JPH0869081A - Silver halide photographic emulsion and silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To obtain a photosensitive material superior in reciprocity law failure characteristics and latent image stability and improved in resistance to fog due to drying at the time of coating in manufacturing the photosensitive material and capable of stably forming an image high in quality by allowing the silver halide photographic emulsion to have a specified silver halide composition and incorporate silver halide grains containing at least 2 kinds of specified compounds. CONSTITUTION: The silver halide grains have a silver chloride content of >=10mol% and a silver bromide content of >=0.1mol% and contains the compound represented by the formula: Y1 n11 M1 Brn12 X1 n13 and the compound represented by the formula: Y2 n21 M2 (CN)n22 X2 n23 , and in the formula, M1 is a renium or ruthenium ion or the like; Y1 is a cation coupling with the complex anion of M1 ; X1 is a ligand coordinable by M1 ; n11 is 0, 1, 2, or 3; each of n12 and n13 is an integer of 0 to 6, and n12 >=n13 and n12 +n13 =4 or 6; M2 is the ion of an element of group VII-X; Y2 is a cation coupling with the complex anion of M2 ; X2 is a ligand coordinable by M2 ; n21 is an integer of 0 to 4; and each of n22 and n23 is an integer of 0 to 6 and n22 +n23 =4 or 6.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic emulsion and a silver halide photographic light-sensitive material,
The present invention relates to a silver halide photographic light-sensitive material having excellent latent image stability and excellent resistance to dry fog that occurs when a support having a low oxygen transmission rate such as polyester is used.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials (hereinafter also simply referred to as "light-sensitive materials") have high sensitivity, excellent gradation, sharpness, graininess and color reproducibility.
It is used very often. In recent years, in order to finish a large amount of prints in a short delivery time, a photosensitive material for color photographic paper is required to have rapid processability. Further, due to the widespread use of minilabs, the time required from the end of exposure to the start of development is wide, and it is desired to stabilize the latent image from an extremely short time to a long time. As a means for speeding up, it is known to use a silver chloride emulsion or a silver chlorobromide having a high silver chloride content as a silver halide photographic emulsion to be used. For example, JP-A-58-91444, JP-A-58-94340 and JP-A-58-94340
-106538 and 58-125612.

However, a silver chloride emulsion or a silver chlorobromide having a high silver chloride content has high fog and low sensitivity, and further has a defect in reciprocity law failure characteristics. Various proposals have been made as means for solving the above drawbacks. JPA
Nos. 51-139323 and 59-171947 propose techniques for improving processing stability and reciprocity failure characteristics by incorporating a Group VIII transition metal compound of the periodic table.

It is known that doping an iridium compound is effective for improving the reciprocity law failure of a silver halide photographic emulsion. JP-B-43-4935 proposes that gradation variation can be reduced over a wide range of exposure time by adding an iridium compound during the preparation of silver halide grains.

However, the above technique has a problem that the sensitivity varies greatly depending on the exposure time and the time interval of the developing process, that is, the latent image stability is poor. Journal of Photogr
Apic Science, Vol. 33, p. 201, when an iridium compound is doped into a silver halide photographic emulsion as a reciprocity improving compound, the latent image stability of 15 seconds to about 2 hours after exposure is relatively short (hereinafter referred to as the initial stage). It has been disclosed by Wicky that the latent image stability of (1) is significantly deteriorated.

Japanese Unexamined Patent Publication (Kokai) No. 1-105940 discloses a technique for improving initial latent image stability by doping iridium into a specific region. In JP-A-3-188437, by incorporating an iridium compound and an iron compound in the surface side of 50% or more of the grain volume of silver halide grains, reciprocity law failure and latent image stability over time from exposure to development processing are achieved. Is disclosed. However, the above technology
There is no description about the bromine ligand of the iridium compound, and as a result of the study by the present inventors, the gradation fluctuates due to the change with time until after the post-exposure treatment, and the latent image stability is not sufficiently satisfactory. I knew it wasn't. JP-A-6-102604
In No. 6, the use of rhenium, ruthenium, osmium, platinum, palladium, and iridium complexes with bromide ion as a ligand provides high-grade gradation, reciprocity law improperness, and latent image stabilization in a short time from exposure to development processing. It is described that the sex is improved. However, it has been found that the latent image stability in the middle period is rather deteriorated.

As described above, a silver halide light-sensitive material excellent in reciprocity law failure property and capable of satisfying latent image stability over a wider range of time from exposure to development has not been obtained.

On the other hand, in recent years, a paper support coated with a polyolefin such as polyethylene has been often used as a support for general photographic printing paper. Since this polyolefin-coated paper does not allow the treatment chemical to penetrate into the support, it can be rapidly treated and dried, and has been used for most purposes. However, the polyolefin-coated paper has a drawback that since both sides of the paper are coated with the polyolefin resin, irregularities due to the fibers of the paper inevitably appear on the surface, and it is impossible to obtain a completely smooth flat surface. . Although a method of thickening the polyolefin layer can be used as a means for overcoming these drawbacks, it has been difficult to achieve the required smoothness with a soft resin such as polyolefin. In general snapshots, even a support with this level of smoothness was almost acceptable, but in still life photographs for advertising, it was not sufficient to express the subtle texture of the material, and a smoother flat surface was used. There was a need for a support with.

A polyester support is known as a support providing a very smooth flat surface. In addition to a transparent polyester support, barium sulfate is contained in a polyester resin, and titanium oxide is provided on a reflective support or a transparent support obtained by scattering light by barium sulfate and minute voids generated during production. There is provided a silver halide photographic light-sensitive material using a material provided with a hydrophilic colloid layer.

However, it has been found that when such a support is used, there is a drawback that dry fog occurs depending on the drying conditions at the time of coating the photosensitive material. In order to improve the productivity, it is necessary to increase the coating speed and shorten the drying time. Therefore, it is necessary to improve the dry fog resistance. As a result of various analyses, the influence of the support on the dry fog resistance is large, and when a low oxygen permeability support such as a polyester support is used, the silver chloride content of the silver halide photographic emulsion used is also high. It was found that the higher the value, the more pronounced it appears.

In Japanese Patent Laid-Open No. Sho 63-30846, on a specific support defined by the ratio of reflected light intensities measured at different angles,
A silver halide photographic light-sensitive material having a hydrophilic colloid layer containing at least one pyrazoloazole-based coupler can be obtained without diminishing the effect of increasing the color saturation by using the pyrazoloazole-based coupler. Is disclosed. In the above-mentioned patent, it is stated in the Examples that a titanium oxide-containing polyester base is used. However, the present invention is a specific support satisfying the condition defined by the ratio of the reflected light intensities measured at different angles, that is, according to the description on the above-mentioned patent page 10, excellent smoothness, specular reflection It is characterized by the use of a support, no description is given regarding the oxygen permeability, and no problem is suggested when using this support.

In JP-A-5-61152, the oxygen permeability is 2.0 ml.
/ M ² · hr · atm or less A silver halide photographic light-sensitive material containing a specific pyrazolone-based magenta coupler on a support gives a silver halide photographic light-sensitive material excellent in color reproducibility and light resistance. Is disclosed. However, this technique relates to the characteristics of magenta dyes produced from the above-mentioned couplers, and the reciprocity law failure characteristics, latent image stability, and low oxygen transmittance of the light-sensitive materials caused by silver halide photographic emulsions are supported. There is no mention of the problem of dry fog resistance that occurs when the body is used, and no suggestion is made as to the solution.

The above-mentioned JP-A-1-105940 and JP-A-3-188437,
No. 6-102604 does not mention any problems that may occur when such a low oxygen permeability support is used, and does not suggest a solution.

[0014]

In view of the above problems, an object of the present invention is to provide stable reciprocity by improving reciprocity law failure characteristics, latent image stability, and improving dry fog resistance during coating of a photosensitive material. It is an object of the present invention to provide a silver halide photographic emulsion and a silver halide photographic light-sensitive material capable of obtaining a high quality image.

[0015]

The above object of the present invention can be achieved by the following constitutions.

1. The silver halide composition has a silver chloride content of 10 mol% or more and a silver bromide content of 0.1 mol% or more, and is represented by at least one compound represented by the following general formula (I) and the following general formula (II). A silver halide photographic emulsion containing silver halide grains containing at least one of the compounds described above.

General formula (I) Y ₁ n ₁₁ M ₁ Brn ₁₂ X ₁ n ₁₃ [wherein M ₁ is rhenium, ruthenium, osmium,
An ion selected from platinum, palladium and iridium, Y ₁ is a cation paired with the complex anion of M ₁ , X ₁
Represents a ligand capable of coordinating to M ₁ (excluding cyanide ion). n ₁₁ represents an integer of 0 to 3, n ₁₂ , n
₁₃ is 0 satisfying n ₁₂ ≧ n ₁₃ , n ₁₂ + n ₁₃ = 4 or 6
During 6 of an integer] general formula _{(II) Y 2 n 21 M} 2 (CN) n 22 X 2 n 23 [wherein, M ₂ is an ion selected from the Periodic Table Group 7-10 element, Y ₂ is a cation paired with the complex anion of M ₂ ,
X ₂ represents a ligand capable of coordinating with M ₂ . n ₂₁ represents an integer of 0 to 4, n _22, n ₂₃ represents an integer of 0 to 6 satisfying n ₂₂ + n ₂₃ = 4 or 6 (however, n ₂₂ is 0 and not)] 2. In a silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on a support having an oxygen permeability of 2.0 ml / m ² · hr · atm or less, at least one halogen in the silver halide photographic emulsion layer A silver halide photographic light-sensitive material, wherein the silver halide photographic emulsion is the silver halide photographic emulsion described in 1 above.

3. 3. The silver halide photographic light-sensitive material as described in 2 above, wherein in the general formula (II), M ₂ is iron ion and n ₂₂ is 6.

The present invention will be described in detail below.

The compound represented by the general formula (I) of the present invention is a compound generally called a complex salt or a complex, and is characterized by having at least one bromide ion as a ligand. There is. M ₁ in the general formula (I) is an ion selected from rhenium, ruthenium, osmium, platinum, palladium and iridium, preferably iridium, palladium and platinum, more preferably iridium. The ligand represented by X ₁ is, for example, halide ion, water, ammonia, hydroxide ion,
Such as nitrosyl. Y ₁ is a cation that forms a pair with the complex anion of M ₁ , and examples thereof include alkali metals such as potassium and sodium. n ₁₁ represents an integer of 0 to 3, n ₁₂ , n
₁₃ is 0 to satisfy n ₁₂ ≧ n ₁₃ , n ₁₂ + n ₁₃ = 4 or 6
Represents an integer of 6.

Examples of the compound represented by formula (I) of the present invention are shown below, but the invention is not limited thereto.

(I-1) K ₃ RuBr ₆ (I-2) K ₂ RuBr ₆ (I-3) Na ₃ RuBr ₆ (I-4) Na ₂ RuBr ₆ (I-5) K ₃ RuBr ₄ Cl ₂ (I-6) K ₂ RuBr ₄ Cl ₂ (I-7) K ₂ RuBr ₃ Cl ₃ (I-8) K ₃ RuBr ₃ Cl ₃ (I-9) K ₃ RuBr ₅ Cl (I-10) K ₂ RuBr ₅ Cl (I-11) K ₃ RuBr ₅ (H ₂ O) (I-12) K ₃ RuBr ₄ (H ₂ O) ₂ (I-13) K ₃ RuBr ₅ I (I-14) K ₂ RuBr ₅ I (I-15) K ₃ IrBr ₆ (I-16) K ₂ IrBr ₆ (I-17) Na ₃ IrBr ₆ (I-18) Na ₂ IrBr ₆ (I-19) K ₃ IrBr ₄ Cl ₂ ( I-20) K ₂ IrBr ₄ Cl ₂ (I-21) K ₂ IrBr ₃ Cl ₃ (I-22) K ₃ IrBr ₃ Cl ₃ (I-23) K ₃ IrBr ₅ Cl (I-24) K ₂ IrBr ₅ Cl (I-25) K ₃ IrBr ₅ (H ₂ O) (I-26) K ₃ IrBr ₄ (H ₂ O) ₂ (I-27) K ₃ IrBr ₅ I (I-28) K ₂ IrBr ₅ I (I-29) K ₃ OsBr ₆ (I-30) K ₂ OsBr ₆ (I-31) Na ₃ OsBr ₆ (I-32) Na ₂ OsBr ₆ (I-33) K ₃ OsBr ₄ Cl ₂ (I -34) K ₂ OsBr ₄ Cl ₂ (I-35) K ₂ OsBr3Cl ₃ (I-36) K ₃ OsBr ₃ Cl ₃ (I-37) K ₃ OsBr ₅ Cl (I-38) K ₂ OsBr ₅ Cl ( I-39) K ₃ OsBr ₅ (H ₂ O) (I-40) K ₃ OsBr ₄ (H ₂ O) ₂ (I-41) K ₃ OsBr ₅ I (I-42) K ₂ OsBr ₅ I (I -43) K ₃ ReBr ₆ (I-44) K ₂ ReBr ₆ (I-45) Na ₃ ReBr ₆ (I-46) Na ₂ ReBr ₆ (I-47) K ₃ ReBr 4Cl ₂ (I-48) K ₂ ReBr ₄ Cl ₂ (I-49) K ₂ ReBr ₃ Cl ₃ (I-50) K ₃ ReBr ₃ Cl ₃ (I-51) K ₃ ReBr ₅ Cl (I-52) K ₂ ReBr ₅ Cl (I-53) K ₃ ReBr ₅ (H ₂ O) (I-54) K ₃ ReBr ₄ (H ₂ O) ₂ (I-55) K ₃ ReBr ₅ I (I-56) K ₂ ReBr ₅ I (I-57) K ₂ PdBr ₄ (I-58) K ₂ PdBr ₆ (I-59) Na ₂ PdBr ₄ (I-60) K ₂ PtBr ₄ (I-61) K ₂ PtBr ₆ (I-62) K ₂ Ru (NO) Br ₅ (I-63) K ₂ Os (NS) Br ₅ The compound of the general formula (II) used in the present invention is generally a complex salt,
Or a compound called a complex, at least 1
It is characterized by having one cyano ligand. General formula (I
M _{2 in} I) is Group 7 to Group 10 of the Periodic Table (according to the revised IUPAC Nomenclature of Inorganic Chemistry (1989)), and among these metals,
Preferred are iridium, ruthenium, cobalt, rhenium, osmium and iron, more preferred metal is iron.

Examples of Y ₂ include a cation paired with the complex anion of M ₂ , for example, an alkali metal ion such as potassium or sodium.

The ligand represented by X ₂ is, for example, a halide ion, water, a hydroxide ion, nitrosyl or the like.

N ₂₁ represents an integer of 0 to 4, n ₂₂ and n ₂₃ represent an integer of 0 to 6 satisfying n ₂₂ + n ₂₃ = 4 or 6 (however, n ₂₂ does not become 0).

The compound represented by formula (II) is most preferably a hexacoordinate cyano complex. Examples of the compound represented by the general formula (II) are shown below, but the invention is not limited thereto.

(II-1) K ₂ Ni (CN) ₄ (II-2) K ₂ Fe (NO) (CN) ₅ (II-3) K ₂ Ru (NS) (CN) ₅ (II-4) K ₂ Ir (CN) ₅ Cl (II-5) K ₂ Re (NO) (CN) ₅ (II-6) K ₃ Fe (CN) ₆ (II-7) K ₄ Fe (CN) ₆ (II- 8) K ₄ Ru (CN) ₆ (II-9) K ₃ Ir (CN) ₆ (II-10) K ₃ Co (CN) ₆ (II-11) K ₄ Re (CN) ₆ General formula of the present invention Compounds represented by formula (I) and general formula (II) (hereinafter referred to as "compound (I)" and "compound (II)", respectively)
To prepare silver halide photographic emulsion grains containing
The compound may be added to the mixing vessel before the formation of the silver halide grains, or may be continuously added during the whole or a part of the process during the formation of the silver halide grains.
At this time, the compound may be added alone as a solution or may be dissolved together with a halide salt and added.
It may also be added during physical ripening after the formation of silver halide grains. These compounds may be added to the same position of the silver halide grain or may be added to different regions.

When the compound (I) is added to the silver halide photographic emulsion, the amount is 1 × 10 ^-9 per mol of silver halide.
More than or equal to 1 × 10 ^-2 mol is more preferable, especially 1 ×
It is preferably 10 ⁻⁸ mol or more and 5 × 10 ⁻⁶ mol or less.

The amount of the compound (II) added to the silver halide photographic emulsion is 1 × 10 ^-9 per mol of silver halide.
More than or equal to 1 × 10 ^-2 mol is more preferable, especially 1 ×
It is preferably 10 ⁻⁷ mol or more and 5 × 10 ⁻⁴ mol or less.

The silver halide grains of the present invention have a halogen composition having a silver chloride content of 10 mol% or more and a silver bromide content of 0.1 mol% or more. Preferably, it is a silver chlorobromide grain substantially containing no iodine, and the silver chloride content is preferably 95 mol% or more and 99.9 mol% or less, more preferably 98 to 99.9 mol%. . The silver bromide content is preferably 0.
It is 1 to 2.0 mol%.

The silver halide grains of the present invention may be grains having a uniform composition or grains having a localized silver bromide phase on the surface or inside thereof. The silver halide photographic emulsion of the present invention comprises
Silver halide grains other than the silver halide grains of the present invention may be contained within a range not impairing the effects of the present invention.
The grain size of the silver halide grains of the present invention is not particularly limited,
Considering photographic performance such as rapid processability and sensitivity,
It is preferably 3 μm or less, more preferably 2.0 μm or less, still more preferably 1.2 μm or less. The grain size of silver halide grains can be measured by various methods generally used in the technical field. A typical method is Loveland's "particle size analysis method" (A.
STM Symposium on Right Microscopy, pages 94-122, 1955) or the method described in "Theory of Photographic Processes, Third Edition" (Mies and James, Chapter 2, Macmillan, 1966). Can be mentioned.

This particle size can be expressed using the diameter of a circle having the same projected area as the projected area of the particle.

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 a silver halide photographic emulsion, various methods known in the art can be used.

The silver halide photographic emulsion of the present invention 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.

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 the reaction mother liquor as disclosed in JP-A-57-92523 and 57-92524, published in Germany. An apparatus for continuously changing the concentration of a water-soluble silver salt and a water-soluble halide salt aqueous solution described in Patent 2,921,164, etc., and taking out the reaction mother liquor from the reactor described in JP-B-56-501776 and the like, 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, a silver halide solvent such as thioether may be used if necessary. Also, aminoazaindene, pyrimidine, aminoazine, thiourea, triazole, 3-amino-1H-1,2,4triazole, 3,5-diamino1H-
A crystal habit controlling agent such as 1,2,4 triazole, imidazole or xanthinoid, a compound having a mercapto group or a compound such as a sensitizing dye may be added during the formation of silver halide grains.

As the sulfur sensitizer applied to the silver halide photographic emulsion used in the present invention, thiosulfate, allylthiocarbamidothiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, triethylthio. Examples include urea and inorganic sulfur. The addition amount of the sulfur sensitizer used in chemically ripening the silver halide photographic emulsion used in the present invention is preferably changed depending on the silver halide photographic emulsion to be applied, but it is 5 × per mol of silver halide. A range of 10 ^{−10 to} 5 × 10 ⁻⁵ mol,
The range of 5 × 10 ^{−8 to} 3 × 10 ⁻⁵ mol is preferable.

As the gold sensitizer used when chemically sensitizing the silver halide photographic emulsion of the present invention, various gold complexes other than chloroauric acid, gold sulfide and the like 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), (I-21), described in JP-A-5-113617, pages 118-123. IV-
1) and (V-1) can be mentioned. The amount of the gold compound, the kind of silver halide photographic emulsion, the type of compound used, but are not and ripening conditions, is usually 1 mol of silver halide per 1 × 10 ^-4 mol to 1 × 10 ^- It is preferably ⁸ mol. More preferably 1 × 10 ⁻⁵ mol to 1 ×
It is 10 ^-8 mol.

The silver halide photographic emulsion of the present invention has the purpose of preventing fog that occurs during the process of preparing a silver halide photographic light-sensitive material, reducing performance fluctuations during storage, and preventing fog that occurs during development. Although the antifoggants and stabilizers known in (1) can be used, the compound represented by the following general formula (IV) is preferable.

[0043]

Embedded image

In the formula, Q represents an atomic group necessary for forming a nitrogen-containing heterocycle optionally having a substituent or a nitrogen-containing heterocycle condensed with a benzene ring.

M represents a hydrogen atom, an alkali metal atom or an ammonium group.

Examples of the nitrogen-containing heterocycle formed by Q in the general formula (IV) include an imidazole ring, a triazole ring, a tetrazole ring, a thiazole ring, an oxazole ring,
Examples thereof include selenazole ring, thiadiazole ring, benzimidazole ring, naphthimidazole ring, benzothiazole ring, naphthothiazole ring, benzoselenazole ring and benzoxazole ring.

Of these compounds, those having a tetrazole ring are preferably used.

Specific examples of the compound represented by formula (IV) are shown below.

[0049]

Embedded image

[0050]

[Chemical 3]

These compounds are added in the steps of preparing silver halide photographic emulsion grains, chemical sensitization step, completion of chemical sensitization step, coating solution preparation step and the like depending on the purpose. When chemical sensitization is carried out in the presence of these compounds, 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol per mol of silver halide.
It is preferably used in a molar amount. When added at the end of chemical sensitization, the amount is preferably about 1 × 10 ⁻⁶ mol to 1 × 10 ⁻² mol per mol of silver halide, and 1 × 10 ⁻⁵ mol to about 1 × 10 ⁻⁵ mol.
5 × 10 ⁻³ mol is more preferable. When added to the silver halide photographic emulsion layer in the coating solution 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. More preferably, it is 1 × 10 ^-2 mol. When it is added to a layer other than the silver halide photographic emulsion layer, the amount in the coating film is preferably about 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mol per 1 m ² .

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

Any known compound can be used as the spectral sensitizing dye used in the silver halide photographic emulsion of the present invention, and as the blue-sensitive sensitizing dye, JP-A-3-25 can be used.
BS-1 to BS-8 described on page 28 of JP 1840 can be preferably used alone or in combination. Examples of the green-sensitizing sensitizing dye include GS-1 to GS-1 described on page 28 of the same publication.
5 is 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.
4-285950, IRS-1 to 11 described in pages 6 to 8
The above dyes 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 addition amount of the sensitizing dye depends on the kind of the sensitizing dye, the halogen composition of the silver halide photographic emulsion to be applied, the grain size and the like, but is preferably 5 × 10 ⁻⁵ to 1 mol of silver halide. 4 × 10 ⁻³ mol, more preferably 1 × 10 ⁻⁴
It is used in the range of 1 × 10 ⁻³ mol.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization. Further, as a method of adding these dyes, water or methanol, ethanol, fluorinated alcohol, acetone, may be dissolved in a water-miscible organic solvent such as dimethylformamide and added as a solution, or dissolved. Alternatively, it may be added as a dispersed suspension.

The silver halide photographic light-sensitive material of the present invention comprises
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. Particularly, as the dye having absorption in the visible region, the dyes disclosed in JP-A
The dyes of AI-1 to 11 described on page 308 of JP-A 3-251840 are preferably used, and as the infrared absorbing dye, the general formula described in JP-A 1-280750, page 2, lower left column
The compounds represented by formulas (I), (II) and (III) have preferable spectral characteristics, and are preferable because they do not affect the photographic characteristics of the silver halide photographic emulsion and stain 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.

The coupler used in the silver halide photographic light-sensitive material of the present invention forms 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. Although any compound to be obtained can be used, particularly typical ones include 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, and a wavelength. The one known as a cyan coupler having a spectral absorption maximum wavelength in the region of 600 to 750 nm is typical.

The coupler used in the silver halide photographic light-sensitive material of the present invention forms 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. Although any compound to be obtained can be used, particularly typical ones include 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, and a wavelength. The one known as a cyan coupler having a spectral absorption maximum wavelength in the region of 600 to 750 nm is typical.

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

As the magenta coupler which can be preferably used in the silver halide photographic light-sensitive material of the present invention, a compound represented by the general formula (M-
Examples thereof include couplers represented by I) and (M-II). Specific compounds include those described as MC-1 to MC-11 in 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 from blue to purple and red and are excellent in the depiction of details.

The yellow coupler which can be preferably used in the silver halide photographic light-sensitive material of the present invention is represented by the general formula (YI) described in JP-A-4-114154, page 3, upper right column.
A coupler represented by Specific compounds are described in YC-1 to YC- in the lower left column on page 3 of the same publication.
Those listed as 9 can be mentioned. Among them, YC-8 described in the upper left column on page 4 of the publication,
YC-9 is preferable because it 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, it is usually added to a water-insoluble high-boiling point organic solvent having a boiling point of 150 ° C. or higher, if necessary. A low-boiling point and / or water-soluble organic solvent is 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).

The compound (d-1) described on page 33 of JP-A-4-114152 is used for the purpose of shifting the absorption wavelength of the color forming dye.
Compounds such as the compound (A'-1) described in 1) and page 35 of the patent can be used. Other than this, the fluorescent dye-releasing compounds described in US Pat. No. 4,774,187 can also be used.

It is advantageous to use gelatin as a binder that can be used in preparing a silver halide photographic light-sensitive material using the silver halide photographic emulsion of the present invention, but if necessary, other gelatin, A hydrophilic colloid such as a gelatin derivative, a graft polymer of gelatin and another polymer, a protein other than gelatin, a sugar derivative, a cellulose derivative, or a synthetic hydrophilic polymer substance such as a homopolymer or a copolymer can also be used.

The support of the present invention has an oxygen permeability of 2.0 ml / m 2.
It is characterized by being less than ² · hr · atm. The increase of fog during the drying of a silver halide photographic light-sensitive material is a problem that appears remarkably on such a support having a low oxygen permeability, and the present invention solves the problem under such conditions. is there. The oxygen permeability of the support can be measured by a known method, and for example, the method defined in ASTM D-1434 method can be used. Oxygen permeability 2.0 ml / m ² · hr · a
When any of the known supports having a thickness of tm or less is used, the above problem occurs, but the silver halide photographic light-sensitive material of the present invention solves this problem. Examples of such a support having a low oxygen permeability include various plastic films.

As the polymer forming the plastic film, homopolymers or copolymers of polyester (eg polyethylene terephthalate), vinyl alcohol, vinyl chloride, vinyl fluoride, vinyl acetate, etc.,
Examples thereof include homopolymers and copolymers of cellulose acetate, acrylonitrile, acrylic acid alkyl ester, methacrylic acid alkyl ester, methacrylonitrile, alkyl vinyl ester, alkyl vinyl ether, polyamide and the like. Particularly preferred of these polymers is polyester.

These plastic films can be used as a transparent support, or can be used as a reflective support by incorporating a white pigment in the plastic film. Further, by providing a hydrophilic colloid layer containing a white pigment on the transparent support, a light-sensitive material similar to the reflective support can be obtained.

As the white pigment used for the reflective support, at least one compound selected from inorganic and organic white pigments can be used, and preferably inorganic white pigment is 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, oxidation Examples include titanium, zinc oxide, talc and clay. The white pigment is preferably barium sulfate or titanium oxide.

When a hydrophilic colloid layer containing a white pigment is provided on a support, examples of the white pigment include rutile type titanium dioxide, anatase type titanium dioxide, barium sulfate, barium stearate, silica, alumina,
Zirconium oxide, kaolin and the like can be used.
Of these, titanium dioxide is preferably used. The white pigment is dispersed in a hydrophilic colloid capable of penetrating a processing liquid such as gelatin and applied as a hydrophilic colloid layer. The amount of white pigment applied is usually in the range of 0.1 to 50 g per m ² , and more preferably 0.5 to 10 g.

In addition to the white pigment, colorants such as yellow, gray, blue and black colloidal silver, inorganic colored pigments, organic colored pigments and dyes can be added to the hydrophilic colloid layer. As the colorant, various known filter dyes can be used in addition to yellow, gray, blue and black colloidal silver.

Further, the hydrophilic colloid layer may contain hollow fine particles such as microcapsules containing air. As a material for forming such microcapsules, use polyvinyl chloride, polystyrene, polyvinyl acetate, vinyl chloride-vinylidene chloride copolymer, cellulose acetate, ethyl cellulose, novolac resin, polymethyl methacrylate, polyacrylamide, etc. However, a styrene-acrylic acid copolymer is preferable.
By including these, sharpness can be improved and the detail descriptive power of the highlight part can be enhanced.

Further, in the silver halide photographic light-sensitive material of 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, etc. are known, and in the silver halide photographic light-sensitive material of the present invention. Any known hardener can be preferably used.

In the photographic emulsion layer and other hydrophilic colloid layers of the silver halide photographic light-sensitive material of the present invention, an antifungal agent typified by phenol is generally used for the purpose of preventing the decay of hydrophilic colloid such as gelatin. Use agents.

The silver halide photographic light-sensitive material of the present invention comprises
In addition to the above compounds, various photographic additives can be added.

As such an example, for example, an ultraviolet absorber (for example, benzophenone compound, benzotriazole compound, etc.), a development accelerator (for example, 1-aryl-3-pyrazolidone compound, etc.), a film physical property improving agent (liquid) Paraffin, polyalkylene glycol, etc.), color turbidity preventing agent (diffusion-resistant hydroquinone compound, etc.), color image stabilizer (eg hydroquinone derivative, gallic acid derivative, etc.), water-soluble or oil-soluble fluorescent brightener, ground color tone There are regulators, etc.

In addition to these, competitive couplers, fogging agents, development inhibitor-releasing couplers (so-called DIR couplers), development inhibitor-releasing compounds and the like can be added if necessary.

The light-sensitive material using the silver halide photographic emulsion of the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment or the like on the surface of the support, if necessary, and then directly or undercoat layer (on the surface of the support) Applied via one or more subbing layers) to improve adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, antihalation properties, friction properties and / or other properties) May be.

At the time of coating the light-sensitive material, a thickener may be used in order to improve coatability. As the coating method, extrusion coating and curtain coating which can simultaneously coat two or more layers are particularly useful.

To form a photographic image using the silver halide photographic light-sensitive material of 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 let it be baked,
Once the image is converted to digital information, the image is CRT
An image may be formed on a (cathode ray tube), and this image may be formed on a silver halide photographic light-sensitive material to be printed and printed, or scanning is performed by changing the intensity of laser light based on digital information. You may bake it.

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.

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 change 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, Technical Report of the Department of Electronic Communication, Volume 80, No. 244, and Movie Television Technical Journal 1984 / 6
(382), pages 34-36, etc.

As a light source used for exposing the silver halide photographic light-sensitive material of the present invention, a blue light source is a helium-cadmium laser (about 442 nm), a green light source is a helium-neon laser (about 544 nm), A gas laser such as a helium / neon laser (about 633 nm) or a semiconductor laser is preferably used as the red light source. Any semiconductor laser may be used as long as it has sufficient intensity at a predetermined wavelength, such as GaAsP and AlGaA.
s, InGaAsP, AlGaAsSb and the like. Among them, semiconductor lasers of 670, 750, 780, 810, 830 and 880 nm are advantageously used in terms of light intensity and handling of silver halide photographic light-sensitive materials. In addition, a solid-state laser used as an excitation light source, a light source combining a semiconductor laser and a non-linear optical element (SHG element), for example, a GaAlAs laser as an excitation light source is used to excite a YVO ₄ solid-state laser, and a second KTP crystal is used.
It is possible to use the one in which the higher harmonic is taken out, the one in which the YAG laser is excited by using the GaAlAs laser as the excitation light source, and the second higher harmonic is taken out by the KNbO ₃ crystal.

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

Known compounds can be used as the aromatic primary amine developing agent that can be used for developing the light-sensitive material using the silver halide photographic emulsion of the present invention. 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) methanesulfone Amido 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 The color developer used in the present invention contains In addition to the developing agent, Known developer component compounds can be added. Usually, an alkaline agent having a pH buffering action, a chloride ion, a development inhibitor such as benzotriazole, a preservative, a chelating agent and the like are used.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching treatment and fixing treatment after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process,
Usually, a washing process is 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. It may be an endless belt system in which the photosensitive material is fixed and conveyed,
A method of forming a processing tank in the shape of a slit and supplying the processing liquid to the processing tank while conveying the photosensitive material, a spray method of spraying the processing liquid, and a web method of contacting a carrier impregnated with the processing liquid. A method using a viscous treatment liquid can also be used.

[0090]

The present invention will be described in detail 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 a paper pulp having a basis weight of 180 g / m ² . However, on the side where the silver halide photographic emulsion layer was coated, a molten polyethylene containing 15% by weight of surface-treated anatase type titanium oxide dispersed therein was laminated to prepare a reflective support. The thickness of polyethylene at this time is 25μ on both sides.
m. 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 photographic 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 a coating aid, a surfactant (SU-
2) and (SU-3) were added to adjust the surface tension.

Using the coating solution prepared as described above,
A silver halide photographic light-sensitive material, Sample 101, was prepared. The layer structure is shown in the table below.

[0095]

[Table 1]

[0096]

[Chemical 4]

SU-1: Sodium tri-i-propylnaphthalene sulfonate SU-2: Di (2-ethylhexyl) sulfosuccinate sodium salt 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 photographic emulsion) Incubated at 40 ℃ 2 % (A solution) and (B solution) in 1 liter of gelatin aqueous solution
Was simultaneously added while controlling pHAg = 6.5 and pH = 3.0, and the following (C liquid) and (D liquid) were simultaneously added over 120 minutes while controlling pAg = 7.3 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 78.7 g Potassium bromide 0.157 g Water was added 446 ml (Solution D) 190 g of silver nitrate Water was added and 380 ml was added, and then desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate, and then mixed with a gelatin aqueous solution and averaged. A monodisperse cubic silver halide photographic emulsion (EMP-101) having a grain size of 0.40 μm, a coefficient of variation (S / R) = 0.07 and a silver chloride content of 99.5 mol% was obtained.

EMP-101 means the compound (V-
A silver halide photographic emulsion was prepared, which was different only in that 1) was added at 1 × 10 ^-8 mol per mol of silver halide.
It was set to EMP-102.

V-1: K ₂ IrCl ₆ Next, EMP-102 means the compound (II-1) in addition to the compound (V-1) in (C liquid) at 1 × 10 ⁻⁷ mol per silver mol. A silver halide photographic emulsion was prepared which differed only in the addition, and was designated as EMP-103.

In the preparation of EMP-103, (C solution) was replaced with (E
Liquid): (F liquid) = 3: 1 divided into (F liquid)
To the compound (V-1) and the compound (II-6) so that the content per silver mole is equal to EMP-103.
Solution) and (solution F) were added in this order, and the compound (V
EMP-104 was prepared by preparing a silver halide photographic emulsion having different regions containing -1) and compound (II-6).

In the preparation of EMP-103, the compound (I-16) was used instead of (V-1) to obtain EMP-105.

Furthermore, in the preparation of EMP-102, (V-
Compound (I-16) was used instead of 1) to obtain EMP-106.
And

(Preparation of Green-Sensitive Silver Halide Photographic Emulsion) Next, (EMP-101) was optimally chemically sensitized with the following compound at 60 ° C. to obtain a green-sensitive silver halide photographic emulsion (Em-G
I got 101).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer (IV-10) 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye (GS-1) 3 × 10 ⁻⁴ mol / Molar AgX

[0106]

[Chemical 5]

Green-sensitive silver halide photographic emulsion Em-G102 was prepared in the same manner as in the preparation of green-sensitive silver halide photographic emulsion Em-G101 except that EMP-101 was replaced with EMP-102 to EMP-106.
~ Em-G106 was prepared.

In the preparation of Sample 101, Em-G101 was replaced with Em-G
102-Em-G106
6 was prepared.

The samples thus obtained were evaluated for sensitometry, reciprocity law failure, and latent image stability by the following methods, and the results are shown in Table 2.

(1) Sensitometry After wedge exposure with green light for 0.05 seconds and color development according to the following processing steps, the density was measured using an optical densitometer PDA-65 (manufactured by Konica Corporation). , The sensitivity is expressed by the reciprocal of the exposure amount required to obtain a density 0.8 higher than the fog density, and is expressed as a relative value with Sample 101 as 100. The gradation is the average slope of the characteristic curve between 0.2 and 0.7 higher than the fog density.

(2) Latent Image Stability The density of the sample developed after 10 seconds (reference) after exposure to green light and 5 minutes and 48 hours after development was measured, and 5 minutes and 48 minutes after exposure. The latent image stability was evaluated by the following ΔS, Δγ, S, and γ, which represent the difference between the sensitivity when the development processing was performed for a certain time, the gradation, and the sensitivity when the development processing was performed 10 seconds after exposure and the gradation.

ΔS = S (development at 5 minutes and 48 hours after exposure)
/ S (developed 10 seconds after exposure) Δγ = γ (developed 5 minutes and 48 hours after exposure) -γ (post exposure)
Development in 10 seconds) S: Logarithm of reciprocal of exposure required to obtain density higher than fog density γ: Average slope of characteristic curve between density higher than fog density and higher than fog density (3) Reciprocity law Failure property Wedge exposure was performed with green light under the same conditions as in the above sensitometry with an exposure time of 10 seconds, and the sensitivity was expressed as a relative value with the sensitivity at exposure time 0.05 seconds being 100.

The development processing steps and processing solution formulations were as follows. The amount of replenishment is expressed by the amount per 1 m ² of the photographic material. The silver halide photographic light-sensitive materials Nos. 101 to 114 prepared using this silver halide photographic emulsion were subjected to optical wedge exposure by a conventional method and then subjected to the following development processing. 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.

(Processing step) Processing step Processing temperature Time Replenishment amount Color development 35.0 ± 0.3 ℃ 45 seconds 80 ml Bleach fixing 35.0 ± 0.5 ℃ 45 seconds 80 ml Stabilization 30-34 ℃ 90 seconds 250 ml Dry 60-80 ℃ 60 seconds Development The compositions of the tank liquid and the replenisher of the processing liquid are shown below.

(Color developer 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 sulfone Acid derivative) 1.0g 1.8g Potassium carbonate 27g 27g Add water to make the total volume 1 liter.
Adjust to 10 and replenisher to pH = 10.60.

(Bleach-fixing solution tank solution and replenishing solution) 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 To 1 liter and adjust to pH = 5.7 with potassium carbonate or glacial acetic acid.

(Stabilizing Solution Tank Solution and Replenishing Solution) 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 Fluorescent whitening agent (4,4'-diaminostilbenedisulfonic 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.

[0118]

[Chemical 6]

[0119]

[Table 2]

As can be seen from Table 2, compound (V-1)
The silver halide photographic emulsion containing (A) is more excellent in reciprocity law failure than the one not containing (V-1), but the latent image stability is deteriorated immediately to 5 minutes, and the fluctuation of γ becomes large. When the compounds (V-1) and (II-6) are contained, the reciprocity law failure is improved, but the latent image stability is not sufficiently improved. In the silver halide photographic emulsion containing the compounds (V-1) and (II-6) at the same time on the surface layer side, the reciprocity law failure and the initial latent image stability are not sufficiently improved, and No improvement in latent image stability is seen. The silver halide photographic emulsion containing the compound (I-16) is excellent in reciprocity law failure and latent image stability in a short time from exposure to development, but the required time from exposure to development is 48 hours. At that time, sensitivity fluctuation was observed, and it was found that the latent image stability was poor.

The compound having a bromine ligand of the present invention (I-
16) and a compound (II-6) having a cyano ligand, reciprocity law failure characteristics, latent image stability with time change from exposure to development processing (immediately to 5 minutes, immediately to 48 hours) Was confirmed to be improved.

Example 2 In the same manner as in the preparation of Samples 101 to 106 of Example 1, except that the support was changed from a polyethylene-coated paper support to a polyester film support containing 100 g of polyethylene terephthalate and 20 g of barium sulfate. Sample 201
~ 206 was prepared. Similarly, in the preparation of Samples 205 and 206, the support was changed to a vinyl chloride-vinylidene chloride copolymer resin film support containing 20 g of barium sulfate in 100 g of vinyl chloride-vinylidene chloride copolymer resin to prepare Sample 20.
7, 208 was prepared.

The oxygen permeability of each support was measured under the conditions of 20 ° C.
410 ml / m ² · hr · atm, 0.3 ml / m ² · for polyester support
hr · atm, 0.5 ml / m ² · hr · atm for the vinyl trichloride-vinylidene chloride copolymer resin film support.

The samples thus obtained were evaluated for sensitometry and dry fog density by the following methods, and the results are shown in Table 3.

(1) Dry Fog After drying the coated sample at 40 ° C. and 60 ° C., the unexposed sample was color-developed and processed with an optical densitometer (X-RITE; 310 Photog).
Raphic Densitometer) to measure the concentration, drying temperature 40
The difference between the fog when the temperature was set to ℃ and the fog when the drying temperature was set to 60 ℃ was expressed as ΔFog.

ΔFog = Fog ₁ (drying temperature 60 ° C.) − Fog ₂ (drying temperature 40 ° C.)

[0127]

[Table 3]

As can be seen from Table 3, when a support having a low oxygen transmission rate is used, the dry fog resistance is greatly deteriorated. It can be seen that when the silver halide photographic emulsion of the present invention is used, even if a support having a low oxygen transmission rate is used, the deterioration of fog caused when the drying conditions are changed is hardly seen. It was also confirmed that the effects of the present invention of reciprocity law failure and improvement of latent image stability can be obtained without being affected by the type of the support.

Example 3 In the preparation of the silver halide photographic emulsion (EMP-106) of Example 1, a silver halide photographic emulsion was prepared by changing various kinds of compounds to be added.

For some silver halide photographic emulsions,
Silver halide photographic emulsions were prepared by changing the amounts of potassium bromide of the silver halides of (A liquid) and (C liquid) to 7 mol%. Using this, Em-G301 to Em-G313 were prepared in the same manner as in Example 1 except that EMP-106 was replaced with the above silver halide photographic emulsion. The contents are shown in Table 4.

[0131]

[Table 4]

Then, silver halide photographic light-sensitive materials, Samples 301 to 313, were prepared in the same manner as in Sample 206 of Example 2.

In the same manner as in Example 1, sensitometry, reciprocity law failure characteristics, latent image stability, and dry fog resistance were evaluated. The results are shown in Table 5 below.

[0134]

[Table 5]

It has been confirmed that the silver halide photographic emulsions of the present invention are excellent in reciprocity law failure and latent image stability, regardless of the type of compound, and the dry fog resistance during coating is improved. Regarding the influence of the silver halide composition, the higher the silver chloride content, the more the dry fog resistance tends to deteriorate, but when the silver halide photographic emulsion of the present invention is used, the effect is improved regardless of the silver halide composition. It was confirmed that the effect was obtained.

Example 4 In the preparation of the silver halide photographic emulsion (Em-G106) of Example 1, the additive (IV-10) was used in combination with the additive (IV-10),
(IV-9) and (STAB-1) were used only to prepare silver halide photographic emulsions, and these were each used as Em-G4.
01, Em-G402 and Em-G403.

Combined Stabilizer 1 × 10 ⁻⁴ mol / mol AgX STAB-1: 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene Then, in the same manner as in Sample 206 of Example 2. Samples 401 to 403 were prepared as silver halide photographic light-sensitive materials.

In the same manner as in Example 1, sensitometry, reciprocity law failure characteristics, latent image stability, and dry fog resistance were evaluated. The results are shown in Table 6 below.

[0139]

[Table 6]

Stabilizers (IV-10), (IV-9), (STAB-1)
Are all well-known compounds effective for improving the fog resistance. Using samples 206, 401 to 403, evaluation of dry fog resistance was performed (IV-10), (IV
-9) confirmed that the effect was further improved,
No effect was observed with (STAB-1). From this,
It was found that a mercaptotetrazole compound is more preferable as the stabilizer used in the present invention.

Example 5 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 silver halide photographic emulsion layer was coated, a molten polyethylene containing 15% by weight of surface-treated anatase type titanium oxide dispersed therein 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 501.
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, anti-staining agent (HQ-1) 0.33 g, compound A5.
60 ml of ethyl acetate to 0 g and 5.0 g of high boiling organic solvent (DBP)
20% surfactant (SU-1)
A yellow coupler dispersion was prepared by emulsifying and dispersing in 220 ml of 10% gelatin aqueous solution containing 7 ml using an ultrasonic homogenizer. This dispersion was mixed with the following blue-sensitive silver halide photographic emulsion (Em-B501) to prepare a coating solution for the first layer.

The coating liquids for the second to seventh layers were also prepared so that the coating amounts shown in Tables 8 and 9 were the same as the coating liquids for the first layer.

As hardeners (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 .

[0144]

[Table 7]

[0145]

[Table 8]

[0146]

[Chemical 7]

[0147]

Embedded image

[0148]

[Chemical 9]

[0149]

[Chemical 10]

[0150]

[Chemical 11]

DOP: Di (2-ethylhexyl) phthalate PVP: Polyvinylpyrrolidone H-2: 2,4-dichloro-6-hydroxy-s-triazine / sodium Compound A: p- (t-octyl) phenol Blue-sensitive halogen The silver halide photographic emulsion and the green light-sensitive silver halide photographic emulsion were prepared by the following methods.

(Preparation of Blue-Sensitive Silver Halide Photographic Emulsion) In the preparation of (EMP-105) and (EMP-106) of Example 1, (A
(EMP-10 except that the addition time of liquid) to (D liquid) is changed.
5) A silver halide photographic emulsion was prepared in the same manner as (EMP-106). As a result, a cubic silver halide photographic emulsion having an average grain size of 0.85 μm and a silver chloride content of 99.5 mol% (EMP-50
1) and (EMP-502) were obtained.

Then, the silver halide photographic emulsion (EMP-50
1) and (EMP-502) were optimally chemically sensitized at 60 ° C using the following compounds to obtain a blue-sensitive silver halide photographic emulsion (Em-B
501) and (Em-B502) were obtained.

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer (IV-9) 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 photographic emulsion) Example 1 (EMP
-104) and (EMP-105) in preparation of (solution A) to (solution D)
A silver halide photographic emulsion was prepared in the same manner as in (EMP-104) and (EMP-105) except that the addition time was changed. This resulted in a cubic silver halide photographic emulsion with an average grain size of 0.50 μm.
(EMP-503) and (EMP-504) were obtained.

Then, the above silver halide photographic emulsion (EMP-50
3) and (EMP-504) were optimally chemically sensitized at 60 ° C. using the following compounds to obtain a red-sensitive silver halide photographic emulsion (Em-R
501) and (Em-R502) were obtained.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer (IV-10) 6 × 10 ⁻⁴ mol / mol AgX stabilizer (IV-19) 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

[0157]

[Chemical 12]

In preparing silver halide photographic light-sensitive material, Sample No. 501, a blue-sensitive silver halide photographic emulsion (Em-B501) was used.
To (Em-B502) and a green-sensitive silver halide photographic emulsion (Em-G10).
5) to (Em-G106) and red-sensitive silver halide photographic emulsion (Em-R
Sample No. 501 except that (501) was replaced with (Em-R502)
Sample No. 502 was prepared in the same manner as in. In addition, samples 501 and 5
Sample No. 50 was prepared in the same manner as in Sample Nos. 501 and 502, except that the paper support coated with polyethylene in the preparation of 02 was changed to a polyester film support containing 20 g of barium sulfate in 100 g of polyethylene terephthalate.
3, 504 were prepared.

Using the sample thus obtained, Example 1
Exposure and treatment were carried out in the same manner as in, and the same evaluation as in Example 1 was performed. The results are shown below.

[0160]

[Table 9]

As is clear from Table 9, even in the multilayer silver halide color photographic light-sensitive material, the great effect of the present invention is recognized in the improvement of reciprocity law failure characteristics, latent image stability and dry fog resistance. In particular, it can be seen that the sample 504 using a support having a low oxygen transmission rate is significantly superior in dry fog resistance to the comparative sample 503.

[0162]

INDUSTRIAL APPLICABILITY The silver halide photographic emulsion and the silver halide photographic light-sensitive material according to the present invention are excellent in reciprocity law failure characteristics and latent image stability, and are stable by improving the dry fog resistance at the time of coating for manufacturing a light-sensitive material. To obtain high quality images

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Claims (3)

[Claims] 1. A silver halide composition having a silver chloride content of 10 mol% or more and a silver bromide content of 0.1 mol% or more, and at least one compound represented by the following general formula (I): A silver halide photographic emulsion containing silver halide grains containing at least one compound represented by formula (II). General formula (I) Y ₁ n ₁₁ M ₁ Brn ₁₂ X ₁ n ₁₃ [wherein M ₁ is rhenium, ruthenium, osmium,
An ion selected from platinum, palladium and iridium, Y ₁ is a cation paired with the complex anion of M ₁ , X ₁
Represents a ligand capable of coordinating to M ₁ (excluding cyanide ion). n ₁₁ represents an integer of 0 to 3, n ₁₂ , n
₁₃ is 0 satisfying n ₁₂ ≧ n ₁₃ , n ₁₂ + n ₁₃ = 4 or 6
During 6 of an integer] general formula _{(II) Y 2 n 21 M} 2 (CN) n 22 X 2 n 23 [wherein, M ₂ is an ion selected from the Periodic Table Group 7-10 element, Y ₂ is a cation paired with the complex anion of M ₂ ,
X ₂ represents a ligand capable of coordinating with M ₂ . n ₂₁ represents an integer of 0 to 4, n _22, n ₂₃ represents an integer of 0 to 6 satisfying n ₂₂ + n ₂₃ = 4 or 6 (however, n ₂₂ is 0 and not)] 2. A silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on a support having an oxygen transmission rate of 2.0 ml / m ² · hr · atm or less, said silver halide photographic emulsion layer. 2. A silver halide photographic light-sensitive material characterized in that at least one layer of the silver halide photographic emulsion of claim 1 is the silver halide photographic emulsion of claim 1. 3. The silver halide photographic light-sensitive material according to claim 2, wherein in the general formula (II), M ₂ is iron ion and n ₂₂ is 6.