JP2517300B2 - Highly sensitive silver halide photographic light-sensitive material with improved raw storability - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material (hereinafter referred to as a light-sensitive material), and more specifically, it has high sensitivity and resistance to performance fluctuation due to storage of the light-sensitive material. The present invention relates to a light-sensitive material excellent in (storability of raw sample).

[Background of the Invention]

In recent years, highly sensitive photosensitive materials have been increasingly demanded from various viewpoints, and sensitization techniques have been studied in various fields. As a study of the sensitization technology for silver halide grains, for example, the quantum efficiency of silver halide is theoretically calculated,
A study that considers the influence of particle size distribution is related to the progress of photography.
It is described in "Interactions Between Lights and Materials for Photographic Applications", page 91, "80th Tokyo Symposium Proceedings". This study suggests that making a monodisperse emulsion is effective for improving quantum efficiency, that is, it is possible to increase sensitivity.

On the other hand, as a study of sensitization techniques, studies have been made to perform optimal chemical sensitization on these silver halide emulsions. As a sensitizer used for chemical sensitization, conventionally, a sulfur sensitizer,
Selenium sensitizers, reduction sensitizers, precious metal sensitizers and the like are well known. These chemical sensitizers may be used alone or in combination of two or more kinds.

Further, it is also a well-known technique to add a sensitizing dye to a silver halide emulsion to expand the intrinsic wavelength range of the silver halide emulsion to spectrally sensitize it. It is also known that when a sensitizing dye used at this time has a high spectral sensitizing efficiency, it can remarkably contribute to increasing the sensitivity of the light-sensitive material.

As the sensitizing dye to be used for the above purpose, the spectral sensitizing wavelength range is appropriate, and it should not diffuse into other photosensitive layers or interact with additives other than the sensitizing dye. Those having various desirable properties are selected.

Further, as a more preferable condition, when the light-sensitive material containing a sensitizing dye is stored, a decrease in sensitivity, the occurrence of fog or the occurrence of dye stain after the sensitizing process is small, etc. are satisfied. Required. Especially when a sensitizing dye is used in a multilayer color photographic light-sensitive material,
It is necessary to have higher sensitivity and excellent color reproducibility, and to maintain these photographic characteristics stably even when stored for a long period of time.

As a sensitizing dye used for a green-sensitive or red-sensitive emulsion, certain trimethine dyes are known to be very useful, but these sensitizing dyes may be It has the following drawbacks.

(1) Fog is likely to occur in silver halide emulsions containing these sensitizing dyes.

(2) When the light-sensitive material containing these sensitizing dyes is stored under high humidity, the tone becomes large.

As in the above (1), if the generation of fog is more than the permissible level, it becomes a fatal defect as a light-sensitive material. Therefore, in order to prevent it, a compound conventionally known as an antifoggant or a stabilizer is used. These compounds have been added, but the use of these compounds often causes desensitization and softening, and further adversely affects storage stability.

Among the performances required of the light-sensitive material, such as the storage stability in (2), quality stability is important. It is necessary that the characteristics of the light-sensitive material are always stable, and when these characteristics fluctuate, the image quality finally obtained also inevitably fluctuates. Further, if it is attempted to correct this variation each time, the handling of the photosensitive material becomes extremely complicated.
Among various characteristic variations, gradation variation has a great influence, and gradation variation must be minimized so that there is no practical problem.

The manufactured light-sensitive material is stored until it is used, but gradation may vary depending on the storage conditions. However, it is very difficult to control the storage state after shipping. The improvement of quality stability under various storage conditions is an important issue, and there are several techniques related to this, for example, as a means for improving the storability of raw samples,
JP-A-48-43320, 58-176637, 60-225143,
60-225145, 60-232545, 61-112142, 61-91
There are technologies of 652 and 61-203447, but these are insufficient in that they cannot improve the gradation change without affecting the performance of any of them.
Therefore, there is a demand for the development of an excellent raw sample storability.

Therefore, the inventors of the present invention have conducted various studies to improve the preservation of raw samples, which is a drawback of the above-mentioned trimethine dye, and as a result, by using the trimethine dye and inorganic sulfur together, the photosensitive material obtained was obtained. It was discovered that the raw storability was remarkably improved, and the present invention was completed.

[Object of the Invention]

The object of the present invention is to provide a light-sensitive material containing a trimethine dye sensitized in a green region or a red region, with high sensitivity,
Another object of the present invention is to provide a light-sensitive material with improved raw sample storability.

[Structure of Invention]

The above-mentioned object of the present invention is a silver halide photographic light-sensitive material having at least one photographic constituent layer containing a silver halide emulsion layer on a support, and the silver halide emulsion layer is represented by the general formula [I]. A sensitizing dye is contained and inorganic sulfur is added to at least one of the photographic constituent layers on the side having the silver halide emulsion layer with respect to the support, It has been achieved by a silver halide photographic light-sensitive material characterized in that the inorganic sulfur added to the photographic constituent layer diffuses and substantially exists in the silver halide emulsion layer.

[In the formula, Z ₁ and Z ₂ each represent an atomic group necessary for forming a benzene ring or a naphthalene ring.

R ₁ and R ₂ each represent a substituted or unsubstituted alkyl group, alkenyl group or aryl group. R ₃ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. X ₁ ^-
Represents an anion, and n represents 0 or 1.

Y ₁ and Y ₂ each represent an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or ═N—R ₄ or ═N—R ₅ . R ₄ and R ₅ each represent H, a substituted or unsubstituted alkyl group, an alkenyl group or an aryl group. The present invention will be described in more detail below.

In the compound represented by the general formula [I] used in the present invention, the benzene ring or naphthalene ring formed by Z ₁ and Z ₂ may be substituted with various substituents. Is a halogen atom, an aryl group, an alkyl group or an alkoxy group.

R ₁ and R ₂ each represent an alkyl group, an alkenyl group or an aryl group, preferably an alkyl group. Most preferably, it is an alkyl group having 1 to 5 carbon atoms.

R ₃ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
It preferably represents a hydrogen atom, a methyl group or an ethyl group.
X ₁ ⁻ represents an anion, and n represents 0 or 1.

The sensitizing dye represented by the general formula [I] used in the present invention is, for example, F Chem Harmer, The Chemistry of Heterocyclic Compounds (The Chem.
Istry of Heterocyclic Compounds, Vol. 18, The Cyanine Dyes and Related Compounds (A. Weis
It can be easily synthesized by the method described in Sherger ed. Interscience, New York 1964).

The optimum concentration of the sensitizing dye of the general formula [I] can be determined by a method known to those skilled in the art. For example, there may be mentioned a method in which a certain same emulsion is divided, each emulsion is made to contain a different concentration of sensitizing dye, and the performance of each emulsion is measured.

The addition amount of the sensitizing dye in the present invention is not particularly limited, but 2 × 10 ⁻⁶ mol to 1 × 10 ⁶ mol per mol of silver halide.
^It is preferable to use ^-2 mol, more preferably 5 × 10 ⁻⁶ mol to 5 × 10 ⁻³ mol.

A method well known in the art can be used to add the sensitizing dye to the emulsion. For example, these sensitizing dyes can be directly dispersed in an emulsion, or can be dissolved in a water-soluble solvent such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, or a mixture thereof, or diluted with water. Or dissolved in water and added to the emulsion in the form of these solutions. Ultrasonic vibration can also be used during the dissolution process.
Further, as described in U.S. Pat.No. 3,469,987, a dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and the dispersion is added to an emulsion. As described in JP-A-46-24185, a method in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved and this dispersion is added to an emulsion is also used. Further, the dye can be added to the emulsion in the form of a dispersion according to the acid dissolution dispersion method. To add to other emulsions,
U.S. Pat.Nos. 2,912,345, 3,342,605, 2,996,
The method described in each specification of 287 and 3,425,835 can also be used. The sensitizing dye represented by the general formula [I] used in the present invention may be added to the emulsion at any time during the production process from the formation of silver halide grains to immediately before coating on the support. It can be added.

Specifically, before the formation of silver halide grains, during the formation of silver halide grains, after the formation of silver halide grains and before the start of chemical sensitization, at the start of chemical sensitization, during chemical sensitization, and chemical sensitization. It may be any time selected from the time of completion and from the time of completion of chemical sensitization to the time of application. Moreover, you may add in multiple times. Further, the sensitizing dye represented by the general formula [I] is
It can also be used in combination with other sensitizing dyes as a so-called supersensitizing combination. In this case, each sensitizing dye may be dissolved in the same or different solvent, and these solutions may be mixed or added separately to the emulsion prior to addition to the emulsion. When they are added separately, their order and time interval can be arbitrarily determined according to the purpose.

Specific compounds of the sensitizing dye represented by the general formula [I] are shown below, but the sensitizing dye used in the present invention is not limited to these compounds.

The sensitizing dye used in the present invention is a compound represented by the general formula [I]
When Y ₁ and Y ₂ are oxygen atoms, the spectral sensitization is high when used in combination with inorganic sulfur, and the effect of improving the preservation of raw samples is great.

The term "inorganic sulfur" used in the present invention is:
This means so-called elemental sulfur that does not form a compound with other elements. Therefore, sulfur-containing compounds known in the art as photographic additives, such as sulfides, sulfuric acid (or salts thereof), sulfites (or salts thereof),
Thiosulfuric acid (or its salt), sulfonic acid (or its salt), thioether compound, thiourea compound, mercapto compound, sulfur-containing heterocyclic compound, etc. are not included in the "inorganic sulfur" in the present invention.

It is known that elemental sulfur used as “inorganic sulfur” in the present invention has several allotropes, but any of these allotropes may be used. Among these allotropes, the one stable at room temperature is α-sulfur belonging to the orthorhombic system, and it is preferable to use this α-sulfur in the present invention.

When adding the “inorganic sulfur” according to the present invention, it may be added as a solid, but it is more preferable to add it as a solution. Although inorganic sulfur is insoluble in water, it is known to be soluble in carbon disulfide, sulfur chloride, benzene, diethyl ether, ethanol and the like, and it is preferable to add it after dissolving it in these solvents. Among these inorganic sulfur solvents, ethanol is particularly preferably used because of its handling and adverse effects on photography.

The amount of inorganic sulfur added varies depending on the type of silver halide emulsion applied and the magnitude of the expected effect, but
The amount is 10 ^-5 mg to 10 mg per mol of silver halide. As for the addition amount, the whole amount may be added at one time, or may be added a plurality of times and divided into a plurality of times.

The photographic constituent layer to which the inorganic sulfur according to the present invention is added is added to the photographic constituent layer on the side having the silver halide emulsion layer with respect to the support. The photographic constituent layer may be any of a light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer such as a protective layer and an intermediate layer, but is preferably added to the light-sensitive silver halide emulsion layer. When inorganic sulfur is added to the non-photosensitive hydrophilic colloid layer, after the addition, a part of the inorganic sulfur diffuses and migrates to the emulsion layer, which is the same as when added to the photosensitive silver halide emulsion layer. Produce an effect.

Regarding the timing of adding the inorganic sulfur to the silver halide emulsion layer, it can be added in any step until the chemical sensitization of the silver halide emulsion is completed. That is, before the formation of silver halide grains, during the formation of silver halide grains, after the formation of silver halide grains and before the start of chemical sensitization, at the start of chemical sensitization, during chemical sensitization, and chemical sensitization. It may be any time selected from the time of completion and from the time of completion of chemical sensitization to the time of application. It is preferably added at the start of chemical sensitization, during chemical sensitization, or until the end of chemical sensitization, and more preferably at the start of chemical sensitization.

The chemical sensitization start step refers to a step of adding a chemical sensitizer, and in this step, the time when the chemical sensitizer is added is the start of chemical sensitization.

Further, the above chemical sensitization can be stopped by a method known in the art. As a method of terminating the chemical sensitization, a method of lowering the temperature, a method of lowering the pH, a method of using a chemical sensitization terminator, and the like are known. Is preferred.
Examples of the chemical sensitizer include halide salts (for example, potassium bromide, sodium chloride, etc.), organic compounds known as antifoggants or stabilizers (for example, 7-hydroxy-5-methyl-1,3, 4,7a-tetrazaindene etc.)
It has been known. These are used alone or in combination of a plurality of compounds.

The inorganic sulfur according to the present invention is added in the chemical sensitization stopping step, and the "chemical sensitization stopping step" here means a step of adding the chemical sensitization stopping agent. In this case, the time of adding the inorganic sulfur may be substantially during the chemical sensitization stopping step, and specifically, at the same time as the addition of the chemical sensitization stopping agent or within 10 minutes before or after the addition, preferably at the same time. Or the time when it is added within 5 minutes before or after that.

The silver halide grains contained in the silver halide emulsion according to the present invention may be any of silver chloride, silver chlorobromide, silver bromide, silver iodobromide and silver chloroiodobromide. May be mixed.

Among them, a silver chloride-containing emulsion is more preferable, and a high silver chloride emulsion is particularly preferable because it is remarkably excellent in rapid processability.

However, the high silver chloride emulsion has a drawback that it has lower sensitivity than other silver halide emulsions, and therefore it is necessary to perform sensitization with the sensitizing dye represented by the general formula [I]. In this case, although high sensitivity can be achieved, there is a drawback that the optimum point of gradation and the optimum point of sensitivity and fog at the time of chemical sensitization are deviated. Addition of inorganic sulfur to the emulsion under such a situation can improve this defect, achieve high sensitivity, and improve raw storability.

Therefore, the inorganic sulfur according to the present invention and the general formula [I]
From the viewpoint that the effect of combining the sensitizing dyes shown in 1 above becomes more remarkable, the high silver chloride-containing silver halide grains have a silver chloride content of 80 mol% or more, preferably 90 mol% or more. The silver bromide content is preferably 20 mol% or less, preferably 10 mol% or less, and the silver iodobromide content is preferably 0.5 mol% or less. More preferably, the silver bromide content is 0 to 5 mol%.

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 The proportion of silver halide grains of 90 mol% or more is 60 wt% or more, preferably 80 wt% or more.
Further, when the silver halide grains containing a high silver chloride are used in combination with the inorganic sulfur, preferred sensitizing dyes represented by the general formula [I] are those represented by the general formula [I].
This is the case where Y ₁ and Y ₂ are oxygen atoms.

The composition of the silver halide grain used in the present invention may be uniform from the inside to the outside of the grain,
The composition inside and outside the particle 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 grain used in the present invention is not particularly limited, but considering 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. It is in the range of μm.

The particle diameter can be measured by various methods generally used in the art. As a typical method, Loveland's “Analysis Method of Particle Size”, ASTM Symposium on Light Microcopy, 1955, page 94122 or “Theory of Photographic Process” co-authored by Mies and James, 3rd edition, published by Macmillan (1966), Chapter 2.

This particle size can be measured using the projected area of the particle or a direct approximation.

If the particles are of substantially uniform shape, the particle distribution can be fairly accurately represented as a diameter or projected area.

The grain size distribution of the silver halide grains according to the present invention may be polydisperse or monodisperse, but a monodisperse emulsion is preferred. More preferred are monodispersed silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, in the particle size distribution of the silver halide grains.

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 grain size of each grain, ni represents the number thereof, and the grain size referred to here is the diameter in the case of spherical silver halide grains, and in the case of cubic or non-spherical grains,
It represents the diameter when the projected image is converted into a circular image of the same area.

The silver halide grains used in the emulsion of the present invention may be those obtained by an acidic method, a neutral method or an ammonia method. The particles may be grown temporarily, or may be grown after seed particles have been made.

The method for producing the seed particles and the method for growing the seed particles may be the same or different.

The form in which the soluble silver salt and the soluble halogen salt are reacted may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like, but those obtained by the simultaneous mixing method are preferable. As one form of the simultaneous mixing method,
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.

Further, a compound such as a mercapto group-containing compound, a nitrogen-containing heterocyclic compound or a sensitizing dye may be added during the formation of silver halide grains or after the completion of grain formation. The silver halide grains according to the present invention may have any shape. Can be used.

One preferable example is a cube having a {100} plane as a crystal surface. Also, U.S. Pat.
4,225,666, Japanese Patent Publication No. 55-26589, Japanese Patent Publication No. 55-42737, etc. and references such as The Journal of Photographic Science (J.photogr.Sci), 21, 39 (1973) By the method described, grains 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 may be cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or a complex salt thereof, rhodium salt or a complex salt thereof, The metal ions can be added to the inside of the particles and / or on the surface of the particles by using a salt or a complex salt thereof, and can be reduced inside the particles and / or on the surface of the particles by placing in an appropriate reducing atmosphere. Nucleus can be imparted.

The emulsion of the present invention may have unnecessary soluble salts removed after the completion of silver halide grain growth, or may remain incorporated.

The removal of the salts can be carried out according to Research Disclosure 17643.

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

In the present invention, a chemical sensitizer such as a chalcogen sensitizer can be used. The chalcogen sensitizer is a general term for sulfur sensitizers, selenium sensitizers, and tellurium sensitizers.
For photographic use, sulfur sensitizers and selenium sensitizers are preferable. Known sulfur sensitizers can be used. Examples thereof include thiosulfate, allylthiocarbazide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, and rhodanine. Others, U.S. Pat.Nos. 1,574,944, 2,410,689, 2,
No. 278,947, No. 2,728,688, No. 3,501,313, No.
The sulfur sensitizers described in, for example, 3,656,955, West German Application Publication (OLS) 1,422,869, JP-A-56-24937 and JP-A-55-45016 can also be used. The amount of sulfur sensitizer added is
Although it varies depending on various conditions such as pH, temperature, and size of silver halide grains, it is preferably about 10 ^-7 to 10 ^-1 mol per mol of silver halide.

A selenium sensitizer can be used instead of the sulfur sensitization. As the selenium sensitizer, aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenamides, selenocarboxylic acid can be used. Selenides such as salts and esters, selenophosphates, diethyl selenide, diethyl diselenide and the like can be used, and specific examples thereof are described in US Pat.
No. 1,574,944, No. 1,602,592, No. 1,623,499 and the like. Further, reduction sensitization can be used together. The reducing agent is not particularly limited, and examples thereof include known stannous chloride, thiourea dioxide, hydrazine, polyamine and the like. Also noble metal compounds such as platinum compounds,
A palladium compound or the like can be used.

As the gold sensitizer, the oxidation number of gold may be +1 or +3, and other kinds of gold compounds may be used. Representative examples are chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric azide, ammonium aurothiocyanate, pyridyl trichlorogold, gold sulfide, gold selenide, etc. Can be mentioned.

The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is 10 ^-8 mol to 10 ^-1 mol, and preferably 10 ^-7 to 10 ^-2 mol, per mol of silver halide. Further, these compounds may be added at any time during grain formation of silver halide, during physical ripening, during chemical ripening, and after completion of chemical ripening. When a gold compound is used in the present invention, a light-sensitive material having more excellent raw sample storability can be obtained.

The emulsion of the present invention is chemically sensitized and / or chemically sensitized for the purpose of preventing fogging and / or keeping photographic performance stable during the manufacturing process of a light-sensitive material, during storage, or during photographic processing. At the end and / or after the end of the chemical sensitization and before coating the silver halide emulsion, compounds known as antifoggants or stabilizers in the photographic art can be added.

Examples of stabilizers that can be used in the present invention include tetrazaindene compounds such as 7-hydroxy-5-methyl-1,3,4,7a-tetrazaindene.

In the present invention, the inhibitor used effectively has a solubility product (Ksp) with silver ion of 1 × 10 ⁻¹⁰ or less, preferably Ksp.
Is 1 × 10 ^-11 or less. A compound having a solubility product exceeding this value, that is, a compound having a smaller ability to form a salt with silver ions, cannot be expected to have the desired effect. For the measurement and calculation of the solubility product, "New Experimental Chemistry Course Vol. 1" (Maruzen), pages 233 to 250 can be referred to.

The inhibitor according to the present invention is, for example, a chemical and
Formal Viewlet (Chemical and P
harmaceutical Bulletin) (Tokyo) Volume 26, 314 (197
8), JP-A-55-79436, Berichte der Deutschen Chemischen Geesels Draft
Deutschen Chemischen Gesellsdraft) 82,121 (194
8), U.S. Pat.Nos. 2,843,491, 3,017,270, British Patent 940,169, JP-A-51-102639, Journal of American Chemical Society, 44, 1502-15
10 Beilsteins Handbuch der Organi
schen Chemie) 26 , 41, 43, 58, etc., and can be synthesized according to the methods described in these documents.

Furthermore, when a purine derivative compound or a mercapto group-containing compound represented by the following general formula [II] is used as the inhibitor, it is possible to increase the gradation by using it in combination with inorganic sulfur. Also, an excellent effect can be obtained.

In formula (II) Z ₀ -SM [wherein, Z ₀ is nitrogen-containing heterocyclic residue, M is a hydrogen atom, an alkali metal atom or ammonium. The inhibitor according to the present invention may be used alone or in combination of two or more, and may be used in combination with a stabilizer other than the inhibitor according to the present invention, or a fog inhibitor.

In the present invention, the time when the inhibitor is contained in the silver halide emulsion layer, 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 before the start of chemical sensitization, During chemical sensitization, any time selected from the end of chemical sensitization and from the end of chemical sensitization to the time of coating may be used. Preferably, it is added at the start of chemical sensitization or / and at the end of chemical sensitization. The addition may be carried out all at once or may be added in a plurality of times. In addition, it can be added to the coating solution for the adjacent non-photosensitive hydrophilic colloid layer. In this case, after the coating, the inhibitor migrates to the emulsion layer, and is contained in the silver halide emulsion layer. .

To contain the inhibitor according to the present invention in the silver halide emulsion layer or the non-photosensitive hydrophilic colloid layer, water or an organic solvent optionally miscible with water (for example, methanol, ethanol, etc.) is dissolved and then added. Good.

The amount of the inhibitor added to the silver halide emulsion layer is not particularly limited, but is usually 1 × 10 5 per mol of silver halide.
^-6 mol to 1 × 10 ^-1 mol, preferably 1 × 10 ^-5 mol to 1 × 10 ^-2 mol. When an inhibitor is added to the non-photosensitive hydrophilic colloid layer, the amount added is 1.5 to 3 times the coating amount as compared with the amount added when the inhibitor is added to the silver halide emulsion layer. It is preferable.

Typical examples of the inhibitor according to the present invention are shown below, but the present invention is not limited thereto.

Various dye-forming substances are used when the present invention is applied to a color light-sensitive material, and a typical example is a dye-forming coupler.

As the yellow dye-forming coupler, a known acylacetanilide type coupler can be preferably used. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous. Specific examples of yellow couplers that can be used include U.S. Pat.No. 1,077,874,
JP-B-45-40757, JP-A-47-1031, 47-26133, 4
8-94432, 50-87650, 51-3631, 52-115219
No. 54-99433, No. 54-133329, No. 56-30127, U.S. Patent Nos. 2,875,057, 3,253,924, 3,265,506.
Nos. 3,408,194, 3,551,155, 3,551,156,
3,64,841, 3,725,072, 3,730,722, 3,8
91,445, 3,900,483, 3,929,484, 3,933,50
No. 0, 3,973,968, 3,990,896, 4,012,259,
No. 4,022,620, No. 4,029,508, No. 4,057,432, No. 4,1
06,942, 4,133,958, 4,269,936, 4,286,05
No. 3, 4,304,845, 4,314,023, 4,336,327,
Nos. 4,356,258, 4,386,155, and 4,401,752.

The diffusion resistant yellow coupler used in the light-sensitive material of the present invention is preferably represented by the following general formula [Y].

In the formula, R ₁ represents a halogen atom or an alkoxyl group. R ₂ represents a hydrogen atom, a halogen atom or an alkoxy group which may have a substituent. R ₃ is an optionally substituted acylamino group, an alkoxycarbonyl group, an alkylsulfamoyl group, an arylsulfamoyl group,
It represents an aryl sulfonamide group, an alkylureido group, an arylureido group, a succinimide group, an alkoxy group, or an aryloxy group. Z ₁ represents a group capable of splitting off upon coupling with an oxidized product of a color developing agent.

In the present invention, as the magenta dye image forming coupler, couplers represented by the following general formulas [a] and [aI] can be preferably used.

[In the formula, Ar represents an aryl group, Ra ₁ represents a hydrogen atom or a substituent, and Ra ₂ represents a substituent. Y represents a hydrogen atom or a substituent capable of leaving by reaction with an oxidized form of a color developing agent, and W represents -NH-, -NHCO- (N atom is bonded to a carbon atom of a pyrazolone nucleus) or -NHCONH-. , M is an integer of 1 or 2. Preferred examples of the compound represented by the general formula [a] are as follows.

In the magenta coupler represented by, Za represents a nonmetal 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 substituent which can be eliminated by reaction with an oxidized form of a color developing agent. Ra represents a hydrogen atom or a substituent.

Examples of the substituent represented by Ra include a halogen atom,
Alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, Bridged 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,
Examples thereof include an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group and a heterocyclic thio group.

These are, for example, U.S. Pat.Nos. 2,600,788 and 3,062.
No. 1,432, No. 3,062,653, No. 3,127,269, No. 3,3
No. 11,476, No. 3,152,896, No. 3,419,391, No. 3,
No. 519,429, No. 3,555,318, No. 3,684,514, No.
No. 3,888,680, No. 3,907,571, No. 3,928,044, No. 3,930,861, No. 3,930,866, No. 3,933,500, etc., JP-A-49-29639, No. 49-111631, No. 49-12
No. 9538, No. 50-13041, No. 52-58922, No. 53-62454,
No. 55-118034, No. 56-38043, No. 57-35858, No. 60-23
Each publication of 855, British Patent No. 1,247,493, Belgian Patent No. 769,116, No. 792,525, West German Patent No. 2,156,111, Japanese Patent Publication No. 46-60479, JP 59-125,732,
59-228,252, 59-162,548, 59-171,956,
60-33,552, 60-43,659 publications, West German Patent No. 1,07
No. 0,030 and US Pat. No. 3,725,067.

Hereinafter, typical specific examples of the magenta coupler represented by the general formula (aI) used in the present invention will be given.
This is an example, and the present invention is not limited to this.

Typical cyan dye image-forming couplers are phenol-based and naphthol-based 4-equivalent or 2-equivalent cyan dye image-forming couplers. US Pat. No. 2,306,410
Issue 2, Issue 3,356,475, Issue 2,362,598, Issue 2,367,531,
2,369,929, 2,423,730, 2,474,293, 2,4
76,008, 2,498,466, 2,545,687, 2,728,66
0, 2,772,162, 2,895,826, 2,976,146,
3,002,836, 3,419,390, 3,446,622, 3,4
76,563, 3,737,316, 3,758,308, 3,839,04
4, British Patent Nos. 478,991, 945,542 and 1,084,480
Nos. 1,377,233, 1,388,024 and 1,543,040, and Japanese Patent Laid-Open Nos. 47-37425 and 50-10135,
50-25228, 50-112038, 50-117422, 50-1
No. 30441, No. 51-6551, No. 51-37647, No. 51-52828,
51-108841, 53-109630, 54-48237, 54-6
6129, 54-131931, 55-32071, 59-146050
No. 59-31953 and No. 60-117249.

As the cyan image forming coupler, couplers represented by the following general formulas [E] and [F] can be preferably used.

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

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

Gelatin is advantageously used as the hydrophilic colloid for dispersing the silver halide of the present invention, but other hydrophilic colloids can also be used.

As a preferred example of the hydrophilic colloid, gelatin such as alkali-treated gelatin or acid-treated gelatin is most common, and a part of this gelatin is phthalated gelatin,
Derivative gelatin such as phenylcarbamoyl gelatin,
It can be replaced by albumin, agar, gum arabic, alginic acid, partially hydrolyzed cellulose derivative, partially hydrolyzed polyvinyl acetate, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone and copolymers of these vinyl compounds.

The silver halide photographic light-sensitive material of the present invention can contain various known photographic additives. As such examples, for example, ultraviolet absorbers (for example, benzophenone compounds and benzotriazole compounds), dye image stabilizers (for example, phenol compounds, bisphenol compounds, hydroxychroman compounds, bisspirochroman compounds, hydantoin compounds). Compounds, dialkoxybenzene compounds, etc.), stain inhibitors (eg hydroquinone derivatives etc.), surfactants (eg sodium alkylnaphthalene sulfonate, sodium alkylbenzene sulfonate, sodium alkylsuccinate sulfonate, polyalkylene glycol etc.) , Water-soluble anti-irradiation dyes (for example, azo compounds, styryl compounds, styryl compounds, triphenylmethane compounds, oxonol compounds and anthraquinone compounds) Etc.), a film hardener (for example, a halogen s-triazine compound, a vinyl sulfone compound, an acryloyl compound, an ethyleneimino compound, an N-methylol compound epoxy compound and a water-soluble aluminum salt), a film physical property improving agent ( For example, glycerin, aliphatic polyhydric alcohols, polymer dispersions (latex), solid / or liquid paraffin, colloidal silica, etc.), optical brighteners (eg diaminostilbene compounds) and various oil-soluble paints, etc. Can be mentioned.

As a photographic layer constituting the silver halide photographic light-sensitive material of the present invention, in addition to each emulsion layer, each layer such as an undercoat layer, an intermediate layer, a yellow filter layer, an ultraviolet absorbing layer, a protective layer and an antihalation layer is required. It can be provided as appropriate.

Examples of the support of the silver halide photographic light-sensitive material of the present invention include supports such as paper, glass, cellulose acetate, cellulose nitrate, polyester, polyamide, and polystyrene, or, for example, paper and polyolefin (such as polyethylene and polypropylene). A laminate of two or more substrates, such as a laminate of the above, can be used as appropriate according to the purpose.

The support is generally subjected to various surface treatments to improve the adhesion to the silver halide emulsion layer,
For example, it is also possible to use those which have been roughened with a mechanical or suitable organic solvent, subjected to surface treatment such as electron impact treatment or flame treatment, or subjected to undercoating treatment for providing an undercoat layer.

The silver halide photographic light-sensitive material of the present invention can form an image by being subjected to development processing known in the art.

Examples of the black and white developing agent used in the present invention include T.
The Theory of photographic Process, 4th Edition by H. James
Those described on pages 291 to 326 can be used.

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. These compounds are generally used in the form of a salt, for example, the hydrochloride or sulfate, for stability in the free state. Further, these compounds are generally used in the color developing solution 1
Is used in a concentration of about 0.1 g to about 30 g, preferably about 1 g to about 15 g for color developer 1.

Examples of aminophenol developers include o-aminophenol, p-aminophenol, and 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-based color developing agents are N, N '
-Dialkyl-p-phenylenediamine compound, wherein the alkyl group and the 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'-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-hydroxy Ethylaminoaniline, 4-
Amino-3-methyl-NN'-diethylaniline, 4
-Amino-N- (2-methoxyethyl) -N-ethyl-
Examples thereof include 3-methylaniline-p-toluenesulfonate.

A known developer component compound can be added to the developer used in the processing of the silver halide photographic light-sensitive material of the present invention, in addition to the above-mentioned developer. For example, an alkali agent such as sodium hydroxide and 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 are optionally contained. You can also.

The temperature of the developing solution is preferably 15 ° C. or higher, and generally 30 ° C. for rapid processing at 20 ° C. to 50 ° C. Of developer
The pH value is usually 7 or higher, most usually from about 10 to about 13.

In the practice of the present invention, when a silver halide photographic material containing a high silver chloride emulsion is used as the silver halide emulsion, it is preferable to use a developer containing substantially no bromine ions.

That is, the presence of bromine ions significantly impairs rapid developability. The developing solution containing substantially no bromine ions means a processing solution containing bromine ions in an amount of 1 × 10 ⁻³ M or less.

High chloride silver halide is partially silver bromide,
It may contain silver iodide. For this reason, when silver bromide is contained, a small amount of bromide ions are eluted into the developing solution during development. This eluted bromine ion is partially replaced by the halogen ion in the part other than the image area, that is, the chloride ion in the high chloride silver halide that is not developed even in the developing solution, and the halogen ion is partially replaced by the difference in solubility to silver. It is considered that the silver color photographic light-sensitive material is held in the silver color photographic light-sensitive material and taken out to the next step. However, as described above, it is not possible to keep the bromine ion concentration in the developer completely zero as long as the bromine 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 bromine ions" as used in the present invention means that only bromine ions unavoidably mixed in, such as bromine ions eluted in a trace amount by development, are not contained.
^-3 M indicates the maximum upper limit of the concentration of bromine ions inevitably mixed.

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 forming a color developing agent under alkaline conditions, a Schiff base type precursor with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a phthalic acid imide derivative precursor,
Examples thereof include phosphoric acid amide derivative precursors, 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. 4, each specification, JP-A Nos. 53-185628 and 54-79035, Research Disclosure 15159, 121
46 and 13924.

It is necessary to add these aromatic primary amine color developing agents or their precursors so that sufficient amount of color can be obtained only by the amount when activated. This amount is largely different depending on the kind of the light-sensitive material, but is generally in the range of 0.1 to 5 mol, preferably 0.5 to 3 mol per mol of silver halide. These color developing agents or their precursors can be used alone or in combination. To be incorporated in the light-sensitive material, it can be dissolved in an appropriate solvent such as water, methanol, ethanol, or acetone and added, or dibutyl phthalate,
A high boiling point organic solvent such as dioctyl phthalate or tricresyl phosphate can be added as an emulsified dispersion, or can be added after impregnating a latex polymer as described in Research Disclosure No. 14850.

The silver halide photographic light-sensitive material of the present invention, after color development,
Bleached and fixed. The bleaching process may be performed simultaneously with the fixing process. As the bleaching agent, many compounds are used, but among them, polyvalent metal compounds such as iron (III), cobalt (III), and copper (II), especially complex salts of these polyvalent metal cations and organic acids, such as ethylenediamine tetra Aminopolycarboxylic acids such as acetic acid, nitrilotritriacetic acid, N-hydroxyethylethylenediaminediacetic acid, metal complex salts such as malonic acid, tartaric acid, malic acid, diglycolic acid, dithioglycolic acid or ferricyanate, dichromic acid, etc. Or a suitable combination thereof is used.

As the fixing agent, a soluble complexing agent that dissolves 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. These specific conditions are described in JP-A-58-134,6.
Reference can be made to Publication No. 36, etc.

The silver halide photographic light-sensitive material to which the present invention is applied includes black-and-white or color photographic light-sensitive materials, but is preferably a direct-view photographic light-sensitive material to be viewed as a final image, such as black-and-white printing paper and color printing. Examples include paper, color reversal film, and color reversal paper.
Of these, high silver chloride color photographic light-sensitive materials using a high silver chloride emulsion having a silver chloride content of 80 mol% or more, especially color papers, can obtain high sensitivity without sacrificing rapid processing properties, and can preserve raw samples. It is preferable because it is excellent in image quality and therefore a good image can be obtained.

〔Example〕

The present invention will be described more specifically by way of examples, but this is one embodiment of the present invention, and the present invention is not limited thereto.

Example 1 [Preparation of Silver Halide Emulsion (Em-A)] The amounts of additives used in the preparation of emulsions below are per mol of silver halide unless otherwise specified.

A silver nitrate solution and a solution containing potassium bromide and potassium iodide were added to an aqueous solution of inert gelatin by the double jet method at 150
Minutes. The temperature at this time was kept at 50 ° C. and pAg = 8.0.

Then, it was desalted and washed with water by a conventional method to obtain Em-A. Em-A consists of tetradecahedral silver iodobromide grains having an average grain size of 0.6 μm and a coefficient of variation of 11.0% (silver iodide content 4 mol%). 4.5 mg for Em-A
Chemical sensitization was performed by adding sodium thiosulfate. Chemical sensitization is carried out at 57 ° C., and 2 g of 4-hydroxy-6-methyl-1,3,3a-7-tetrazaindene is used as a stabilizer for a time period in which optimum sensitometric performance (sensitivity, gradation) is obtained. (S-16) was added and the temperature was lowered to complete the chemical sensitization. At this time, 10 minutes before the completion of the chemical sensitization, a sensitizing dye was added as shown in Table-1, and further 5 minutes before the completion of the chemical sensitization, the inorganic sulfur (Wako Pure Chemical Industries, Ltd.) was added as shown in Table-1. Manufactured) was added to obtain Em-1 to Em-21.

[Preparation of coating sample] Sodium dodecylbenzenesulfonate and gelatin and a hardening agent [H-1] were added to each emulsion as a coating aid.
10 mg per 1 g was added, and the obtained emulsion was coated on a polyethylene terephthalate support at a silver amount of 4.0 g / m ² and gelatin of 5.0 g.
It was applied so as to be g / m ² . Further, 2.0 g / m ² of gelatin was applied as a protective layer thereon to prepare Sample Nos. 1 to 21.
Each sample was exposed to green light with a three primary color separation filter using a sensitometer KS-7 type (manufactured by Konica Corporation), and then processed according to the development processing step-A shown below. After the treatment was completed, sensitometric measurement was performed with a PDA-65 type densitometer (manufactured by Konica Corporation).

[Raw sample storability]

Each sample was stored under conditions of 40 ° C. and 80% RH for 1 week, and then sensitometric measurement was performed to measure gradation change.
Here, γa is a value indicating the gradation represented by the reciprocal of the logarithmic difference of the respective exposure amounts for obtaining the densities of 0.3 and 0.8, and the larger the value, the harder the gradation. Δγa is the difference between γa when the emulsion after storage is used and when it is used on the same day. The results are shown in Table 1.

[Processing step-A] Development 20 ° C 12 minutes Stop 20 ° C 30 seconds Fixing 20 ° C 10 minutes Water wash 5 minutes [Developer composition] Metol 2.5g l-Ascorbic acid 10.0g Potassium bromide 1.0g Sodium metaborate 35g Water In addition 1 [Stop solution] Acetic acid (28%) 48cc Water 1000cc [Fixer] Water 500cc Sodium thiosulfate 240g Anhydrous sodium sulfite 10g Sodium acid sulfite 25g Water 1000cc As is clear from Table 1, the sensitizing dye used in the present invention can achieve higher sensitivity than the comparative dye, but fog is likely to occur, and the raw sample storability is poor.
The addition of inorganic sulfur to these dyes reduces fog and improves raw sample keeping, with little sacrifice in sensitivity. Also, when inorganic sulfur is added to the comparative dye, the desensitization is large. In the present invention, the addition amount of inorganic sulfur is used in a wide range, but if it is too small, the effect of the present invention is reduced, and if it is added excessively, desensitization occurs and fog tends to increase.

Example 2 [Preparation of EM-B to F] A silver nitrate solution and a solution containing potassium bromide and sodium chloride were placed in an inert gelatin by a double jet method to give a table-2.
Was added so as to maintain the conditions described in (1). Then, desalting and washing with water were carried out by a conventional method to prepare silver chlorobromide emulsions EM-B to F.

Next, 3 mg of sodium thiosulfate was added to the above primitive emulsion, and 5 minutes after that, the sensitizing dye [D-16] was added at 4 × 10 ^-4 mol /
Chemical sensitization was performed by adding AgX mol. Chemical sensitization is 55 ℃
The compound shown in Table 3 was added at the time at which the optimum sensitometric performance was obtained, and then the temperature was lowered to terminate the chemical sensitization. In addition, 1 minute after the addition of sodium thiosulfate, inorganic sulfur was added as shown in Table 3 to obtain Em-22 to 37.

(Preparation of coating sample)

Each emulsion was dissolved in dibutyl phthalate to prepare 0.25 mol of magenta coupler M-4, sodium dodecylbenzenesulfonate, gelatin, and [H-1] per 1 g of gelatin.
Add 10mg, 0.4g silver coating on polyethylene coated paper
/ m ² and gelatin were applied so as to be 4.0 g / m ² . Further, 3.0 g / m ² of gelatin was applied as a protective layer on top of it to prepare Sample No. 22.
~ 37 were made.

The obtained sample was exposed with a sensitometer KS-7 and then processed according to the following development processing step-B. After the treatment, sensitometric measurement was performed with a PDA-65 type densitometer. The raw sample storability test was carried out in the same manner as in Example 1. Here, γB is represented by the reciprocal of the logarithmic difference of the respective exposure doses for obtaining the densities of 0.5 and 1.5. Further, a rapid processability test was conducted by the following method.

[Quick processing test]

The exposed sample was processed according to the following color development step-C, and the maximum density (Dmax) was measured. The results are shown in Table-3.

[Color development processing step-B]

(1) Color development 38 ° C 3 minutes 30 seconds (2) Bleach fixing 33 ° C 1 minute 30 seconds (3) Washing treatment 25 ° C to 30 ° C 3 minutes (4) Drying 75 ° C to 80 ° C 2 minutes [Treatment liquid] Composition] (Color developer) Benzyl alcohol 15ml Ethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide 1.3g Sodium chloride 0.2g Potassium carbonate 30.0g Hydroxylamine sulfate 3.0g Polyphosphoric acid (TPPS) 2.5g 3-Methyl-4-amino -N-Ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate 5.5g Fluorescent bleach (4,4'-diaminostilbenedisulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Add water to bring the total amount to 1 And adjust the pH to 10.20.

(Bleach-fixing solution) ethylenediaminetetraacetic acid ferric ammonium dihydrate
60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid and add water to bring the total volume to 1.

[Treatment Step-C]

Temperature Time Color development 30 ± 0.3 ℃ 15 seconds or 30 seconds Bleach fixing 30 ± 0.5 ℃ 45 seconds Stabilization 30-34 ℃ 90 seconds Dry 60-80 ℃ 60 seconds [Color developer] Pure water 800ml Triethanolamine 10g N , N-Diethylhydroxylamine 10g Potassium chloride 2g Potassium sulfite 0.3g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0g Ethylenediaminetetraacetic acid 1.0g Catechol-3,5-disulfonic acid disodium salt 1.0g N-ethyl-N -Β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline sulfate 4.5 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.0 g Water is added to adjust the total amount to 1 and pH is adjusted to 10.10.

[Bleaching fixer]

Ethylenediaminetetraacetic acid ferric ammonium dihydrate
60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% aqueous solution) 100ml Ammonium sulfite (40% aqueous solution) 27.5ml Adjust the pH to 6.2 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 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g ethylenediaminetetraacetic acid 1.0 g ammonium hydroxide (20% solution) 3.0 g Ammonium sulphate 3.0g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1.5g Add water to make 1 and add sulfuric acid or potassium hydroxide.
Adjust the pH to 7.0.

As is clear from Table 3, when a high silver chloride emulsion is used, a reduction in fog and rapid processing are achieved, and further, the use of inorganic sulfur in the emulsion improves fog reduction and emulsion storability. At the same time, the sensitivity / fog in chemical sensitization and the optimum point of gradation can be made coincident with each other, so that it can be practically used as a silver halide emulsion for rapid processing having an appropriate gradation. Further, when a compound having a purine ring or a mercapto compound is used as an inhibitor, the effect of the present invention can be made more remarkable.

Example 3 [Preparation of EM-G to J] A silver nitrate solution and a solution containing potassium bromide and sodium chloride were added to an inert gelatin by a double jet method. At this time, the temperature was kept at 50 ° C., pH = 6.0 and pAg = 7.5, and the compounds shown in Table 4 were added. Then, desalting and water washing were performed to produce EM-G to J.

All of EM-G to J were emulsions composed of cubic silver chlorobromide grains having an average grain size of 0.45 μm (silver chloride content 99.9%).

Next, it was chemically sensitized under the following conditions.

At 55 ° C., 1 × 10 ^-4 mol of [S-42] was added to the primitive emulsion, the chemical sensitizers shown in Table 5 were added, and after 5 minutes, [D-9].
5 × 10 ^-4 mol or [D-9] and [D-3] are added for chemical sensitization, and 40 mg of [S-36] is added at the time when optimum sensitometric performance is obtained. The temperature was lowered and the chemical sensitization was completed.

At this time, the inorganic sulfur was added at the addition time shown in Table-5.

(Preparation of coating sample)

It was produced in the same manner as in Example 2. However, the compounds shown in Table 5 were added as needed when preparing the coating solution.

Then, in the same manner as in Example 2, sensitometric evaluation and raw sample storability were evaluated. However, the development process is
The development time was 45 seconds.

 The results are shown in Table-5.

As is clear from Table 5, the timing of adding inorganic sulfur is effective in any case, but it is more preferable to add it before the end of chemical sensitization. Further, the gold sensitizer, when used alone or in combination with sodium thiosulfate, has a higher sensitivity and improves the fog increase in the preservation of raw samples. Further, by adding a mercapto compound, the effect can be further promoted and an excellent light-sensitive material can be obtained.

Example 4 A multilayer silver halide photographic light-sensitive material was prepared by sequentially coating the following seven layers on a polyethylene resin-coated paper. In addition, the addition amount shown below is the amount per 1 m ² unless otherwise specified.

First layer: 1.2 g gelatin, 0.35 g (metal silver equivalent,
The same applies hereinafter) of blue-sensitive silver chlorobromide emulsion (average grain size 0.8 μm,
Silver bromide content 0.3 mol%), 0.9 g of yellow coupler YC-
Dioctyl phthalate (hereinafter referred to as HQ-1) in which 1 and 0.015 g of 2,5-di-t-octylhydroquinone (hereinafter referred to as HQ-1) are dissolved
(Referred to as DOP).

Second layer: a layer containing 0.7 g of gelatin and 0.06 g of HQ-1 dissolved in DOP.

Third layer: 1.25 g of gelatin, 0.35 g of green-sensitive silver chlorobromide emulsion Em-38, 0.53 g of Magellata captor M-3 and 0.12 g
[A-1] and 0.2 g of [A-2] 0.015 g of HQ-1 dissolved in a layer containing DOP.

Fourth layer: a layer containing 1.3 g of gelatin, 0.08 g of HQ-1 and 0.5 g of a UV absorber (UV-1) dissolved in DOP.

Fifth layer: 1.4 g of gelatin, 0.3 g of red-sensitive silver chlorobromide emulsion (average grain size 0.5 μm, silver bromide content 0.1 mol%) and
Layer containing DOP with 3 g of cyan coupler CC-1, 0.2 g of CC-2 and 0.02 g of HQ-1 dissolved.

6th layer: 1.0 g gelatin, 0.032 g HQ-1 and 0.2 g
Layer containing 0.14 g DOP with UV-1 dissolved.

Seventh layer: a layer containing 0.003 g of silicon dioxide and 0.5 g of gelatin.

As a hardener, [H-1] is 5 mg per 1 g of gelatin, [H-1]
2] was added at 10 mg per 1 g of gelatin.

Em-50: except that Comparative Dye-1 was used as the sensitizing dye
An emulsion prepared under the same conditions as Em-38.

Multilayer silver halide color light-sensitive material as described above
No. 50 was produced. Next, change the following points and No. 51-53
Was produced.

No.51 ... The green-sensitive emulsion Em-50 of the third layer of No. 50 is designated as Em-38.

No. 52 ... The green-sensitive emulsion Em-50 of the third layer of No. 51 is designated as Em-47.

No.53: 0.3 mg of [S-37] is added to the second layer of No. 52, and 0.2 mg of [S-37] is added to the fourth layer.

Sample Nos. 50 to 53 were evaluated by the method described in Example 3. The evaluation results of the third layer (green sensitive layer) are shown in Table-6.

As is apparent from Table-6, even when a sensitizing dye of the present invention and inorganic sulfur are used together to prepare a multilayer silver halide color light-sensitive material, the effects of the present invention are sensitometric performance and raw sample storage. You can get enough sex.

〔The invention's effect〕

In the present invention, by using the sensitizing dye represented by the general formula [I] and inorganic sulfur in combination, a light-sensitive material having high sensitivity and excellent raw sample storage stability can be obtained.

Front page continuation (72) Inventor Shigeo Tanaka 1 Sakura-cho, Hino-shi, Tokyo Inside Konishi Rokusha Shin Kogyo Co., Ltd. (56) Reference JP 59-185330 (JP, A) JP 61-80237 ( JP, A) JP 61-279849 (JP, A) JP 51-1116 (JP, A) JP 63-301039 (JP, A) JP 63-311245 (JP, A) JP Sho 63-301038 (JP, A) JP-A-53-20923 (JP, A)

Claims (1)

(57) [Claims] 1. A silver halide photographic light-sensitive material having at least one photographic constituent layer containing a silver halide emulsion layer on a support, wherein the silver halide emulsion layer has the general formula [I].
Manufactured by adding inorganic sulfur to at least one of the photographic constitutional layers on the side having the silver halide emulsion layer with respect to the support, which contains the sensitizing dye represented by
The silver halide photographic light-sensitive material is characterized in that the inorganic sulfur added to the photographic constituent layers other than the silver halide emulsion layer diffuses and substantially exists in the silver halide emulsion layer. [In the formula, Z ₁ and Z ₂ each represent an atomic group necessary for forming a benzene ring or a naphthalene ring. R ₁ and
R ₂ represents a substituted or unsubstituted alkyl group, alkenyl group or aryl group, respectively. R ₃ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. X ₁ ⁻ represents an anion, and n represents 0 or 1. Y ₁ and Y ₂ each represent an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, or N—R ₄ or N—R ₅ . R ₄
And R ₅ each represent H, a substituted or unsubstituted alkyl group, an alkenyl group or an aryl group. ]