the presence of Dmin, the minimum density (Dmin) increases and the photographic image quality is significantly impaired.

In this way, in a system that uses a light-sensitive material containing a high chloride silver halide emulsion and a color developing solution that does not substantially contain bromide ions, and has an extremely fast color development speed, the sulfite ion concentration can be simply reduced. That doesn't mean it's good,
It has been found that only within the above-mentioned specific range can the minimum concentration be sufficiently suppressed and the rapid processability both satisfied at the same time.

Furthermore, more surprisingly, the silver halide photographic light-sensitive material containing the system of the present invention, that is, silver halide grains having a silver chloride content of 90 mol % or more and the compound [3] according to the present invention, can be used with bromide ions. In a system processed with a color developing solution that does not substantially contain sulfite ions and contains sulfite ions in a specific range of 2 x 10-4 to 1 x 10-2 mol/l,
It has a great advantage in terms of quality stability, with extremely small fluctuations in photographic performance such as gradation fluctuations of dye images obtained due to mixing of bleach-fixing solution into the color developing solution and differences in I)H fluctuations of the color developing solution. This is what we discovered.

The sulfite ion concentration in the above color developer is 2X10-4 ~
The object of the present invention can be achieved if I
It is 10-3 mol/l.

Sulfite ions can be used, for example, in the form of alkali metal sulfites, alkali metal bisulfites or ammonium salts of sulfite or bisulfite. In the color developing solution used in the present invention, in order to maintain the sulfite ion at the above specified low concentration and to stabilize the color developing solution,
Dihydroxyacetones described in U.S. Patent No. 3,615.503, hydroxyureas described in JP-A No. 52-27638, monosaccharides such as pentoses described in JP-A-52-102727, Aromatic secondary alcohols, etc. described in No. 7729 may also be used, such as a method of roughly replenishing a large amount of color developer, a method of keeping the developer in a nearly sealed state and preventing contact with air as much as possible, and sulfurous acid. By adding a compound to the developer that keeps the ion concentration low and forms a stable sulfite ion adduct in an equilibrium state, the color developer can be stabilized and have a low sulfite M content.
It may be kept at e degree.

Compounds that form stable sulfite ion adducts with sulfite ions include, for example, compounds having an aldehyde group,
Examples include compounds containing a cyclic hemiacetal, compounds having an α-dicarbonyl group, and compounds having a nitrile group.

The color developing agent used in the color developing solution in the present invention includes known color developing agents that are widely used in various color photographic processes.

These developers include aminophenol and p-phenylenediamine derivatives. Since these compounds are more stable than their free states, they are generally used in the form of salts, such as hydrochlorides or sulfur salts. Additionally, these compounds generally have a concentration of about 0.1σ to about 3(l) per color developer, preferably about 1g to about 15g per 1i of color developer.
Use at a concentration of o.

Examples of aminophenol-based developers include 0-7minophenol, p-aminephenol, and 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1°4-dimethylbenzene and the like.

Particularly useful primary aromatic amine color developers are N, N'
-Dialkyl-p-phenylenediamine compound, and 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-〇-phenylenediamine hydrochloride,
, 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- and droxyethylaminoaniline,
4-amino-3-methyl-N.

N'-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-
Examples include toluene sulfonate.

In addition to the above-mentioned primary aromatic amine color developer, known developer component compounds can be added to the color developer applied to the present invention. For example, sodium hydroxide,
Alkali agents such as sodium carbonate and potassium carbonate, alkali metal sulfites, alkali gold [i-sulfites, alkali metal thiocyanine Mm, alkali gold dihalides, benzyl alcohol, water softeners, thickeners, etc.] may optionally be contained. You can also do it.

The color developer ct3 ElH value is usually greater than or equal to 7, most commonly from about 10 to about 13.

The color development temperature is usually 15°C or higher;
°C~50. 'C range. 30 for quick development
It is preferable to carry out the reaction at a temperature of ℃ or higher. Further, the color development time is generally preferably carried out within a range of 20 seconds to 60 seconds, more preferably within a range of 30 seconds to 50 seconds.

The silver halide photographic material according to the present invention may contain these color developing agents in the hydrophilic colloid layer either as the color developing agent itself or as its precursor, and may be processed in an alkaline activation bath. The color developing agent brecasa is a compound that can produce a color developing agent under alkaline conditions, and includes a Schiff 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. The precursors of these aromatic primary amine color developing agents are:
For example, U.S. Patent No. 3.342.599, U.S. Pat.
7.114, 2,695,234, 3,7
No. 19,492, specifications of British Patent No. 803.783, Japanese Patent Application Publication No. 185628/1983, and Japanese Patent Application Publication No. 54-79035.
Issues of publications, Research Disclosure Magazine 1515
These aromatic primary amine color developing agents or their precursors described in No. 9, No. 12146, and No. 13924 should be added in an amount sufficient to provide sufficient color development only along the sides when activated. It is necessary to keep it. The amount varies depending on the type of photosensitive material, but it is generally used in a range of 0 to 5 moles, preferably 0.5 to 3 moles, per mole of silver halide. These color developing agents or their precursors can be used alone or in combination. In order to incorporate it into a photosensitive material, it can be dissolved in a suitable solvent such as water, methanol, ethanol, acetone, etc.
It can also be added as an emulsified dispersion using a high boiling point solvent such as dibutyl phthalate or tricresyl phosphate, or it can be added by impregnating a latex polymer as described in Research Disclosure No. 14850. can.

After color development, the silver halide photographic material of the present invention is subjected to bleaching and fixing. Bleaching treatment may be performed simultaneously with fixing treatment. Many compounds are used as bleaching agents, among them iron (1), cobalt (■), and copper (II).
polyvalent metal compounds, especially complex salts of these polyvalent metal cations and organic acids, such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, N-hydroxyethylethylenediaminediacetic acid, malonic acid, tartaric acid, malic acid. , diglycolic acid, dithioglycolic acid, metal complex salts, ferricyanates, dichromates, etc. alone or in appropriate combinations.

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 an alternative to the water washing treatment, a stabilization treatment may be performed, or both may be used in combination. The stabilizing liquid used in the stabilization treatment can contain an OH regulator, a chelating agent, an anti-spill agent, and the like. These specific conditions are described in Japanese Unexamined Patent Publication No. 5
8-134636 etc. can be referred to.

[Specific Effects of the Invention] According to the dye image forming method of the present invention having the structure as explained above, the minimum density of the dye image formed is suppressed to a sufficiently low level, and excellent rapid processability is achieved, resulting in rough color development. Developer B
It was also excellent in F contamination resistance and pH fluctuation resistance.

[Specific Examples of the Invention] Hereinafter, the present invention will be specifically explained using Examples, but the embodiments of the present invention are not limited thereto.

Example-1 Preparation of silver halide emulsion EMP-1 A silver nitrate aqueous solution and a sodium chloride aqueous solution were added and mixed into an inert gelatin aqueous solution with stirring by a double jet method. At this time, the temperature was 60℃, 1) H-3,0, D
It was controlled to maintain AIJ at -7 and -8. Next, desalting was performed by a conventional method to obtain EMP-1. EMP
-1 was a cubic monodispersed silver chloride emulsion with an average grain size of 0.7 μl (7).

EMP-2 A silver nitrate aqueous solution and a halide aqueous solution (mixed aqueous solution of potassium bromide and sodium chloride) were added and mixed into an inert gelatin aqueous solution by a double jet method. At this time, the temperature was controlled to be maintained at 60 DEG C. and the pH at -3.0 DEG pAo -7.8 according to the method described in JP-A-59-45437. Next, desalting was performed by a conventional method to obtain EMP-2.
I got it. EMP-2 has an average particle size of 0.7 μm and silver bromide of 90%.
The emulsion was a monodisperse emulsion consisting of tetradecahedral silver chlorobromide grains containing mol %.

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

Sulfur sensitizer: Sodium thiosulfate 2.5 mg 1 mol AgX Sensitizing dye: D-110010/Mo/L+AgX
Compound [8]: S-81,5X10-3 mol AoX temperature
Temperature: 60°C Time: 60 minutes Sensitizing dye (D-1) Next, a dispersion of yellow coupler was prepared by the following method.

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

YC-1 Next, using the emulsions EMB-1 and EMB-2,
Photosensitive materials [A] and [B] were prepared with the following configurations.

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

Photosensitive material [A] and photosensitive material [B] thus obtained
Rapid processing is possible using the method shown below.
was evaluated.

[Evaluation of Rapid Processability] Using a KS-7 sensitometer (manufactured by Konishi Roku Photo Co., Ltd.), exposure was carried out through an optical wedge, and then the following treatments were performed. However, for the color development process, the processing time was 20 seconds, 45 seconds, and 90 seconds, and the following color developer compositions were 4 types (A), (B), (C), and (D). .

[Processing process] Temperature Time Color development 34.7±0.3℃ 20 seconds, 45 seconds, 9
Bleach-fix for 0 seconds Stabilize for 45 seconds at 34.7±0.5℃ Dry for 90 seconds at 30-34℃
60 to 80°C for 60 seconds [Color developer composition] Pure water was added to each of the components A to 0 above to make 12, and I)H was adjusted to 10.2 with sulfuric acid or potassium hydroxide.

(Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 601) Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100d Ammonium sulfite (40% solution) 27.51fi
Adjust the pH to 7.I with potassium carbonate or glacial acetic acid, and add water to bring the total volume to 12.

(Stabilizing liquid) 5-chloroo-2-methyl-4-isothiazolin-3-one 1g 1-hydroxyethylidene-1,1-diphosphonic acid 2g Add water to make 11, and adjust DH to 7 with sulfuric acid or potassium hydroxide. Adjust to .0.

The anti@ concentration of the obtained sample was measured using a densitometer (PDA-65: Konishiroku Photo Co., Ltd.), and the characteristic values defined below were determined.

Gradation (γ): The slope of the straight line connecting the density 0.5 and 1.5 points of the characteristic curve.

Minimum temperature (Dmin): Display the density results of the unexposed area.
Shown in 1. In Table 1, it is clear from Table 1 that the lower D sin, the sufficient γ value, and the smaller the change in characteristic values between time steps of color development, the faster the processing speed.
Comparative experiment 1 using silver chlorobromide particles with low silver chloride content
-5 to 1-8 are basically unsatisfactory in terms of rapid processing. In addition, when a sample with a high silver chloride content is processed with a color developing solution containing bromide ions exceeding the limit specified in the present invention (Comparative Experiments 1-4), the rapid processability is unsatisfactory. Furthermore, when processed with a color developer containing sulfite ions exceeding the level specified in the present invention (
Comparative experiment 1-1) also had an unsatisfactory level of rapid processability, while the rapid processability was satisfactory in the case of processing with a color developer containing no sulfite ions (comparative experiment 1-3). An increase in the minimum concentration of what is possible is observed;
Both samples have problems. On the other hand,
Experiments 1-2 of the present invention were satisfactory in terms of both rapid processability and minimum concentration level.

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

Sulfur sensitizer: Sodium thiosulfate 2.5 mol 1 mol AOX Sensitizing dye: D-240 mg 1 mol AOX Auric chloride: (Conditions shown in Table-2) Compound [81: (Conditions shown in Table-2) Temperature
= 55℃ Note that the sensitizing dye was added after 5 minutes of adding sodium thiosulfate, and the chlorauric acid was added to compound [S] after 60 minutes of addition of thiosulfate and silium.
were added 70 minutes after addition of sodium thiosulfate,
The addition of compound [S] marked the end of chemical sensitization.

(D-2) Next, monodispersed cubic silver chlorobromide particles having an average particle size of 0.5 μl and containing 2.0 mol% of silver bromide were prepared in the same manner as EMP-2 of Example-1. Emulsion EMP-3 was prepared.

This EMP-3 was chemically sensitized under the same conditions as EMR-1 to EMR-7, and EMR-8 to EM
He wears R-21.

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

[Dispersion method of cyan coupler] Cyan coupler (CG-1) 40 (+ was dissolved in a mixed solvent of 10 nQ of dibutyl phthalate and ethyl acetate, and this solution was added to an aqueous gelatin solution containing dodecylbenzenesulfonic acid). After that, it was dispersed using an ultrasonic homogenizer.

Next, the above coupler dispersion and the above emulsion EMR-1
Samples 2-1 to 2-20 were prepared using EMR-20 and the following configurations.

The rapid processability of Samples 2-1 to 2-21 was evaluated in the same manner as in Example-1.

However, for the color developing solution, only the composition [B] was used. The results are shown in Table-2.

Furthermore, BFF entry resistance and p
H fluctuation resistance was evaluated.

[BF Contamination Resistance Test The above color developer [8] Color developer [E] to which 0.5 d and 1.0 d of the above bleach-fix solution were added per 1ffi, [E], [
F] was prepared.

Using these color developing solutions, processing was performed according to the same color development process as in the evaluation of rapid processability, and sensitometric measurements were performed. However, the color development time was only 45 seconds.

The results are shown in Table-2. In the table, Δ[] sin refers to the range of variation when processing with a color developer mixed with a bleach-fix solution, based on the minimum density (Dmin) when processed with a color developer containing a bleach-fix solution. The smaller the value shown, the better the resistance to BF contamination.

[+18 Fluctuation Resistance Test 1 Color developing solutions having the same composition as the color developing solution [B] and having DH-9, 8, and 10.6 were prepared.

Using these color developing solutions [B1], the samples were processed according to the same color development process as in the evaluation of rapid processability, and sensitometric measurements were performed. However, the color development time was only 45 seconds.

The results are shown in Table-2. In the table, ΔQ win means I) H=
The lowest S degree (Dmi) when processed with a color developer of 9.8
This value indicates a change in temperature when processed with a color developing solution having a different pH based on n).

The structural formulas of Comparative Compounds (SC-1) and (SC-2) of Compound [81] used in Table 2 are as follows.

G-1 c-i As is clear from Table 2, even when using the color developer according to the present invention, sample 2-1.2-2 using the comparative compound of compound [S] according to the present invention .2-8 and 2-9, the minimum concentration increased significantly, and
The F contamination resistance and 11H fluctuation resistance are also at a problematic level. On the other hand, in samples 2-3 to 2-7 and 2-10 to 2-21 using compound [S] according to the present invention, the minimum concentration was kept sufficiently low, and the rapid processability was also satisfied. It also has extremely good resistance to BF contamination and resistance to pH fluctuation. Looking in more detail, the effects of the present invention, such as reducing the minimum concentration, rapid processability, resistance to BF contamination, and resistance to pH fluctuations, are efficiently achieved by adding a gold compound, and the addition of a gold compound to a gold compound containing a trace amount of silver bromide By using silver halide grains with a silver chloride content, the minimum concentration can be further reduced and the resistance to BF contamination and resistance to I)H fluctuations can be improved.

Example-3 Emulsions EMP-1 to EM prepared in Examples-1 and 2
P-3 was chemically sensitized under the following conditions to obtain EM-1 to EM-12. Note that the conditions for adding the sensitizing dye, chloroauric acid, and compound [S] were the same as in Example-2.

Temperature = 55°C Sulfur sensitizer: Sodium thiosulfate 2 x 1 mol A (IX
Next, using the above EM-1 to EM-12, samples 3-1 to 3-8 were prepared with the configuration shown in Table 3 and under the conditions shown in Table 4.
It was created. However, the hardening agent shown in Table 4 was added to the seventh layer.

Table 3 Ultraviolet absorber (UV-1> Magenta coupler (MC-1) Z Sensitizing dye (D-3) S (J z /) Same method as Example 2 for Samples 3-1 to 3-8 The rapid processability, resistance to BFff! entry, and initial resistance to pi-1 were evaluated.The results are shown in Table 4.

As is clear from Table 4, Samples 3-1 J3 and 3-5, whose silver chloride content is outside the scope of the present invention, are unsatisfactory in both rapid processability J3 and minimum temperature of 111 degrees, and are also unsatisfactory in terms of BFIII resistance and l) The l-1 fluctuation tolerance was also at a problematic level. In addition, in samples 3-2 and 3-6 using comparative compounds of compound [3], although the rapid processability was satisfactory, the minimum concentration, BF contamination resistance and pH *
The dynamic resistance has deteriorated significantly. On the other hand, samples 3-3.3-4.3-7 and 3-8 of the present invention showed excellent properties in both rapid processing and minimum concentration, and also showed excellent BFiI resistance and pl-1 variation. Resistance has also been greatly improved. A more detailed look shows that the effects of the present invention can be achieved more efficiently by using a chlorotriazine compound as a hardening agent.

Claims (1)

[Scope of Claims] A dye image obtained by imagewise exposing a silver halide photographic material having at least one silver halide emulsion layer containing a dye-forming coupler on a support, and then subjecting it to photographic processing including color development processing. In the formation method, at least one of the silver halide emulsion layers 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 photosensitive silver halide. The color developer used in the color development process has a sulfite ion content of 2 x 10^-^4 to 1 x 10^-^2 mol/l.
1. A method for forming a dye image, characterized in that it contains substantially no bromide ions. General formula [S] ▲Mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Z is a benzenetriazole ring, or 1, 2,
Represents the atomic group necessary to complete the 3,4-thiatriazole ring. )