JPH07128829A - Photographic image forming method - Google Patents

Abstract

PURPOSE:To provide such a photographic image forming method that rapid processing can be done and picture images of high picture quality having high contrast and high max. density can be stably obtd. even under such processing conditions for less environmental pollution with a low replenishing amt. of a developer. CONSTITUTION:A silver halide photographic material has at least one silver halide photographic emulsion layer containing >=95mol% silver chloride on a supporting body. This photosensitive material is exposed for imaging and developed. In this image forming method, the silver halide photographic emulsion layer contains silver halide particles containing such a complex near the surface of the particle that at least one element in groups 5 to 10 of the periodic, table is the center metal and at least one ligand on the 4-fold axis among of six unidentates is different from others. Further, the replenishing amt. of the developer is 20-60ml per one m<2> of the photosensitive material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is capable of rapid processing and stabilizes a high-quality image with high contrast and high density even under processing conditions of low pollution load in which the replenishment amount of the developing solution is reduced. The present invention relates to a photographic image forming method that can be obtained.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials, particularly silver halide color photographic light-sensitive materials, are widely used today because of their high sensitivity and excellent gradation. However, the development processing of a silver halide color photographic light-sensitive material is a so-called wet processing, and it takes time to prepare a processing solution, it becomes dirty, a waste solution containing various chemicals is discharged, a dark room is required, and after the operation is started. There were drawbacks such as the long time it took to obtain the first print. In order to make up for these drawbacks and make full use of the advantages of the silver halide color photographic light-sensitive material described above, a system in which a skilled engineer concentrates from the development of color negatives to the production of color prints in a few large development laboratories. Has been taken.

In the wet processing method, it is relatively easy to maintain a constant temperature or a uniform concentration of components in the processing liquid by performing appropriate agitation, so that images without unevenness can be continuously formed. It is an excellent method that can obtain a large amount. In this system, a replenisher is added according to the amount of the photosensitive material that has been developed, and the photosensitive material is continuously processed while keeping the concentration of components in the processing solution constant. I'm calling. Substances in the processing solution during running are eluted from the photosensitive material (for example, halide ions, organic inhibitors, etc.), and brought in from the replenishing solution (for example,
Constant by balancing the development agent, alkali, etc.), consumption due to development processing reaction (development agent, etc.), carry-out by moving photosensitive material to the next processing tank containing processing solution, and overflow due to addition of replenishing solution Kept in. However, the eluate from the light-sensitive material is not contained at the beginning of the processing and gradually accumulates as the running is continued, so that some degree of compositional change cannot be avoided. As a means to avoid this, before starting the process,
Means such as adding a small amount of a halide salt have been taken in advance, and measures have been taken to keep the photographic performance stable.

In recent years, there has been an increasing demand for shortening the time from photographing to producing a color print.
In consideration of the environment, a development processing system with less pollution load has been desired. Under these circumstances, a high chloride silver halide photographic emulsion consisting of a high concentration of silver chloride is used for color paper, and the replenishment amount of the developing solution is being reduced. Under a condition where the amount of replenisher is small, the amount taken out by overflow decreases, so that the concentration of the compound eluted from the light-sensitive material becomes high and the development tends to be inactive. In a light-sensitive material using a high chloride silver halide photographic emulsion, since the halide ion eluted from the light-sensitive material is a chloride ion, the ability to suppress development is weak and it is not so inactive even in the running state. It was thought that the softening of the shoulder of the characteristic curve and the decrease of the maximum density (Dmax) were unexpectedly large. Further, as a drawback of the light-sensitive material using the high chloride silver halide emulsion, the gradation near the minimum density was soft, but this was also emphasized.

JP-A-3-204636 discloses that adenine and guanine are contained in a silver halide emulsion containing a silver chloride content of 90 mol% or more and 10 ^-7 to 10 ^-3 mol of iron ion per mol of silver halide. 3ppm as the average content in gelatin
It is disclosed that by the following, rapid processing is possible and high sensitivity and high contrast characteristics are obtained. JP-A-4-335348 discloses a technique in which a silver chloride content of 90 mol% or more and a selenium-sensitized high chloride silver halide emulsion and a specific yellow coupler are used in combination. It is disclosed that the yellow dye produced from the coupler can realize the required high contrast property in connection with the poor match with the human visual property. Kohei
No. 5-204105 discloses that in a silver halide photographic light-sensitive material containing a specific phenolic cyan coupler, the content of iron in gelatin is 5 ppm or less so that the durability of the image is excellent and even under the condition of low replenishment. It is disclosed that variations in gradation are unlikely to occur. Japanese Unexamined Patent Publication (Kokai) No. 5-204111 discloses that in a silver halide photographic light-sensitive material containing a specific magenta coupler, the content of iron in gelatin is set to 5 ppm or less so that the replenishment amount of the color developer is Quantity 1
It is disclosed that variations in gradation due to running under the condition of 20 to 60 ml per m ² can be suppressed.

However, these techniques have not yet obtained sufficient characteristics, and gradation and maximum density are insufficient.

JP-A-51-139323 and JP-A-59-171947 disclose that inclusion of a Group VIII metal compound can improve reciprocity law failure and increase sensitivity. In addition, Japanese Patent Publication No. 49-33781, Japanese Patent Laid-Open No. 50-23618,
52-18310, 58-15952, 59-214028, 61-6784
No. 5 and the like disclose that inclusion of a rhodium compound or an iridium compound can improve reciprocity law failure and achieve a high contrast. However, although such a technique improves the reciprocity law failure of a silver halide emulsion containing a high concentration of silver chloride, D
It did not have a sufficient effect on problems such as a decrease in max and softening.

JP-A-2-124567 discloses that the silver chloride content is 95
Silver chlorobromide or silver chloride emulsion containing at least mol% and at least 10 ^-9 mol per mol of silver halide of Group VIII metal ion, Group II transition metal ion, lead ion or thallium ion of the periodic table After scanning exposure of a color photographic light-sensitive material having at least one silver halide emulsion layer containing grains, the replenishment amount is 200 ml or less per 1 m ^{2 of the} silver halide color photographic light-sensitive material, and benzyl alcohol is substantially contained. It is disclosed that a change in Dmax and gradation due to continuous processing can be reduced by a color image forming method characterized in that continuous processing is performed with a color developing solution that does not specifically contain it. The publication exemplifies potassium pentacyanoammine iron (II) ate and potassium pentacyanonitrosyl iron (III) ate as the compound containing the metal ion. It is only mentioned as an example of the compound to be contained, and the effect obtained by allowing these compounds to exist in the vicinity of the particle surface is not mentioned at all. When the amount of the replenisher is within a specific amount range, the silver halide photographic light-sensitive material used in the present invention has the effects of increasing Dmax and increasing the contrast by running. The technique disclosed in the publication is a completely different technique, in that the decrease in Dmax due to running and the softening of gradation that occur in relation to high-illuminance exposure are simply suppressed.

US Pat. No. 4,933,372 discloses a halogen having a face-centered cubic lattice containing a complex having a nitrosyl or thionitrosyl ligand as a central metal and having a metal element belonging to Groups 5 to 10 of the periodic table. It is disclosed that the silver halide photographic emulsion improves reciprocity law failure and obtains high contrast characteristics. Further, US Pat. No. 5,252,451 contains a complex having a Group 8 metal element as a central metal inside the particle, and a grain surface having a Group 5-10 metal element as a center metal on the particle surface. It is disclosed that a silver halide emulsion containing a complex having a nitrosyl or thionitrosyl ligand can provide high contrast characteristics. These specifications neither mention nor suggest any problems that may occur under low replenishment conditions.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to enable rapid processing and to obtain high image quality with high contrast and high maximum density even under processing conditions of low pollution load in which the replenishment amount of the developing solution is reduced. An object of the present invention is to provide a photographic image forming method capable of stably obtaining an image.

[0011]

While the inventors of the present invention diligently researched a photographic light-sensitive material using a silver halide photographic emulsion containing a high concentration of silver chloride, the object of the present invention was to find a support on a support. In a photographic image forming method, wherein at least one silver halide photographic light-sensitive material having a silver halide photographic emulsion layer having a silver chloride content of 95 mol% or more is subjected to development processing after image exposure, the silver halide photographic emulsion layer contains , At least one metal element of Groups 5 to 10 of the periodic table in the vicinity of the particle surface as a central metal, and at least one of the six monodentate ligands on the rotation axis of four is A photographic image forming method comprising silver halide grains containing a complex which is a different ligand, and a replenishing amount of a developing solution being 20 to 60 ml per 1 m ^{2 of a} light-sensitive material. Found out that the present invention was completed. It has come to be achieved.

The composition of the silver halide photographic emulsion used in the present invention is characterized in that it is a silver halide emulsion containing 95 mol% or more of silver chloride. , Silver chlorobromide, silver chloroiodobromide and the like may be used, but silver chlorobromide containing substantially no silver iodide is preferable. Silver chlorobromide containing silver chloride of preferably 97 mol% or more, and more preferably 98 to 99.9 mol% is preferable.

The complex to be contained in the vicinity of the grain surface of the silver halide photographic emulsion used in the present invention has a z-axis as a rotation axis of 4 times in the O-xyz coordinate space where the central metal atom is the origin O. There are two ligands on this axis, x, y
It is characterized in that four kinds of the same kind of ligand are present on the axis, and at least one of the ligands on the z axis is different from the ligands on the x and y axes.

The central metal of the complex used in the present invention is a group 5 to 10 of the periodic table (IUPAC inorganic compound nomenclature revised version (19
89)), and examples thereof include manganese, iron, cobalt, nickel, molybdenum, ruthenium, rhodium, palladium, tungsten, rhenium, osmium, and iridium. Among these, iron, osmium, and ruthenium can be mentioned as preferable metal elements.

In the ligand of the complex used in the present invention, at least one of the ligands present on the z axis is different from the ligands present on the x and y planes. Is characterized by. As the ligand existing on the x and y planes, chloride ion, bromide ion, iodide ion, cyanide ion and the like are preferable, and chloride ion, bromide ion and cyanide ion are particularly preferable. As the ligand existing on the z axis, chloride ion, bromide ion, nitrosyl, thionitrosyl, carbonyl, and water (aco) ligand are preferable. Of these, nitrosyl, thionitrosyl and carbonyl ligands are preferable.

The complex used in the present invention is characterized in that it is contained near the surface of silver halide grains. The term “particle surface” as used herein refers to an area from the particle surface to the inside by about 0.015 μm.

In order to contain the above-mentioned complex in the silver halide emulsion used in the present invention, the complex is incorporated into the silver halide emulsion during each step of the physical ripening during the formation of the silver halide grain and after the formation of the silver halide grain. It may be added at any place. To obtain a silver halide emulsion satisfying the above-mentioned conditions, the complex is dissolved together with a halide salt and continuously added during the whole or a part of the grain forming step, or a fine grain silver halide containing a complex in advance is added. Alternatively, after forming the host particles and forming the host particles, the host particles may be added and precipitated on the host particles. As the time for containing the complex,
It is preferably added at the stage where grain growth is occurring.

When the silver halide emulsion used in the present invention has a portion where silver bromide is localized at a high concentration,
It is advantageous to localize in the high concentration phase.

The above complex is 1 × 1 per mol of silver halide.
It is preferably contained in an amount of 0 ^-9 mol or more and 1 x 10 ^-2 mol or less, and particularly preferably 1 x 10 ^-8 mol or more and 5 x 10 ^-5 mol or less.

Examples of the complex used in the present invention include the followings, but the present invention is not limited thereto.

(I-1) Cs ₂ [Os (NO) Cl ₅ ] (I-2) K ₂ [Ru (NO) Cl ₅ ] (I-3) K ₂ [RuCl ₅ (H ₂ O)] ( I-4) K ₃ [Os (SnCl ₃ ) ₅ Cl] (I-5) K ₂ [IrBrCl ₅ ] (I-6) K ₂ [Ir (CN) ₅ Cl] (I-7) K ₂ [Ru (CO) Cl ₅ ] (I-8) Cs ₂ [Os (CO) Cl ₅ ] (I-9) K ₂ [Fe (NO) (CN) ₅ ] (I-10) K ₂ [Ru (NO) Br ₅ ] (I-11) K ₂ [Ru (NO) I ₅ ] (I-12) K ₂ [Re (NO) (CN) ₅ ] (I-13) K ₂ [Re (NO) Cl ₅ ] (I-14) K [Ir (NO) Cl ₅ ] (I-15) K ₂ [Ru (NS) Cl ₅ ] (I-16) K ₂ [Os (NS) Br ₅ ] (I-17) K ₂ [Ru (NS) (CN) ₅ ] (I-18) K ₂ [Ru (NS) (SCN) ₅ ] Further, it is possible to use a heavy metal compound other than the above complex within a range that does not impair the effects of the present invention. it can. Examples of heavy metal compounds that can be preferably used include the following compounds.

(II-1) FeCl ₂ (II-2) FeCl ₃ (II-3) (NH ₄ ) Fe (SO ₄ ) ₂ (II-4) K ₃ [Fe (CN) ₆ ] (II-5 ) K ₄ [Fe (CN) ₆ ] (II-6) K ₂ [IrCl ₆ ] (II-7) K ₃ [IrCl ₆ ] (II-8) K ₂ [PtCl ₆ ] (II-9) K ₂ [Pt (SCN) ₄ ] (II-10) K ₂ [NiCl ₄ ] (II-11) K ₂ [PdCl ₆ ] (II-12) K ₃ [RdCl ₆ ] (II-13) CdCl ₂ (II- 14) ZnCl ₂ (II-15) K ₃ [Re (CNO) ₆ ] (II-16) K ₃ [Mo (OCN) ₆ ] (II-17) K ₄ [Fe (CNO) ₆ ] (II-18 ) K ₄ [Ru (CNO) ₆ ] (II-19) K ₂ [Ni (CN) ₄ ] (II-20) PbCl ₂ (II-21) K ₃ [Co (NH ₃ ) ₆ ] (II-22 ) K ₅ [Co ₂ (CNO) ₁₁ ] (II-23) K ₃ [Re (CNO) ₆ ] (II-24) K ₄ [Os (CNO) ₆ ] (II-25) K ₂ [Cd (CNO ) ₄ ] (II-26) K ₂ [Pt (CNO) ₄ ] (II-27) K ₃ [IrBr ₆ ] (II-28) K ₂ [IrBr ₆ ] (II-29) Ga (NO ₃ ) ₃ In order to contain these heavy metal compounds in the silver halide grains, the heavy metal compounds are added before the formation of silver halide grains, during the formation of silver halide grains, and during the physical ripening after the formation of silver halide grains. It may be added at any place in the process. Among them, hexachloroiridium (III), (IV)
When the acid compound, hexabromoiridium (III), and (IV) acid compound are added to the inside of the particles, the effect of the present invention is great, which is preferable. The addition amount of these compounds is more preferably 1 × 10 ⁻⁹ mol or more and 1 × 10 ⁻² mol or less, and particularly preferably 1 × 10 ⁻⁸ mol or more and 5 × 10 ⁻⁵ mol or less per mol of silver halide. preferable.

The silver halide grains used in the present invention may have any shape. One preferable example is a cube having a (100) plane as a crystal surface.
Also, U.S. Pat.Nos. 4,183,756 and 4,225,666, JP-A-55
-26589, Japanese Patent Publication No. 55-42737, and The Journal of Photographic Science (J.Photogr.Sci.)
Particles having a shape such as an octahedron, a tetradecahedron, and a dodecahedron can be prepared by the method described in the literature such as 21, 39 (1973) and the like, and used. Further, grains having twin planes may be used.

The silver halide grains used in the present invention are
The grains having a single shape may be used, and the grain size of the silver halide grains used in the present invention is not particularly limited,
Considering other photographic properties such as rapid processing property and sensitivity, preferably 0.1 to 1.2 μm, more preferably 0.2 to 1.2 μm.
It is in the range of 1.0 μm. The particle diameter can be measured by various methods generally used in the technical field. A typical method is Loveland's "Particle Size Analysis Method" (ASTM Symposium on Light.
Microscopy, pp. 94-122, 1955) or "Theory of Photographic Processes 3rd Edition" (co-authored by Mies and James,
The method described in Chapter 2, Macmillan, 1966) can be mentioned.

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

The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse.
The monodisperse silver halide grains preferably have a coefficient of variation of 0.22 or less, more preferably 0.15 or less. Here, the coefficient of variation is a coefficient representing the breadth of the particle size distribution and is defined by the following equation.

Coefficient of variation = S / R (where S is the standard deviation of the grain size distribution, and R is the average grain size.) The grain size referred to here is the diameter of spherical silver halide grains. Further, in the case of a particle having a shape other than a cube or a sphere, it represents the diameter when the projected image is converted into a circular image having the same area.

As the apparatus and method for preparing the silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion used in the present invention is
It may be obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after the seed grains are formed. The method for making seed particles and the method for growing seed particles may be the same or different.

The method of reacting the soluble silver salt and the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc., but the one obtained by the simultaneous mixing method. Is preferred. Further, the pAg controlled double jet method described in JP-A-54-48521 can be used as one type of the simultaneous mixing method.

Further, a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device arranged in a reaction mother liquor described in JP-A-57-92523, 57-92524, etc., published in Germany An apparatus for continuously adding and changing the concentration of a water-soluble silver salt and a water-soluble halide salt aqueous solution described in Japanese Patent No. 2921164, and the reaction mother liquor is taken out of the reactor described in Japanese Patent Publication No. 56-501776. You may use the apparatus etc. which perform grain formation, keeping the distance between silver halide grains constant by concentrating by an ultrafiltration method.

Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added and used during the formation of silver halide grains or after the completion of grain formation.

The silver halide emulsion used in the present invention is
A sensitizing method using a gold compound, a sensitizing method using a chalcogen sensitizer, and a sensitizing method such as a reduction sensitizing method can be used alone or in combination. The silver halide emulsion subjected to gold sensitization is preferable because the effect of the present invention is large.

The sulfur sensitizer applied to the silver halide emulsion used in the present invention includes thiosulfate, allylthiocarbamidothiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, triethylthiourea. , Inorganic sulfur and the like. The addition amount of the sulfur sensitizer used in the chemical ripening of the silver halide emulsion used in the present invention is preferably changed depending on the silver halide emulsion to be applied, but it is 5 × 10 ⁻ per mol of silver halide. The range is ^{10 to} 5 × 10 ^-5 mol, preferably 5
The range of × 10 ^{-8 to} 3 × 10 ^-5 mol is preferable.

As the gold sensitizer used when chemically sensitizing the silver halide emulsion used in the present invention, various gold complexes such as chloroauric acid and gold sulfide can be added.
Examples of the ligand of the gold complex used include dimethyl rhodanine, thiocyanate, mercaptotetrazole, and mercaptotriazole. Specific compounds of the gold complex, exemplified compounds (I-6), (I-18), (I-19), (I-21), described in JP-A-5-113617, pages 118-123,
(IV-1) and (V-1) can be mentioned. The amount of gold compound used varies depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., but is usually from 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ mol per mol of silver halide. It is preferably molar. More preferably 1 × 10 ⁻⁵ mol to 1 ×
It is 10 ^-8 mol.

The sensitizer used for selenium sensitization of the silver halide photographic emulsion used in the present invention can include a wide variety of selenium compounds. For example, US Patent 1,57
4,944, 1,602,592, 1,623,499, JP-A-60-15
0046, JP-A-4-25832, 4-109240, 4-147250
The compounds described in the publications can be mentioned.

Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate), selenoureas (eg, N, N-).
Dimethylselenourea, N, N, N'-triethylselenourea,
N, N, N'-trimethyl-N'-heptafluoroselenourea, N,
N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N '-(4-nitrophenyl) carbonylselenourea, etc., selenoketones (eg, selenoacetone, selenoacetophenone, etc.) ), Selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutylate, etc.), selenophosphates ( For example, Tory p-Triselenophosphate, etc.),
Examples thereof include selenides (diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenoamides, and selenoketones.

Specific examples of techniques for using these selenium sensitizers are disclosed in the following patent specifications. U.S. Patent No. 1,57
4,944, 1,602,592, 1,623,499, 3,2
No. 97,446, No. 3,297,447, No. 3,320,069, No. 3,
408,196, 3,408,197, 3,442,653, and
3,420,670, 3,591,385, French Patent 2,693,
No. 038, No. 2,093,209, Japanese Patent Publication No. 52-34491, No. 52-344
No. 92, No. 53-295, No. 57-22090, JP-A-59-180536
No. 59-185330, 59-181337, 59-187338,
59-192241, 60-150046, 60-151637, 61-
246738, JP 3-4221 A, 3-24537 A, 3-111838 A
No. 3, No. 3-116132, No. 3-148648, No. 3-237450, No. 4-
No. 16838, No. 4-25832, No. 4-32831, No. 4-96059, No.
4-109240, 140738, 4-140739, 4-147250
No. 4, No. 4-149437, No. 4-184331, No. 4-190225, No. 4-
191729, 4-195035, British Patents 255,846, 861,9
Issue 84. In addition, HE Spencer et al., Journal of
It is also disclosed in the chemical literature such as Journal of Photographic Science, Vol. 31, pp. 158-169 (1983).

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but generally about 10 ^-8 to 10 ^-4 mol per mol of silver halide is used. Further, the addition method, depending on the properties of the selenium compound used, water or methanol, a method of adding by dissolving in an organic solvent such as ethanol alone or in a mixed solvent, is also disclosed in JP-A-4-140739. A method, that is, a method of adding in the form of an emulsion dispersion of a mixed solution with a polymer soluble in an organic solvent may be used.

The temperature of the chemical ripening using the selenium sensitizer in the present invention is preferably in the range of 40 to 90 ° C. More preferably, it is 45 ° C or higher and 80 ° C or lower. Also, the pH is 4-9, p
Ag is preferably in the range of 6 to 9.5.

Tellurium sensitizers and sensitizing methods used in the present invention are described in US Pat. Nos. 1,623,499 and 3,320,069.
Issue 3,772,031, Issue 3,531,289, Issue 3,655,394,
British Patent Nos. 235,211, 1,121,496, 1,295,462
No. 1,396,696, Canadian Patent No. 800,958, JP-A-4-
No. 204640 is disclosed. Examples of useful tellurium sensitizers include telluroureas, telluroamides, and the like. The technique for using the tellurium sensitizer may be the same as the technique for using the selenium sensitizer described above.

A known method can be used for reduction sensitizing the silver halide emulsion used in the present invention. For example, it is possible to use a method of adding various reducing agents, a method of aging under conditions where the silver ion concentration is high, or a method of high p
A method of aging under the condition of H can be used.

Examples of the reducing agent used for reduction sensitization of the silver halide emulsion used in the present invention include stannous salts such as stannous chloride, boranes such as tri-t-butylamine borane, sodium sulfite and potassium sulfite. And sulfites, ascorbic acid and other reductones, thiourea dioxide and the like. Among these, thiourea dioxide, ascorbic acid and its derivatives, and sulfite can be preferably used. Compared with the case where reduction sensitization is performed by controlling the silver ion concentration and pH during ripening, the method using a reducing agent as described above is excellent in reproducibility and is preferable.

These reducing agents are dissolved in a solvent such as water or alcohol and added to the silver halide emulsion for ripening, or they are added during the formation of silver halide grains to reduce and increase them simultaneously with grain formation. You may feel.

The amount of these reducing agents added needs to be adjusted according to the pH of the silver halide emulsion, the silver ion concentration, etc., but is generally 10 per mol of the silver halide emulsion.
^-7 to 10 ^-2 mol is preferred.

After the reduction sensitization, a small amount of an oxidizing agent may be used in order to modify the reduction sensitizing nucleus or deactivate the remaining reducing agent. Examples of the compound used for such purpose include
Examples thereof include potassium hexacyanoferrate (III), bromosuccinimide, p-quinone, potassium perchlorate, and hydrogen peroxide solution.

The silver halide emulsion according to the present invention is intended to prevent fog that occurs during the process of preparing a silver halide photographic light-sensitive material, reduce performance fluctuation during storage, and prevent fog that occurs during development. Antifoggant known in
Stabilizers can be used. Examples of compounds that can be used for such purpose include compounds represented by the general formula (II) described in JP-A 2-146036, page 7, lower column, and specific examples thereof include: 8 of the publication
(IIa-1) to (IIa-8) and (I
Examples thereof include compounds Ib-1) to (IIb-7) and compounds such as 1- (3-methoxyphenyl) -5-mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole. These compounds are added in steps such as a silver halide emulsion grain preparation step, a chemical sensitization step, the end of the chemical sensitization step, and a coating solution preparation step depending on the purpose. When chemical sensitization is carried out in the presence of these compounds, 1 × 10 ⁻⁵ mol to 5 mol per mol of silver halide is used.
It is preferably used in an amount of about 10 ^-4 mol. When added at the end of chemical sensitization, 1 x per mol of silver halide
An amount of about 10 ^-6 mol to 1 × 10 ^-2 mol is preferable, and 1 × 10 ^-5
More preferably, it is 5 to 10 × ³ mol. When added to the silver halide emulsion layer in the coating liquid preparation step, the amount is preferably about 1 × 10 ^-6 mol to 1 × 10 ^-1 mol per mol of silver halide, and 1 × 10 ^-5 mol to 1 × 10 ⁻² mol is more preferable. When it is added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mol.

In the silver halide photographic light-sensitive material used in the present invention, dyes having absorption in various wavelength regions can be used for the purpose of preventing irradiation and halation. For this purpose, any of the known compounds can be used. In particular, as dyes having absorption in the visible region, AI-1 to 11 described in JP-A-3-251840, page 308.
The dye is preferably used, and as the infrared absorbing dye,
The compounds represented by the general formulas (I), (II) and (III) described in the lower left column of page 2 of JP-A-1-280750 have preferable spectral characteristics, and are suitable for the photographic characteristics of silver halide photographic emulsions. It is preferable because there is no influence and there is no contamination due to residual color. Specific examples of preferable compounds include Exemplified Compounds (1) to (45) listed on page 3, lower left column to page 5, lower left column. These compounds can be used in appropriate amounts depending on the required sharpness and sensitivity. For example, regarding the red-sensitive emulsion layer, which is currently the most inferior in sharpness, the spectral reflection density at a wavelength of 680 nm is 0.70.
It is preferable to use the amount as described above.

When the silver halide photographic light-sensitive material used in the present invention is used as a color photographic light-sensitive material, it is spectrally sensitized to a specific region in the wavelength range of 400 to 900 nm in combination with a yellow coupler, a magenta coupler and a cyan coupler. A layer containing a silver halide emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

As the spectral sensitizing dye used in the silver halide emulsion used in the present invention, any known compound can be used. As the blue-sensitive sensitizing dye, JP-A-3-251840, page 28, can be used. BS-1 to BS-8 described in 1 above can be preferably used alone or in combination. As the green sensitizing sensitizing dye, GS-1 described on page 28 of the same publication is used.
~ 5 are preferably used. As the red-sensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication are preferably used. When image exposure is performed by infrared light using a semiconductor laser or the like, an infrared-sensitive sensitizing dye needs to be used. The dyes of IRS-1 to 11 described in No. 6 to 8 are preferably used. Further, it is preferable to use the supersensitizers SS-1 to SS-9 described on pages 8 to 9 of the publication in combination with these dyes.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization.

The sensitizing dye may be added by dissolving it in a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone or dimethylformamide or water and adding it as a solution, or as a solid dispersion. You may add.

As a method for obtaining a solid dispersion of a sensitizing dye, other than a method of mechanically pulverizing and dispersing into fine particles of 1 μm or less in an aqueous system using a high speed stirring type disperser, JP-A-58-105
No. 141, a method of mechanically pulverizing and dispersing into fine particles of 1 μm or less in an aqueous system under the conditions of pH 6 to 8 and 60 to 80 ° C., the surface tension described in JP-B-60-6496 is 38 dyne / c
It is possible to use a method of dispersing in the presence of a surfactant whose m or less is suppressed.

As a dispersing device which can be used for preparing a dispersion, for example, in addition to the high-speed stirring type dispersing device shown in FIG. 1 of JP-A No. 4-125631, a ball mill, a sand mill, an ultrasonic dispersing device, etc. Can be mentioned.

When using these dispersing devices, as described in Japanese Patent Laid-Open No. 4-125632, a method of performing wet dispersion after performing pretreatment such as dry pulverization in advance may be adopted.

As the coupler used in the silver halide photographic light-sensitive material used in the present invention, a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidant of a color developing agent is used. Any compound that can be formed can be used, but as a typical example, a yellow coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm. , Wavelength range 600-750nm
The one known as a cyan coupler having a maximum spectral absorption wavelength is typical.

Cyan couplers which can be preferably used in the silver halide photographic light-sensitive material used in the present invention are represented by the general formulas (CI) and (C-II) described in JP-A-4-114154, page 5, lower left column. ) And a coupler represented by Specific compounds include those described as CC-1 to CC-9 in the same publication, page 5, lower right column to page 6, lower left column.

As the magenta coupler which can be preferably used in the silver halide photographic light-sensitive material used in the present invention, the general formulas (MI) and (M-II) described in JP-A-4-114154, page 4, upper right column are described. ) And a coupler represented by Specific compounds include those described as MC-1 to MC-11 in the same publication, page 4, lower left column to page 5, upper right column. Among them, MC-8 to MC-11 described in the upper column of page 5 of the same publication are preferable because they are excellent in the reproduction of colors ranging from blue to purple and red, and are also excellent in the depiction of details.

The yellow coupler which can be preferably used in the silver halide photographic light-sensitive material used in the present invention is a coupler represented by the general formula (YI) described in JP-A-4-114154, page 3, upper right column. Can be mentioned. Specific compounds can be found in YC
The compounds described as -1 to YC-9 can be mentioned. Above all, YC described in the upper left column on page 4 of the same publication
-8 and YC-9 are preferable because they can reproduce a preferable yellow color.

When the oil-in-water type emulsion dispersion method is used to add the coupler used in the silver halide photographic light-sensitive material used in the present invention, it is usually used in a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher. If necessary, a low-boiling point and / or water-soluble organic solvent is also used in combination to dissolve, and a surfactant is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution. As a dispersing means, a stirrer, a homogenizer,
A colloid mill, a flow jet mixer, an ultrasonic disperser or the like can be used. After the dispersion or at the same time as the dispersion, a step of removing the low boiling point organic solvent may be added. As the high boiling point organic solvent that can be used for dissolving and dispersing the coupler, phthalic acid esters such as dioctyl phthalate and phosphoric acid esters such as tricresyl phosphate are preferably used.

In place of the method using a high-boiling point organic solvent, the coupler and the water-insoluble and organic solvent-soluble polymer compound are dissolved in a low-boiling point and / or water-soluble organic solvent, if necessary, to prepare a gelatin aqueous solution or the like. It is also possible to employ a method of emulsifying and dispersing by using various dispersing means using a surfactant in a hydrophilic binder. Examples of the water-insoluble organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

For the purpose of shifting the absorption wavelength of the color forming dye, the compound (d-11) described in JP-A-4-114154, page 9, lower left column, the compound (A'-1), described in page 10, upper left, of the publication.
And other compounds can be used. Besides, the fluorescent dye-releasing compounds described in US Pat. No. 4,774,187 can also be used.

For the silver halide photographic light-sensitive material used in the present invention, it is advantageous to use gelatin as a binder, but if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, Hydrophilic colloids such as proteins other than gelatin, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

As the support used in the silver halide photographic light-sensitive material used in the present invention, any material may be used, including polyethylene coated paper containing white pigment, baryta paper, vinyl chloride sheet, and white pigment. Polypropylene, polyethylene terephthalate support and the like can be used. Above all, a support having a polyolefin resin layer containing a white pigment on its surface is preferable.

As the white pigment used for the reflective support, inorganic and / or organic white pigments can be used, and preferably inorganic white pigments are used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silicic acid, silicas such as synthetic silicates, calcium silicate, alumina,
Alumina hydrate, titanium oxide, zinc oxide, talc, clay and the like can be mentioned. The white pigment is preferably barium sulfate or titanium oxide.

The amount of the white pigment contained in the waterproof resin layer on the surface of the reflective support is preferably 10% by weight or more, more preferably 13% by weight or more, as the content in the waterproof resin layer. Is preferable, and more preferably 15% by weight or more. The dispersity of the white pigment in the water resistant resin layer of the paper support used in the present invention is described in JP-A-2-2864.
It can be measured by the method described in No. 0. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, and even more preferably 0.10 or less as the coefficient of variation described in the above publication.

The silver halide photographic light-sensitive material used in the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support, if necessary, and then directly or undercoat layer (adhesiveness of the surface of the support). , Antistatic property, dimensional stability, abrasion resistance,
It may be applied via one or more subbing layers) to improve hardness, antihalation properties, friction properties and / or other properties.

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

Further, in the silver halide photographic light-sensitive material used in the present invention, various hardeners are used for the purpose of preventing damage or dissolution of the film during processing. As these hardeners, many compounds such as epoxy compounds, aziridine compounds, acryloyl compounds, vinylsulfonyl compounds, chlorotriazine compounds are known, and the silver halide photographic light-sensitive materials used in the present invention are known. Any known hardener can be preferably used as the material.

To form a photographic image using the silver halide photographic light-sensitive material used in the present invention, the image recorded on the negative is optically formed on the silver halide photographic light-sensitive material to be printed. It is common to form an image and print it, but after the image is once converted into digital information, the image is formed on a CRT (cathode ray tube) and the image is printed on a silver halide photographic light-sensitive material. The image may be imaged and printed, or may be printed by changing the intensity of the laser light based on digital information and scanning.

When exposure is carried out using laser light, the exposure time per pixel is not particularly limited, but is 100 nanoseconds to 1 nanosecond.
Often exposed in 00 microseconds. In the case of exposure for an extremely short time, the phenomenon that the slope of the characteristic curve greatly changes at a certain density point often occurs. When the density changes due to running, the image quality is significantly deteriorated, such as a pseudo contour being generated in the image depending on the density range. In the silver halide photographic light-sensitive material used in the present invention, it is possible to remarkably improve the stability also for the characteristics at such exposure of 100 microseconds or less,
It can be preferably used.

The exposure time per pixel is the outer edge of the light flux when the light intensity becomes 1/2 of the maximum value in the spatial variation of the light flux intensity, is parallel to the scanning line, and is the light intensity. When the distance between two points where the line passing through the maximum point and the outer edge of the light flux intersects is the light flux diameter, the (light flux diameter) / (scanning speed) is defined as the exposure time per pixel.

A laser printer device that is considered to be applicable to such a system is, for example, Japanese Patent Laid-Open No. 55-4.
071, JP-A-59-11062, JP-A-63-197947, JP-A
2-74942, Japanese Patent Laid-Open No. 2-236538, Japanese Patent Publication No. 56-14963, Japanese Patent Publication No. 56-40822, European Wide Area Patent 77,410, Department of Electronics and Communication Technology Research Report 80, Volume 244, and Movie Television Technical Journal 1984. /
6 (382), pages 34-36.

A semiconductor laser is also preferably used as a light source used for exposing the silver halide photographic light-sensitive material used in the present invention. As a semiconductor laser,
Any material may be used as long as it has sufficient intensity at a predetermined wavelength, such as gallium / arsenic / phosphorus, aluminum / gallium / arsenic, indium / gallium / arsenic / phosphorus, aluminum / gallium / arsenic / antimony. Can be raised. Among them, 680, 750, 780, 810, 83
A semiconductor laser of 0,880 nm is advantageously used in terms of light intensity and handling of silver halide photosensitive materials.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds may be mentioned as examples of these compounds.

CD-1) N, N-diethyl-p-phenylenediamine CD-2) 2-amino-5-diethylaminotoluene CD-3) 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4) 4-Amino-3-methyl-N-ethyl-N- (β-butoxyethyl) aniline CD-5) 2-Methyl-4- (N-ethyl-N- (β-hydroxyethyl) amino) Aniline CD-6) 4-amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) -aniline CD-7) N- (2-amino-5-diethylaminophenylethyl)
Methanesulfonamide CD-8) N, N-Dimethyl-p-phenylenediamine CD-9) 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline CD-10) 4-Amino-3-methyl- N-ethyl-N- (β-ethoxyethyl) aniline CD-11) 4-amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline.

These compounds are preferably used in the range of 0.001 to 0.2 mol per liter of the developing solution, and
More preferably, it is used in the range of 005 to 0.2 mol.

The color developer used in the present invention may contain the following developer components in addition to the above components.
As the alkaline agent, for example, sodium hydroxide, potassium hydroxide, sodium metaborate, potassium metaborate,
Trisodium phosphate, tripotassium phosphate, borax, silicate, and the like can be used alone or in combination within a range that does not cause precipitation and maintains the pH stabilizing effect. Further, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, borate, etc. are used for the necessity of preparation or for the purpose of increasing ionic strength. can do.

If necessary, inorganic and organic antifoggants can be added. For the purpose of suppressing development, halide salt ions are often used,
In the image forming method according to the present invention, chloride ions are mainly used, and potassium chloride, sodium chloride and the like are used. The amount of chloride ion is approximately 3.0 × 10 ^-2 mol or more, preferably 4.0 × 10 ^-2 , per liter of color developing solution.
It is about 5.0 × 10 ^-1 mol. Bromide ions can be used within a range that does not impair the effects of the present invention, but have a large effect of suppressing development, and are approximately 1.0 × 10 ⁻³ mol or less, preferably 5.0 × 10 ⁻⁴ mol, per liter of color developing solution. The following is desirable.

The preservatives used in the color developing solution used in the present invention include hydroxylamine derivatives (excluding hydroxylamine), hydroxamic acids, hydrazines, hydrazide aminoketones, saccharides, monoamines,
Diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines and the like are particularly effective organic preservatives. Particularly, dialkyl-substituted hydroxylamines such as diethylhydroxylamine and alkanolamines such as triethanolamine are preferably used.

As the chelating agent used in the color developing solution used in the present invention, compounds such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid are used. In particular, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid and 1-hydroxyethylidene-1,1-diphosphonic acid are preferably used.

The processing temperature for color development used in the present invention is usually 15 ° C. or higher, and generally 20 to 50 ° C. The higher the temperature, the shorter the treatment time is, which is preferable. However, it is preferable that the temperature is not so high in view of the stability of the treatment liquid.

The color development time is conventionally 10 seconds to 4 in general.
Minutes, but 10 seconds to 1 for rapid processing
The time is preferably in the range of 10 minutes to 30 seconds when further speeding up is required.

In the present invention, the above color developing solution can be used in any pH range, but from the viewpoint of rapid processing, pH = 9.5.
˜13.0, more preferably pH = 9.8
Used in the range of ~ 12.0.

When the running process is carried out while continuously replenishing the color developing solution, the replenishing amount of the color developing solution is set in order to eliminate the overflow solution of the color developing solution and reduce the pollution problem due to the waste solution. 20-60 per 1 m ^{2 of} photosensitive material
It is preferably ml, but the silver halide photographic light-sensitive material used in the present invention can be preferably used under such conditions. In the present invention, the more preferable replenishing amount of the color developing solution is ^{20 to} 45 ml per 1 m ² of the light-sensitive material.

The processing step essentially consists of a color developing step, a bleach-fixing step, and a water washing step, but steps can be added or replaced with steps having the same meaning as long as the effects of the present invention are not impaired. For example, the bleach-fixing step can be separated into a bleaching step and a fixing step, or the bleaching step can be performed before the bleach-fixing step. As the processing step used in the image forming method of the present invention, it is preferable to provide a bleach-fixing step immediately after the color developing step. 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.

The development processing apparatus used for the development processing of the silver halide photographic light-sensitive material of the present invention may be a roller transport type in which the light-sensitive material is conveyed by sandwiching it between rollers arranged in a processing tank, or a belt. The endless belt method may be used in which the photosensitive material is fixed and conveyed, but the processing tank is formed in a slit shape, the processing solution is supplied to the processing tank and the photosensitive material is conveyed, and the processing solution is sprayed. It is also possible to use a spray method for forming a shape, a web method by contact with a carrier impregnated with a treatment liquid, a method with a viscous treatment liquid, and the like.

[0088]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 A paper support was prepared by laminating high-density polyethylene on both sides of paper pulp having a basis weight of 180 g / m ² . However, on the side where the emulsion layer was coated, a molten polyethylene containing a surface-treated anatase type titanium oxide dispersed in a content of 15% by weight was laminated to prepare a reflective support. Each layer having the following constitution was coated on this reflective support to prepare a silver halide photographic light-sensitive material. The coating liquid was prepared as follows.

Magenta coupler (M-1) 12.14 g, additive (ST-3) 12.14 g, (ST-4) 10.32 g, and high boiling organic solvent (DIDP) 7.9 g, (DBP) 7.9 g ethyl acetate. 60 ml was added and dissolved, and this solution was added with 20% surfactant (SU
1) 220 ml of 10% gelatin aqueous solution containing 12 ml was emulsified and dispersed using an ultrasonic homogenizer to prepare a magenta coupler dispersion.

This dispersion was mixed with a silver halide emulsion (containing 8.5 g of silver) prepared under the following conditions to prepare a coating solution for the first layer. The second layer coating liquid was also prepared in the same manner as the first layer coating liquid. Further, (H-1) was added to the second layer as a hardener. As the coating aid, a surfactant (SU-2),
(SU-3) was added to adjust the surface tension.

Using the coating solution prepared as described above,
A silver halide photographic light-sensitive material was prepared. The layer structure is shown in Table 1 below.

[0093]

[Table 1]

[0094]

[Chemical 1]

SU-1: Sodium tri-i-propylnaphthalene sulfonate SU-2: Sodium salt of di (2-ethylhexyl) sulfosuccinate SU-3: Di (2,2,3,3,4,4) sulfosuccinate , 5,5-Octafluoropentyl) sodium salt DIDP: di-i-decylphthalate DBP: dibutylphthalate H-1: tetrakis (vinylsulfonylmethyl) methane (preparation of silver halide emulsion) 2% kept at 40 ℃ PA of the following (solution A) and (solution B) in 1 liter of gelatin aqueous solution.
Simultaneously added while controlling g = 7.3 and pH = 3.0, and further adding the following (C solution) and (D solution) and (E solution) and (F solution) at pAg = 8.
Simultaneous addition was carried out while controlling 0 and pH = 5.5. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B) Silver nitrate 10.0 g Water was added to 200 ml (Solution C) Sodium chloride 92.1 g Potassium bromide 0.87 g Water was added 538ml (D liquid) Silver nitrate 269g Water added 538ml (E liquid) Sodium chloride 10.6g Potassium bromide 0.13g Water added 62ml (F liquid) Silver nitrate 31g Water added 62ml After addition, Kao Atlas demol After desalting using a 5% aqueous solution of N and a 20% aqueous solution of magnesium sulfate, it was mixed with a gelatin aqueous solution to obtain an average particle size of 0.43 μm, a coefficient of variation (S / R) = 0.08, and a silver chloride content of 99.5 mol. % Monodisperse cubic emulsion (EMP-11) was obtained.

In the preparation of (EMP-11), (E liquid), (F
Liquid) while mixing the exemplified compound of the present invention (metal complex) (I-1)
9.2 × 10 ^-8 mol of monodispersed cubic emulsion (EMP-12),
Using the exemplified compound (II-6) of the present invention, a monodisperse cubic emulsion (E
MP-13) was prepared.

Next, in the preparation of (EMP-11), (solution A),
While mixing (B liquid), 9.2 × 10 9
-8 mol was added to prepare a monodisperse cubic emulsion (EMP-14) and a monodisperse cubic emulsion (EMP-15) using the exemplified compound (II-6) of the present invention.

Next, the above emulsions (EMP-11) to (EMP-15) were optimally chemically sensitized at 60 ° C. using the following compounds,
Green-sensitive silver halide emulsions (Em-G101) to (Em-G105) were obtained.

Sodium thiosulfate 3.0 mg / mol AgX stabilizer (STAB-1) 6 × 10 ⁻⁴ mol / mol AgX stabilizer (STAB-2) 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye (GS-1 ) 4 × 10 ^-4 mol / mol AgX

[0101]

[Chemical 2]

STAB-1: 1- (3-acetamidophenyl) -5-
Mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole Silver halide photographic light-sensitive material prepared using this emulsion N
O. 101 to 105 were subjected to optical wedge exposure by a conventional method, and then the following developing treatments A and B were performed. At this time, the Konica Color QA Paper Type A5 was printed and run as the processing solution in advance until the replenishing solution of twice the tank capacity of the color developing solution was replenished.

The development processing steps and the formulations of the processing solutions were as follows. The amount of replenishment is expressed by the amount per 1 m ² of the photographic material.

(Processing step A) Processing step Processing temperature Time Replenishment amount Color development 35.0 ± 0.3 ° C. 45 seconds 80 ml Bleach fixing 35.0 ± 0.5 ° C. 45 seconds 80 ml Stabilization 30-34 ° C. 90 seconds 250 ml Dry 60-80 ° C. 60 seconds ( Processing step B) Processing temperature Processing temperature Time Replenishment amount Color development 39.0 ± 0.3 ℃ 45 seconds 40ml Bleach fixing 35.0 ± 0.5 ℃ 45 seconds 51ml Stabilization 30-34 ℃ 90 seconds 250ml (3 tank cascade) Dry 60-80 ℃ 60 seconds The compositions of the developing solution tank liquid and the replenisher liquid are shown below.

(Treatment process A color developing solution tank solution and replenisher) (Tank solution) (Replenisher) Pure water 800 ml 800 ml Triethanolamine 10 g 18 g N, N-diethylhydroxylamine 5 g 9 g Potassium chloride 2.4 g -1- Hydroxyethylidene-1,1-diphosphonic acid 1.0g 1.8g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.4g 8.2g Optical brightener (4,4 ' Diaminostilbene sulfonic acid derivative) 1.0g 1.8g Potassium carbonate 27g 27g Add water to make the total volume 1 liter.
Adjust to 0 and replenisher to pH = 10.60.

(Color developer tank solution and replenisher for processing step B) (Tank solution) (Replenisher) Pure water 800 ml 800 ml Triethanolamine 10 g 14 g N, N-diethylhydroxylamine 3.6 g 5 g Potassium chloride 4.5 g-diethylenetriamine Pentaacetic acid 5.0 g-potassium sulfite 0.4 g-N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 12.0 g potassium carbonate 25 g 35 g And the tank liquid is pH = 10.1
At 0, the replenisher is adjusted to pH = 11.50.

(Bleaching and Fixing Solution Tank Solution and Replenishing Solution for Treatment Step A) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Water Is added to bring the total amount to 1 liter, and the pH is adjusted to 5.7 with potassium carbonate or glacial acetic acid.

(Bleaching Fixing Solution Tank Solution and Replenishing Solution for Treatment Step B) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 53 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 123 ml Ammonium sulfite (40% aqueous solution) 51 ml Water In addition, adjust the total volume to 1 liter and adjust the pH to 5.4 with potassium carbonate or glacial acetic acid.

(Stabilizing Solution Tank Solution and Replenishing Solution for Treatment Process A) F-1 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% Aqueous solution) 3.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.5 g Water is added to make the total volume 1 liter, and pH is adjusted to 7.0 with sulfuric acid or aqueous ammonia.

(Stabilizing Solution Tank Solution for Treatment Process B and Replenishing Solution) o-Phenylphenol 0.1 g Ubitex (Ciba Geigy) 1.0 g Zinc Sulfate Heptahydrate 0.1 g Ammonium Sulfite (40% Solution) 5.0 ml 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 g Ethylenediaminetetraacetic acid 1.5 g Water is added to bring the total volume to 1 liter, and pH is adjusted to 7.8 with glacial acetic acid or aqueous ammonia.

[0111]

[Chemical 3]

The density of the formed magenta dye was measured with a PDA-65 densitometer (manufactured by Konica Corp.) to obtain a characteristic curve, and then a characteristic curve between the maximum density (Dmax) and the densities of 0.25 and 0.75 was obtained. The average gradient of the above was calculated and compared. The results are shown in Table 2.

[0113]

[Table 2]

The silver halide emulsion containing the complex gives slightly harder characteristics than the one not containing the complex.
There is not much effect on Dmax. When the replenishment amount was reduced, it was confirmed that the gradation became softer and Dmax was lowered.

Those in which the addition position of the complex was inside the particles had similar characteristics regardless of the kind of the complex. On the other hand, when added to the grain surface, the emulsion to which the complex used in the present invention was added had a high contrast and a high Dmax, and even when the amount of replenishment was decreased, the gradation was slightly increased and the Dmax was increased. . It can be seen that the effect of the present invention depends on the type of complex and the position of addition within the particle.

Then, the above emulsions (EMP-11) to (EMP-15) were optimally chemically sensitized at 60 ° C. using the following compounds,
Green-sensitive silver halide emulsions (Em-G106) to (Em-G110) were obtained.

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer (STAB-1) 6 × 10 ⁻⁴ mol / mol AgX stabilizer (STAB-2) 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye (GS-1) 4 × 10 ^-4 mol / mol AgX Samples prepared using this emulsion in the same manner as Samples 101 to 105 above.
106 to 110 were prepared and evaluated. The results are shown in Table 3.

[0118]

[Table 3]

Gradation tends to be softened by using the gold sensitizer, but softening is hardly observed in the silver halide photographic light-sensitive material used in the present invention. In the comparative sample, Dmax increased slightly due to gold sensitization, and the treatment B
However, in the silver halide photographic light-sensitive material used in the present invention, the effect that the Dmax in the processing B was higher than that in the processing A was more significantly recognized.

It is a preferred embodiment of the present invention to use a gold sensitizer in the chemical sensitization of the silver halide photographic emulsion used in the present invention.

Example 2 In the preparation of the silver halide emulsion (EMP-12) of Example 1,
Emulsions were prepared by variously changing the type of complex to be added. Then, in the preparation of the green light-sensitive emulsion (Em-G107), a green light-sensitive emulsion was prepared in the same manner except that the silver halide photographic emulsion was changed to the one described above, and a silver halide photographic light-sensitive material was prepared in the same manner as in Sample 107. It was made.

Silver halide emulsions for some complexes
According to the preparation method of (EMP-14), a silver halide photographic emulsion was prepared in the same manner except that a complex was added inside the grain. In the preparation of the green-sensitive emulsion (Em-G107), a green-sensitive emulsion was prepared in the same manner except that the silver halide photographic emulsion was changed to the one described above. The material was made.

In the same manner as in Example 1, the gradation and Dmax in processing A and processing B were evaluated. The results are shown in Table 4 below.

[0124]

[Table 4]

The silver halide photographic emulsions used in the present invention are both high in contrast and high in Dma in both the treatments A and B.
It was confirmed that x was obtained. In addition to the comparison with the compound (I-1) of the present invention in Example 1, the effects of the addition position are seen in (I-7) and (I-15). It was confirmed that the effect of the present invention was not obtained by adding it inside the silver halide emulsion grains, and the position of addition was important.

Among the compounds of the present invention, nitrosyl,
It can be seen that the compound having the thionitrosyl and carbonyl ligands on the rotation axis four times has a larger effect particularly in increasing Dmax than other compounds.

Example 3 In the preparation of the silver halide photographic emulsion (EMP-11) of Example 1, after the addition and mixing of (Solution A) to (Solution F) were completed, the exemplified compound (I- 1) was added at 9.2 × 10 ^-8 mol and 40 minutes for 40 minutes
The temperature was maintained at ° C to prepare a monodisperse cubic emulsion (EMP-31).

Next, the silver halide photographic emulsion of Example 1 (EMP
In the preparation of (-12), (E liquid) and (F liquid) and 9.2 × 10 ⁻⁸ mol of the compound (I-1) of the present invention were rapidly added to 100 ml of a 2% gelatin aqueous solution kept at 40 ° C. A fine grain silver chlorobromide emulsion was prepared. On the other hand, separately from this, (A solution) to (D solution) in the preparation of (EMP-12) are mixed to prepare host grains, to which the above-mentioned fine grain silver chloride emulsion is added (EMP-12).
-32) was prepared.

A green-sensitive emulsion was prepared in the same manner as in Example 1 except that the silver halide photographic emulsion was changed from (EMP-12) to (EMP-31) and (EMP-32) in the preparation of (Em-G107). Then, using this, a silver halide photographic light-sensitive material was prepared in the same manner as in Sample 107.

Evaluation was carried out in the same manner as in Example 1 using the above silver halide photographic light-sensitive material. The results are shown in Table 5 below.

[0131]

[Table 5]

In forming the silver halide grains in the portion containing the complex used in the present invention, compared with the sample 107 using (EMP-12) formed by the simultaneous mixing method, fine particles containing the complex were prepared in advance. It has been found that the effect of the present invention is greater in the case of (EMP-32) which is formed by adding it. On the other hand, it was confirmed that the effect of the present invention can be obtained even by adding (EMP-31) during physical ripening after the formation of silver halide grains.

However, the magnitude of the effect was slightly small when added during physical ripening, and it was found that it is preferable to add the complex used in the present invention under the condition that the silver halide photographic emulsion grains grow. It was

Example 4 In the preparation of the silver halide photographic emulsion (EMP-12) of Example 1, the heavy metal compound (II-5) described above was added to the solution (A) at 2 × 10 5.
Silver halide photographic emulsions (EMP-41) to (EMP-43) were prepared in the same manner except that ^-5 mol, (II-6) and (II-28) were added in an amount of 9.2 × 10 ^-8 mol.

Sample 107 was prepared in the same manner as in Example 1 except that the silver halide photographic emulsion was changed from (EMP-12) to the above emulsion in the preparation of the green-sensitive emulsion (Em-G107).
A silver halide photographic light-sensitive material was produced in the same manner as. These samples were evaluated in the same manner as in Example 1. The results are shown in Table 6 below.

[0136]

[Table 6]

Heavy metal compounds (II-5), (II-6), (II-28)
Are all well known compounds that are effective in improving reciprocity law failure. When the reciprocity law failure was evaluated by the conventional method using the samples No. 401 to No. 403, it was confirmed that the effect was not impaired. Table 6
As shown in FIG. 5, it was confirmed that both Treatment A and Treatment B were in a high contrast and showed high Dmax. Among them, a silver halide photographic emulsion in which the heavy metal compounds (II-6) and (II-28) are added inside the grain is a preferred embodiment because the effect of the present invention becomes large.

Example 5 Using the samples 106 to 110 of Example 1, the following processing steps C and D were performed.
The evaluation was performed in the same manner as in Example 1.

(Processing Step C) In the processing step A, the temperature of the color developing step was 39 ° C. and the developing time was 25 seconds. The other processing steps and the composition of the processing liquid are the same as those in the processing step A.

(Processing step D) In processing step B, the temperature of the color developing step was 41 ° C., and the developing time was 25 seconds. The other steps and the composition of the processing liquid are the same as those in the processing step B.

The evaluation results are shown in Table 7.

[0142]

[Table 7]

[0143] As a whole, the change in performance due to the shortened time could not be completely recovered, and the gradation was softened and Dmax was lowered. Among them, the silver halide photographic light-sensitive material used in the present invention It was found that the use of No. 2 caused little change and maintained a high Dmax even when the replenishment amount was reduced.

Next, in the above-mentioned processing steps C and D, the evaluation was repeated using the same processing steps E and F except that the color developing agent in the color developing solution was changed to (CD-11). The evaluation results are shown in Table 8.

[0145]

[Table 8]

It was confirmed that the effects of the present invention can be obtained similarly to the processing steps C and D. Considering the magnitude of performance deterioration when using a comparative silver halide photographic light-sensitive material, the usefulness of the present invention is higher under the condition that the processing time is shortened in the image forming method according to the present invention. I understand.

Example 6 A paper support was prepared by laminating high density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However, on the side where the emulsion layer was coated, a molten polyethylene containing a surface-treated anatase type titanium oxide dispersed in a content of 15% by weight was laminated to prepare a reflective support. Each layer having the following constitution was coated on this reflective support to prepare a silver halide photographic light-sensitive material, Sample 601. The coating liquid was prepared as follows.

First Layer Coating Solution Yellow coupler (Y-1) 23.4 g, dye image stabilizer (ST-1) 3.34 g, dye image stabilizer (ST-2) 3.
34 g, dye image stabilizer (ST-5) 3.34 g, stain inhibitor (HQ-1) 0.33 g, compound A 5.0 g and high boiling organic solvent (DBP) 5.0 g were dissolved by adding ethyl acetate 60 ml. The solution was emulsified and dispersed in 220 ml of 10% gelatin aqueous solution containing 7 ml of 20% surfactant (SU-1) using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with the following blue-sensitive silver halide emulsion (Em-B60
The first layer coating liquid was prepared by mixing with 1).

The coating liquids for the second to seventh layers were prepared in the same manner as the coating liquid for the first layer so that the coating amounts were as shown in Tables 9 and 10.

Further, as a hardener, (H-1), (H-
2) was added. As a coating aid, a surfactant (SU
-2) and (SU-3) were added to adjust the surface tension.
Further, (F-1) was added to each layer so that the total amount was 0.04 g / m ² .

[0151]

[Table 9]

[0152]

[Table 10]

[0153]

[Chemical 4]

[0154]

[Chemical 5]

[0155]

[Chemical 6]

[0156]

[Chemical 7]

[0157]

[Chemical 8]

[0158]

[Chemical 9]

DBP: Dibutyl phthalate DOP: Di (2-ethylhexyl) phthalate PVP: Polyvinylpyrrolidone DIDP: Diisodecyl phthalate Compound A: p- (t-octyl) phenol Blue-sensitive emulsion and green-sensitive emulsion are prepared by the following methods. Was prepared by.

(Preparation of blue-sensitive silver halide emulsion) In the preparation of (EMP-11) and (EMP-12) of Example 1, (solution A) to (F)
A silver halide emulsion was prepared in the same manner as in (EMP-11) and (EMP-12) except that the addition time of the solution was changed. As a result, cubic emulsions (EMP-61) and (EMP-62) having an average grain size of 0.85 μm and a silver chloride content of 99.5 mol% were obtained.

Then, the above emulsions (EMP-61) and (EMP-62) were optimally chemically sensitized at 60 ° C. using the following compounds,
Blue-sensitive silver halide emulsions (Em-B601) and (Em-B602) were obtained.

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer (STAB-3) 8 × 10 ⁻⁴ mol / mol AgX sensitizing dye (BS-1) 4 × 10 ⁻⁴ mol / Molar AgX sensitizing dye (BS-2) 1 × 10 ⁻⁴ mol / mol AgX (Preparation of red-sensitive silver halide emulsion) Example 1 (EMP-1
1) In the preparation of (EMP-12), the silver halide emulsion was prepared in the same manner as in (EMP-11) and (EMP-12) except that the addition time of (A solution) to (F solution) was changed. went. As a result, the average particle size
Cubic emulsions (EMP-63) and (EMP-64) of 0.50 μm were obtained.

Then, the above emulsions (EMP-63) and (EMP-64) were optimally chemically sensitized at 60 ° C. using the following compounds,
Red-sensitive silver halide emulsions (Em-R601) and (Em-R602) were obtained.

Sodium thiosulfate 1.8 mg / mol Ag
X Chloroauric acid 2.0 mg / mol AgX stabilizer (STAB-1) 6 × 10 ^-4 mol / mol AgX stabilizer (STAB-2) 3 × 10 ^-4 mol / mol AgX sensitizing dye (RS-1) 1 × 10 ^-4 mol / mol AgX Sensitizing dye (RS-2) 1 × 10 ^-4 mol / mol AgX

[0165]

[Chemical 10]

STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole In preparing a silver halide photographic light-sensitive material, Sample No. 601, a blue-sensitive silver halide emulsion (Em-B601) was replaced with (Em- B602),
Sample No. 602 was prepared in the same manner except that the green-sensitive silver halide emulsion (Em-G106) was replaced with (Em-G107) and the red-sensitive silver halide emulsion (Em-R601) was replaced with (Em-R602). did.

Image exposure was carried out on the silver halide photographic light-sensitive materials, Samples 601 and 602, through the developed Konica Color XG-400, and development processing was carried out in the processing steps A and B of Example 1 to obtain a color print. With the silver halide photographic light-sensitive material, Sample 602, used in the present invention, a color print excellent in color reproducibility could be obtained even under the condition that the replenishment amount of the color developing solution was small. I was only able to obtain prints with a lack of contrast, poor shadow tightness, and a slight lack of contrast.

Further, prints were prepared by laser exposure using Samples 601 and 602. Image data is 4 × 5
Image of inch size color slide (portrait)
A digital value of 25 × 25 μm per pixel was digitized by a scanner.

The exposure apparatus uses helium.
We prepared a cadmium laser (about 442 nm), a helium-neon laser (about 544 nm) as a green light source, and a helium-neon laser (about 633 nm) as a red light source, and assembled the optical system. The light emitted from the three lasers is modulated according to the image data and then focused into one beam, which is 20mm
Silver halide photographic light-sensitive material conveyed at a speed of
Scanning exposure was performed at a main scanning speed of 160 m / sec at a right angle to the carrying direction. The beam diameter at this time was about 80 μm, and the exposure time per pixel was 500 nanoseconds.

With the silver halide photographic light-sensitive material used in the present invention, Sample 602, a color print excellent in color reproducibility similar to a normal color print could be obtained by laser exposure, but with Sample 601 the highest density was obtained. The shortage is remarkable,
I could only get prints with poor color balance.

As described above, it was confirmed that an excellent color print can be obtained by the photographic image forming method according to the present invention even when the conditions of actual use are approximated.

[0172]

EFFECTS OF THE INVENTION According to the present invention, it is possible to stably obtain a high-quality image having high contrast and high density even under a processing condition of a low pollution load in which the replenishment amount of the developing solution is reduced in a short time. An image forming method is provided.

Claims (1)

[Claims] 1. A method for forming a photographic image in which a silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer having a silver chloride content of 95 mol% or more on a support is subjected to development processing after image exposure. In the silver halide photographic emulsion layer, at least one metal element of Groups 5 to 10 of the Periodic Table is used as a central metal in the vicinity of the grain surface, and among the six monodentate ligands, four times on the rotation axis. Characterized by containing silver halide grains containing a complex in which at least one of the ligands is a ligand different from the other, and the replenishing amount of the developing solution is 20 to 60 ml per 1 m ^{2 of the} light-sensitive material. And a photographic image forming method.