JPH1184604A - Silver halide emulsion, silver halide photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide emulsion and a silver halide photographic sensitive material excellent in gradation, having natural high image forming ability from a highlight part to a shadow part and maintaining superior gradation even in rapid processing and processing under slight replenishment. SOLUTION: This emulsion contains plural silver halide emulsions having sensitivities close to each other, 0-95% of the effective sensitivity range of the lower sensitivity emulsion overlaps the effective sensitivity range of the higher sensitivity emulsion and 50-100% of the effective sensitivity range of the higher sensitivity emulsion overlaps the effective sensitivity range of the lower sensitivity emulsion. This photographic sensitive material contains plural emulsions different in sensitivity so that at least one of the overlaps is <50% or >95%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide emulsion, a silver halide photographic light-sensitive material and an image forming method capable of obtaining a high-quality image. The present invention relates to a silver halide emulsion, a silver halide photographic light-sensitive material, and an image forming method which have a natural and high definition and maintain excellent gradation even in rapid processing and low replenishment processing.

[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, excellent gradation and sharpness.

In the case of silver halide photographic light-sensitive materials, for example, in the case of a photographic light-sensitive material for printing, it is necessary to make the gradation of a highlight part gentle and the gradation of a shoulder part of a high density part hard. . Further, particularly strict requirements are placed on the gradation from the highlight portion to the shadow portion. Also,
It is also required to maintain the above-mentioned preferable gradation even in rapid processing and low replenishment processing.

As a technique for imparting these required gradation properties, silver halide emulsions having substantially the same spectral sensitivity and different sensitivities that develop substantially the same hue are mixed and / or used. It is known to have a plurality of silver halide emulsion layers having substantially the same spectral sensitivity and different sensitivities that develop substantially the same hue. For example, JP
No. 1-116350 discloses a mixture of at least two emulsions having different sensitizing dye amounts added to silver halide grains having substantially the same average grain size and having a relative sensitivity difference of 25% or more. A technique for obtaining a silver halide photographic light-sensitive material having a favorable gradation property by containing the same is disclosed. However, when the human face of the scene is adjusted to have a preferable color balance, it is preferable in the entire region from the highlight portion to the shadow portion such that the color of the shadow portion disappears and the shadow portion lacks neutrality. This technique cannot solve the problem that the gradation cannot be maintained, and the problem that the preferable gradation can be maintained in rapid processing and low replenishment processing.

Japanese Patent Application Laid-Open No. 1-170938 discloses that silver halide grains contained in an emulsion layer close to a support have an average gradation of 5 times higher than silver halide grains contained in an upper emulsion layer. The technique of a black-and-white negative type silver halide photographic light-sensitive material having a low silver content of not less than 0.1% and a defined amount of coated silver is disclosed. However, this technology is a technology that suppresses the occurrence of roller marks while maintaining the current gradation, and is a preferable problem in the problem of compatibility between the human face and the gradation of the shadow portion, rapid processing, and low replenishment processing. It does not suggest any solution to the problem of maintaining tonality.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an excellent gradation property, which has a natural and high descriptive power from a highlight area to a shadow area, and maintains excellent gradation property even in rapid processing and low replenishment processing. It is an object of the present invention to provide a silver halide emulsion, a silver halide photographic light-sensitive material and an image forming method.

[0007]

The above objects of the present invention are as follows. 0% or more and 95% or less of the effective sensitivity range of the low sensitivity emulsion of the emulsion having close sensitivity overlaps with the effective sensitivity range of the high sensitivity emulsion, and 50% or more and 100% or less of the effective sensitivity range of the high sensitivity emulsion. Overlaps the effective sensitivity range of low sensitivity emulsion,
A silver halide emulsion comprising a plurality of silver halide emulsions having different sensitivities in which at least one of the overlapping ranges of the effective sensitivity ranges of the above emulsions is less than 50% or more than 95%;

[0008] 2. In a silver halide photographic material having a silver halide emulsion layer containing at least two or more dye image-forming couplers of substantially the same hue on a support, the sensitivity of the silver halide emulsion layer having a similar sensitivity is considered. 0% to 95% of the effective sensitivity area of the silver halide emulsion layer having a low sensitivity overlaps with the effective sensitivity area of the silver halide emulsion layer having a high sensitivity, and 50% of the effective sensitivity area of the silver halide emulsion layer having a high sensitivity. More than 100% or less overlaps the effective sensitivity range of the silver halide emulsion layer having low sensitivity, and at least one of the overlaps of the effective sensitivity range of the silver halide emulsion layer has a different sensitivity of less than 50% or more than 95%. A silver halide photographic material, characterized by having a silver halide emulsion layer of

3. 0% to 95% of the effective sensitivity range of the silver halide grains of the low-sensitivity emulsion of the emulsion having similar sensitivity overlaps with the effective sensitivity range of the high-sensitivity emulsion. More than 50% of sensitivity range 1
00% or less overlaps the effective sensitivity range of the silver halide grains of the low-sensitivity emulsion, and at least one of the overlaps of the effective sensitivity ranges of the silver halide grains of the emulsion has a sensitivity difference of less than 50% or more than 95%. A silver halide emulsion comprising a plurality of silver halide emulsions,

[0010] 4. 0% or more and 95% or less of the effective sensitivity range of the low sensitivity emulsion of the emulsion having close sensitivity overlaps with the effective sensitivity range of the high sensitivity emulsion, and 50% or more and 100% or less of the effective sensitivity range of the high sensitivity emulsion. A feature is provided by chemical sensitization and / or spectral sensitization that overlaps the effective sensitivity range of the low-sensitivity emulsion and that at least one of the overlaps of the effective sensitivity range of the emulsion is less than 50% or more than 95%. A silver halide emulsion comprising a plurality of silver halide emulsions having different sensitivities,

5. In a silver halide photographic material having a silver halide emulsion layer containing at least two or more dye image-forming couplers having substantially the same hue on a support, the sensitivity of the silver halide emulsion layer having a similar sensitivity is determined. 0% to 95% of the effective sensitivity range of the low-sensitivity silver halide emulsion layer overlaps with the effective sensitivity range of the high-sensitivity silver halide emulsion layer, and 50% or more of the effective sensitivity range of the high-sensitivity silver halide emulsion layer. A feature that 100% or less of the silver halide emulsion layer overlaps the effective sensitivity range of the low-sensitivity silver halide emulsion layer, and at least one of the overlaps of the effective sensitivity range of the silver halide emulsion layer is less than 50% or more than 95% is characterized by silver halide. A silver halide photographic light-sensitive material, which is provided by a dye image-forming coupler contained in an emulsion layer,

6. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, characterized in that the silver halide emulsion described in 1 above is contained in the silver halide emulsion layer. Photographic light-sensitive materials,

7. A silver halide photographic material having at least one silver halide emulsion layer on a support, characterized in that the silver halide emulsion described in 1 above is contained in the silver halide emulsion layer closest to the support. Silver halide photographic light-sensitive material,

8. A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion described in 1 above is contained in a yellow coloring emulsion layer. Photosensitive material,

9. Image forming method characterized in that the replenishing amount of the silver halide photographic light-sensitive material of the color developing solution of the above 2 or 3, wherein the treatment with a color developer is less than the photosensitive material 1 m ² per 120 ml,

10. 4. The image forming method according to the above 2 or 3, wherein the silver halide photographic material is processed with a color development processing time of 30 seconds or less.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The effective sensitivity range of the emulsion according to the present invention is determined by the exposure amount giving Dmin + 0.1 of the characteristic curve of the emulsion and the Dma of the characteristic curve.
It refers to an exposure area between the exposure amount giving x-0.1.

The characteristic curve of the emulsion according to the present invention was obtained by coating the emulsion according to the present invention on a reflective support by the method of Example 1 described later, and exposing and developing the prepared sample by a conventional method. It is obtained by measuring the density of the reflection sample and plotting the density against the common logarithm of the exposure amount. D in the present invention
max indicates the highest density on the characteristic curve, and Dmin indicates the minimum density. In the present invention, the effective sensitivity range of the emulsion is obtained from the characteristic curve when the coating conditions are set so that the Dmax of each emulsion is 2.0 to 2.5. Further, the sensitivity of the emulsion according to the present invention is obtained by calculating the characteristic curve of the emulsion as Dmin + 0.5 ×
It is defined by the reciprocal of the exposure amount that gives the density of (Dmax-Dmin).

The emulsion of the present invention may contain three or more kinds of emulsions. In this case, the overlap of the effective sensitivity ranges between two emulsions having close sensitivities satisfies the claims, and the overlap of the effective sensitivity ranges between emulsions mixed with the emulsion and emulsions having close sensitivities satisfies the claims. Fulfill. In the case of an emulsion containing a plurality of emulsions, all the emulsions satisfy the claims according to the above-mentioned method. When containing multiple emulsions,
The content ratio of each emulsion is such that the content ratio of the two emulsions having similar sensitivity is in the range of 10:90 to 90:10.
Other ratios are substantially the same as containing one type of emulsion, and the effect of the present invention cannot be obtained.

According to the present invention, 0% to 95% of the effective sensitivity range of the low-sensitivity emulsion of the emulsion having close sensitivity overlaps with the effective sensitivity range of the high-sensitivity emulsion, and the effective sensitivity range of the high-sensitivity emulsion is reduced. 50% or more and 100% or less overlap the effective sensitivity range of the low-sensitivity emulsion, and at least one of the overlaps of the effective sensitivity range of the emulsion has a sensitivity of less than 50% or more than 95%. It is a silver halide emulsion characterized by containing.

In particular, the effective sensitivity range of the emulsion of the present invention is such that 20% or more and 95% or less of the effective sensitivity range of the low-sensitivity emulsion of an emulsion having close sensitivity overlaps with the effective sensitivity range of a high-sensitivity emulsion. In addition, 60% or more and 100% or less of the effective sensitivity range of the high-sensitivity emulsion overlaps with the effective sensitivity range of the low-sensitivity emulsion, and at least one of the overlaps of the effective sensitivity ranges of the emulsions is less than 50% or exceeds 95%. Is preferred.

The silver halide grains of the silver halide emulsion according to the present invention may have any composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and silver chloroiodide. Although it may have a halogen composition, silver chlorobromide containing 95 mol% or more of silver chloride and containing substantially no silver iodide is preferred.
From the viewpoint of rapid processing property and processing stability, preferably 97 mol%
As described above, silver halide grains containing 98 to 99.9 mol% of silver chloride are more preferable.

The composition of the silver halide grains according to the present invention is as follows:
The silver halide grains may not be uniform among the silver halide grains, and the halogen composition may be changed so that the effective sensitivity range is within a preferable range.

In order to obtain the silver halide grains according to the present invention, silver halide grains having a portion containing silver bromide at a high concentration may be used. In this case, the portion containing a high concentration of silver bromide may be epitaxy-bonded to silver halide emulsion grains, a so-called core-shell emulsion, or may be formed only partially without forming a complete layer. May simply have regions with different compositions. Further, the composition may change continuously or discontinuously. It is particularly preferable that the portion where silver bromide exists at a high concentration is the top of crystal grains on the surface of silver halide grains. The silver bromide concentration and the size of the region where the silver bromide is present at a high concentration need not be uniform among the respective silver halide grains contained, and the effective sensitivity range is changed so as to be in a preferable range. You may.

In order to obtain the silver halide grains according to the present invention, it is advantageous to include heavy metal ions. Heavy metal ions that can be used for such purposes include iron,
Iridium, platinum, palladium, nickel, rhodium,
Examples include Group 8 to 10 metals such as osmium, ruthenium, and cobalt; Group 12 transition metals such as cadmium, zinc, and mercury; and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferred. These metal ions are
Salts and complex salts can be added to silver halide grains.

When the heavy metal ion forms a complex, its ligand or ion may be cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, nitrate ion, carbonyl ion. , Ammonia and the like. Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable.

In order to allow the silver halide grains according to the present invention to contain heavy metal ions, the heavy metal compound must be physically added to the silver halide grains before, during and after the formation of the silver halide grains. What is necessary is just to add in arbitrary places of each process during ripening. In order to obtain a silver halide emulsion satisfying the above conditions, a heavy metal compound can be dissolved together with a halide salt and added continuously over the whole or a part of the grain forming step.

The amount of the heavy metal ion added to the silver halide emulsion is 1 × 10 5 per mol of silver halide.
^-9 mol or more and 1 × 10 ⁻² mol or less are more preferable,
In particular, it is preferably from 1 × 10 ⁻⁸ mol to 5 × 10 ⁻⁵ mol.

The amount and type of heavy metal ions contained in the silver halide grains according to the present invention, and the location of the heavy metal ions during the addition step during grain formation may not be uniform among the contained silver halide grains. The effective sensitivity range may be changed so as to be in a preferable range.

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having a (100) plane as a crystal surface. U.S. Pat. Nos. 4,183,756 and 4,225,666;
JP-A-55-26589, JP-B-55-42737, and The Journal of Photographic Science (J. Photogr. Sci.) 21, 39.
(1973), etc., particles having an octahedral, tetradecahedral, dodecahedral shape or the like can be prepared and used. Further, particles having a twin plane may be used.

As the silver halide grains according to the present invention, grains having a single shape are preferably used, but it is particularly preferable to add two or more monodispersed silver halide emulsions to the same layer. Further, the shape of the silver halide grains according to the present invention may be changed so that the effective sensitivity range becomes a preferable range.

The grain size of the silver halide grains according to the present invention is not particularly limited, but is preferably 0.1 to 1.2 μm in consideration of other photographic properties such as rapid processing property and sensitivity.
m, more preferably in the range of 0.2 to 1.0 μm.

This particle size can be measured using the projected area of the particle or the approximate diameter. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area. Further, the particle size of the silver halide grains according to the present invention may be changed so that the effective sensitivity range becomes a preferable range.

The grain size distribution of the silver halide grains of the present invention is preferably a monodispersed silver halide grain having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, and particularly preferably 0. .15 or less are added to the same layer. Here, the coefficient of variation is a coefficient representing the width of the particle size distribution, and is defined by the following equation. Coefficient of variation = S / R (where, S represents the standard deviation of the particle size distribution, and R represents the average particle size.) The particle size referred to here is the diameter of a spherical silver halide particle, In the case of particles having a shape other than a cube or a sphere, the diameter represents a 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 emulsion, various methods known in the art can be used.

The silver halide emulsion according to the present invention may be obtained by any of an acidic method, a neutral method, and an ammonia method. The particles may be grown at one time or may be grown after seed particles have been made. The method of producing the seed particles and the method of growing them may be the same or different.

The form in which the soluble silver salt and the soluble halide salt are reacted may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like. Is preferred. Further, as one type of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.

Further, JP-A-57-92523, JP-A-57-92523.
No.-92524, etc., 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, and a water-soluble silver salt and a water-soluble solution described in German Patent Publication No. 292,164. Apparatus for continuously changing the concentration of an aqueous halide salt solution, JP-B-56-50
The reaction mother liquor was taken out of the reactor described in No. 1776, etc.
An apparatus that forms grains while keeping the distance between silver halide grains constant by concentrating by ultrafiltration may be used.

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 at the time of forming silver halide grains or after the completion of grain formation.

The silver halide emulsion according to the present invention can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer.

As the chalcogen sensitizer applied to the silver halide emulsion according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, but a sulfur sensitizer is preferable. Thiosulfates as sulfur sensitizers,
Allyl thiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine, inorganic sulfur and the like can be mentioned.

The addition amount of the sulfur sensitizer according to the present invention is preferably changed depending on the kind of the silver halide emulsion to be applied and the size of the expected effect. The range is preferably ^{-10 to} 5 x ^10-5 mol, and more preferably 5 x ^{10-8 to} 3 x ^10-5 mol.

As the gold sensitizer according to the present invention, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of the gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound to be used, the ripening conditions, etc., but usually from 1 × 10 ⁻⁴ mol to 1 × 1 per mol of silver halide.
It is preferably ^0-8 mol. More preferably, 1
It is from × 10 ⁻⁵ mol to 1 × 10 ⁻⁸ mol. As the chemical sensitization method for the silver halide emulsion according to the present invention, a reduction sensitization method may be used.

The chemical sensitization of the silver halide emulsion according to the present invention is performed by adjusting a gold sensitization method, a sensitization method using a chalcogen sensitizer, and a reduction sensitization method so that the effective sensitivity range is within a preferable range. It is preferable to carry out. The layer containing the silver halide emulsion of the present invention may be at any distance from the support, but the layer closest to the support is particularly preferred because the effect of the present invention is high.

The silver halide emulsion according to the present invention is intended to prevent fogging during the preparation process of the silver halide photographic light-sensitive material, reduce performance fluctuation during storage, and prevent fogging during development. A known antifoggant,
Stabilizers can be used. Examples of preferred compounds that can be used for such a purpose are described in JP-A No. 2-14 / 1990.
The compound represented by the general formula (II) described in the lower column on page 7 of JP-A-6036 can be mentioned, and a more preferred specific compound is (IIa-1) described on page 8 of the same publication. ) To (IIa-8), (IIb-)
1) to (IIb-7), 1- (3-methoxyphenyl) -5-mercaptotetrazole, 1- (4-
Compounds such as (ethoxyphenyl) -5-mercaptotetrazole can be mentioned. These compounds are added in a step of preparing silver halide emulsion grains, a step of chemical sensitization, at the end of the step of chemical sensitization, a step of preparing a coating solution or the like according to the purpose. When chemical sensitization is performed in the presence of these compounds, 1 × 10
It is preferably used in an amount of about ^-5 mol to 5 × 10 ^-4 mol. 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, more preferably 1 × 10 ⁻⁵ mol to 5 × 10 ⁻³ mol. More preferred. In the coating solution preparation step, when added to the silver halide emulsion layer, the amount is preferably about 1 × 10 ⁻⁶ mol to 1 × 10 ⁻¹ mol per mol of silver halide, and more preferably about 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁵ mol. 1 × 10 ⁻² mol is more preferred. When it is added to a layer other than the silver halide emulsion layer, the amount in the coating film is from 1 × 10 ⁻⁹ mol / m ^{2 to} 1 × 10 ⁻⁹ mol / m ^2.
An amount of about 1 × 10 ⁻³ mol is preferred.

In the silver halide photographic light-sensitive material according to the present invention, dyes having absorption in various wavelength ranges 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,
A described on page 308 of JP-A-3-251840
The dyes I-1 to 11 and the dyes described in JP-A-6-3770 are preferably used. As the infrared absorbing dye, the general formula (I) described in the lower left column of page 2 of JP-A-1-280750 is used. The compounds represented by ()), (II) and (III) have preferable spectral characteristics, do not affect the photographic characteristics of the silver halide photographic emulsion, and do not stain with residual color. Specific examples of preferred compounds include Exemplified Compounds (1) to (45) listed on page 3, lower left column to page 5, lower left column of the same publication.

In order to improve the sharpness, the amount of these dyes added is 680 nm for an unprocessed sample of a light-sensitive material.
Is more preferably 0.7 or more, and even more preferably 0.8 or more.

It is preferable to add a fluorescent whitening agent to the light-sensitive material according to the present invention because the white background can be improved. Preferred examples of the compound include a compound represented by the general formula II described in JP-A-2-232652.

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

The effective sensitivity range of the silver halide emulsion layer of the present invention is determined by the Dmin + of the characteristic curve of the silver halide emulsion layer.
It means an exposure area between an exposure amount giving 0.1 and an exposure amount giving Dmax-0.1 of the characteristic curve.

The characteristic curve of the silver halide emulsion layer according to the present invention was obtained by applying the silver halide emulsion layer according to the present invention on a reflective support by the method of Example 3 described later, and preparing a sample prepared by a conventional method. It is obtained by measuring the density of a reflection sample obtained by exposure and development, and plotting the density against a common logarithm of the exposure amount. In the present invention, Dmax indicates the highest density on the characteristic curve, and Dmin indicates the minimum density. In the present invention, the effective sensitivity range of the silver halide emulsion layer is obtained from a characteristic curve when coating conditions are given such that the Dmax of each silver halide emulsion layer is 2.0 to 2.5. Further, the sensitivity of the silver halide emulsion layer according to the present invention is determined by the characteristic curve of the silver halide emulsion layer as Dmin + 0.5 × (Dmax-Dmi).
It is defined by the reciprocal of the exposure amount that gives the density of n).

The silver halide photographic light-sensitive material of the present invention may have three or more silver halide emulsion layers containing dye image forming couplers of substantially the same hue. The silver halide emulsion layer may contain two or more emulsions. In this case, the overlap of the effective sensitivity areas between two silver halide emulsion layers having close sensitivities satisfies the claim, and the characteristics obtained when the two silver halide emulsion layers are simultaneously coated on a support. The overlap of the effective sensitivity region between the curve and the silver halide emulsion layer close to the third sensitivity satisfies the claim.

The overlap of the effective sensitivity range of the silver halide emulsion layer of the present invention is 20% or more of the effective sensitivity range of the low-sensitivity silver halide emulsion layer of a silver halide emulsion layer having a close sensitivity.
5% or less overlaps the effective sensitivity range of the high-sensitivity silver halide emulsion layer, and 60% to 100% of the effective sensitivity range of the high-sensitivity silver halide emulsion layer is effective for the low-sensitivity silver halide emulsion layer. And at least one of the overlaps of the effective sensitivity range of the silver halide emulsion layer is 5
Preferably it is less than 0% or more than 95%.

As the spectral sensitizing dye used in the silver halide emulsion according to the present invention, any known compounds can be used.
BS-1 to 8 described on page 28 of JP-A-251840 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to GS-5 described on page 28 of the same publication are preferably used. RS-1 to 8 described on page 29 of the same publication are preferably used as red-sensitive sensitizing dyes. In the case of performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye. The dyes of IRS-1 to 11 described in JP-A No. 6-8 are preferably used. These infrared, red, green, and blue photosensitive sensitizing dyes may be added to supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pp. 8-9, and JP-A-5-66515. Nos. S-1 to S-17 described on pages 15 to 17
Are preferably used in combination.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization. As a method of adding the sensitizing dye, methanol, ethanol, fluorinated alcohol, acetone, may be added as a solution by dissolving in water-miscible organic solvents such as dimethylformamide or water or added as a solid dispersion. Is also good. The type, amount, and method of addition of the sensitizing dye used in the silver halide emulsion according to the present invention can be adjusted so that the effective sensitivity range falls within a preferable range.

As the coupler used in the silver halide photographic light-sensitive material according to the present invention, a coupling reaction with an oxidized form of a color developing agent is performed to form a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm. Any compound that can be used can be used, and particularly typical examples include a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a wavelength range of 500.
Typical examples are magenta dye-forming couplers having a spectral absorption maximum wavelength in the range of -600 nm and cyan dye-forming couplers having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm.

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

The magenta couplers which can be preferably used in the silver halide photographic light-sensitive material according to the present invention include those represented by general formulas (MI) and (M) described in the upper right column on page 4 of JP-A-4-114154. -II). Specific compounds are listed in the lower left column of page 4 to the upper right column of page 5 in the same publication, MC-1.
To MC-11. Among the above magenta couplers, more preferred are those represented by the general formula (M
-I), among which couplers of the above general formula (MI) in which RM is a tertiary alkyl group have excellent light resistance and are particularly preferred. MC-8 to MC-11 described in the upper column of page 5 of the publication are blue to purple,
It is preferable because it excels in reproducing colors up to red and also has excellent descriptive power of details.

The yellow coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention is represented by the general formula (Y-I) described in the upper right column on page 3 of JP-A-4-114154. Couplers. Specific compounds include those described as YC-1 to YC-9 in the lower left column of page 3 of the same publication. Above all, a coupler in which RY1 of the general formula [Y-1] of the same publication is an alkoxy group or a coupler represented by the general formula [I] described in JP-A-6-67388 can reproduce yellow having a preferable color tone. preferable. Of these, particularly preferred examples of the compounds include YC-8 and YC-9 described in the lower left column of page 4 of JP-A-4-114154, and
-67388, page 13-14
o (1) to (47). The most preferred compound is described in JP-A-4-8184.
It is a compound represented by the general formula [Y-1] described in JP-A-7-page 1 and JP-A-11-page 11-17.

When an oil-in-water emulsion dispersion method is used to add the couplers and other organic compounds used in the silver halide photographic light-sensitive material according to the present invention, the water-insoluble emulsion usually has a boiling point of 150 ° C. or higher. If necessary, a low-boiling point and / or water-soluble organic solvent is used in combination in the boiling point organic solvent, and the mixture is dissolved and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. 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 or at the same time as the dispersion, a step of removing the low boiling organic solvent may be added. Examples of high boiling organic solvents that can be used to dissolve and disperse the coupler include dioctyl phthalate, diisodecyl phthalate, phthalates such as dibutyl phthalate, tricresyl phosphate, and phosphates such as trioctyl phthalate,
Is preferably used. The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0. Further, two or more kinds of high-boiling organic solvents can be used in combination.

In place of the method using a high-boiling organic solvent or in combination with a high-boiling organic solvent, a water-insoluble and organic solvent-soluble polymer compound may be added, if necessary, to a low-boiling and / or water-soluble organic solvent. In a hydrophilic binder such as an aqueous gelatin solution by using a surfactant and emulsifying and dispersing by various dispersing means.
Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

The silver halide emulsion layer according to the present invention has an effective sensitivity range within a preferable range depending on the type and amount of the coupler, the high boiling point solvent and the polymer soluble in an organic solvent, and the method of emulsifying and dispersing them. Can be adjusted to

The coupler contained in the silver halide emulsion layer according to the present invention includes a cyan coupler, a magenta coupler,
Although any of yellow couplers may be used, the case of a yellow coupler is particularly preferable since the effect of the present invention can be largely obtained.

As a compound preferable as a surfactant used for dispersing a photographic additive or adjusting a surface tension at the time of coating, a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule are preferable. Containing. Specifically, A- described in JP-A-64-26854 is described.
1 to A-11. Also, a surfactant in which a fluorine atom is substituted for an alkyl group is preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, and the time until the addition to the coating solution after the dispersion and the time from the addition to the coating solution to the coating are preferably as short as 10 hours each. Preferably within 3 hours, more preferably within 20 minutes.

It is preferable to use an anti-fading agent in combination with each of the above couplers in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include phenyl ether compounds represented by general formulas I and II described on page 3 of JP-A-2-66541 and general formula III described in JP-A-3-174150.
Phenolic compound represented by B
5, an amine compound represented by the general formula A described in JP-A-6-181841;
Metal complexes represented by III, XIV and XV are particularly preferred for magenta dyes. Also, Japanese Patent Laid-Open No. 1-196049
The compound represented by the general formula I 'described in JP-A-2005-146131 and the compound represented by the general formula II described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.

The silver halide emulsion of the present invention is obtained by selecting and using the above-mentioned coupler compound which develops substantially the same hue in order to obtain the effective sensitivity range of the present invention. It is also one of the preferred embodiments to select and use an amount.

For the purpose of shifting the absorption wavelength of the coloring dye, the compound (d-11) described in the lower left column of page 9 of JP-A-4-114154 and the compound described in the lower left column of page 10 of the same publication are disclosed. Compounds such as (A'-1) can be used. In addition, US Pat.
No. 4,187, can be used.

In the silver halide light-sensitive material according to the present invention, a compound which reacts with an oxidized developing agent is added to a layer between the light-sensitive layers to prevent color turbidity or to add a compound to the silver halide emulsion layer. It is preferable to improve fog and the like by adding.
The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkylhydroquinone such as 2,5-di-tert-octylhydroquinone.
Particularly preferred compounds are those represented by the general formula II described in JP-A-4-133056, and the compounds II-1 to II-14 described on pages 13 to 14 of the same publication.
And Compound 1 described on page 17.

It is preferable to add an ultraviolet absorber to the light-sensitive material according to the present invention to prevent static fog and improve the light fastness of the dye image. Preferable ultraviolet absorbers include benzotriazoles. Particularly preferred compounds are compounds represented by the formula III-3 described in JP-A-1-250944 and JP-A-64-66.
No. 646, compounds represented by general formula III, and JP-A-63-187240, UV-1L to UV
-27L, compounds represented by general formula I described in JP-A-4-1633, and compounds represented by general formulas (I) and (II) described in JP-A-5-165144.

In the silver halide photographic light-sensitive material according to the present invention, it is advantageous to use gelatin as a binder. If necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other high polymers, gelatin Other than these, hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as homopolymers and copolymers can also be used.

As the hardener of these binders, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination. JP-A-61-24
It is preferable to use the compounds described in JP-A Nos. 9054 and 61-245153. Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 to the colloid layer in order to prevent the growth of mold and bacteria which adversely affect photographic performance and image storability. It is preferable to add a slipping agent or matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer in order to improve the physical properties of the surface of the photosensitive material or the processed sample.

The support used for the silver halide photographic light-sensitive material according to the present invention is preferably a reflective support, and any material may be used, such as paper coated with polyethylene or polyethylene terephthalate, natural pulp or synthetic pulp. Paper support, vinyl chloride sheet, polypropylene which may contain white pigment, polyethylene terephthalate support, baryta paper, and the like can be used. Among them, a support having a water-resistant resin coating layer on both sides of the base paper is preferable. As the water-resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

As the white pigment used for the 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 silica, silica such as synthetic silicate, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide. The amount of the white pigment contained in the water-resistant resin layer on the surface of the support is preferably 13% by weight or more, and more preferably 15% by weight, for improving sharpness.

The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. 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, as the coefficient of variation described in the above publication. Further, the value of the center plane average roughness (SRa) of the support is 0.15 μm or less, and more preferably 0.1 μm.
It is more preferable that the thickness be 12 μm or less, since the effect of good gloss can be obtained. In addition, trace amounts of ultramarine, oil-soluble dyes, etc. to adjust the spectral reflection density balance of the white background after treatment in the white pigment-containing water-resistant resin of the reflective support or in the applied hydrophilic colloid layer to improve whiteness It is preferable to add a bluing agent or a reddish agent.

The silver halide photographic light-sensitive material according to the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface, if necessary, and then directly or undercoating (adhesion of the support surface, (1 or 2 or more subbing layers for improving antistatic properties, dimensional stability, friction resistance, hardness, antihalation properties, friction properties and / or other properties) Good.

In coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.

In order to form a photographic image using the silver halide photographic light-sensitive material according to the present invention, an image recorded on a negative is optically formed on a silver halide photographic light-sensitive material to be printed. The image may be printed and printed, or once the image is converted into digital information, the image is formed on a CRT (cathode ray tube), and this image is formed on a silver halide photographic material to be printed. Alternatively, the image may be printed by scanning while changing the intensity of the laser beam based on digital information.

The present invention is preferably applied to a light-sensitive material in which a developing agent is not incorporated in the light-sensitive material, and particularly preferably applied to a light-sensitive material which directly forms an image for viewing. For example, color paper, color reversal paper, a photosensitive material for forming a positive image, a photosensitive material for a display, and a photosensitive material for a color proof can be used. It is particularly preferable to apply the invention to a photosensitive material having a reflective support.

As the aromatic primary amine developing agent used in the image forming method of the present invention, known compounds can be used. The following compounds can 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- (N-ethyl-N- (β-hydroxyethyl) amino) 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

In the present invention, the above color developing solution can be used in an arbitrary pH range.
It is preferably from 9.5 to 13.0, and more preferably used in the range of pH 9.8 to 12.0.

In the image forming method of the present invention,
The amount of replenishment of image liquid is photosensitive material 1m²Per 120ml or less,
Preferably, the volume is 10 to 100 ml or less.
It is desirable to achieve the effect of the purpose of light.

The processing temperature for color development according to the present invention is 35
The temperature is preferably from 70 ° C to 70 ° C. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, the higher the temperature, the more preferable.

Conventionally, the color development time is generally about 3 minutes and 30 seconds, but in the present invention, it is preferably within 30 seconds, more preferably from 1 second to 25 seconds. A known developer component compound can be added to the color developing solution in addition to the above-described color developing agent. Usually, alkaline agents having a pH buffering action, chloride ions, development inhibitors such as benzotriazoles, preservatives,
A chelating agent or the like is used.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process,
Usually, a water washing process is performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed. The developing apparatus used for the development 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 between rollers disposed in a processing tank, and the belt may be provided with the light-sensitive material. The processing tank may be formed in a slit shape, and the processing liquid may be supplied to the processing tank and the photosensitive material may be transported, or the processing liquid may be sprayed. Spray method,
A web method by contact with a carrier impregnated with the processing solution,
A method using a viscous treatment liquid can also be used. When processing in large quantities, it is normal to run using an automatic developing machine, but in this case, the replenishment amount of the replenisher is preferably as small as possible. And the method described in JP-A-94-16935 is most preferable.

[0086]

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 high-density polyethylene was laminated on both sides of a paper pulp having a basis weight of 180 g / m ² to prepare a paper support. However, on the side to be coated with the emulsion layer, a molten polyethylene containing surface-treated anatase-type titanium oxide dispersed at a content of 15% by weight was laminated to produce a reflective support. After subjecting this reflective support to a corona discharge treatment, a gelatin undercoat layer was provided, and each layer having the following constitution was further applied to prepare a silver halide photographic light-sensitive material. The coating solution was prepared as described below.

23.4 g of yellow coupler (Y-1),
3.34 g of dye image stabilizer (ST-1), (ST-
2) 3.34 g, (ST-5) 3.34 g, stain inhibitor (HQ-1) 0.34 g, image stabilizer A 5.0 g,
60 ml of ethyl acetate was added to 3.33 g of a high-boiling organic solvent (DBP) and 1.67 g of a high-boiling organic solvent (DNP) to dissolve the solution, and this solution was treated with 7 m of a 20% surfactant (SU-1).
The mixture was emulsified and dispersed in 220 ml of a 10% aqueous gelatin solution containing 1 using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a silver halide emulsion prepared under the following conditions to prepare a first layer coating solution.
A sample 101 was prepared by simultaneously applying the coating solution for the second layer (protective layer) and the support. In addition, (H-1) was added to the second layer as a hardener. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension.

[0088]

[Table 1]

SU-1: Sodium tri-i-propylnaphthalenesulfonate SU-2: Di (2-ethylhexyl) sulfosuccinate sodium salt SU-3: Di (2,2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) sodium salt DBP: dibutyl phthalate DNP: dinonyl phthalate H-1: tetrakis (vinylsulfonylmethyl) methane HQ-1: 2,5-di-tert-octylhydroquinone Image stabilizer A: P -T-octylphenol

[0090]

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(Preparation of Blue-Sensitive Silver Halide Emulsion) 40 ° C.
In a liter of a 2% aqueous gelatin solution kept warm in
Solution) and (solution B) were added simultaneously over 30 minutes while controlling pAg = 7.3 and pH = 3.0, and the following (solution C) and (solution D) were further added at pAg = 8.0, pH = 5.5 and added simultaneously over 180 minutes. At this time, pAg was controlled by the method described in JP-A-59-45437.
H was controlled using sulfuric acid or an aqueous solution of sodium hydroxide.

(Solution A) 3.42 g of sodium chloride 0.03 g of potassium bromide 200 ml by adding water (solution B) 10 g of silver nitrate 200 ml by adding water (solution C) 102.7 g of sodium chloride 102.7 g of K ₂ IrCl ₆ 4 × 10 ^-8 mol / mol _{Ag K 4 Fe (CN) 6} 2 × 10 -5 mol / mol Ag potassium bromide 1.0g water to make 600ml (D solution) Silver nitrate 300g water to make 600ml

After completion of the addition, Demol N manufactured by Kao Atlas Co., Ltd.
And a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to give an average particle size of 0.65 μm, a variation coefficient of the particle size distribution of 0.07, and a silver chloride content of 99. A 5 mol% monodispersed cubic emulsion EMP-1 was obtained. To the above EMP-1, sodium thiosulfate and chloroauric acid were added, and after optimal chemical sensitization at 60 ° C, the following compound was added to add blue-sensitive silver halide emulsion (Em-
B101) was obtained.

Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-3 3 × 10 ⁻⁴ mol / mol AgX Sensitizing dye BS- 14 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-2 1 × 10 ⁻⁴ mol / mol AgX STAB-1: 1- (3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1 -Phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole

[0095]

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After the thus prepared sample was exposed to light wedges by a conventional method, development processing was performed in the following development processing step A. In the development processing step A, the running processing is performed until a color developing replenisher of three times the tank capacity of the color developing solution is replenished. Developing process A Processing process Processing temperature Time Replenishment amount Color development 35.0 ± 0.3 ° C 45 seconds 150ml Bleaching and fixing 35.0 ± 0.5 ° C 45 seconds 120ml Stabilization 30-34 ° C 60 seconds 150ml Drying 60-80 ℃ 30 seconds

The composition of the developing solution is shown below. Color developing solution tank solution and replenisher tank solution Replenisher Pure water 800 ml 800 ml triethylenediamine 2 g 3 g diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N-ethyl-N- (Β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 10.0 g N, N-diethylhydroxylamine 6.8 g 6.0 g triethanolamine 10.0 g 10.0 g sodium diethylenetriaminepentaacetate Salt 2.0 g 2.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Water was added to make a total volume of 1 liter. 10 and replenisher to pH = 10.60 adjust.

Bleach-fix solution and replenisher Ferric ammonium diethylenetriaminepentaacetate dihydrate 65 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4-thiadiazole 2 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Water is added to make up to 1 liter, and the pH is adjusted to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing solution tank solution and replenisher solution o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Fluorescent whitening agent (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP 1 0.0 g ammonia water (25% aqueous ammonium hydroxide solution) 2.5 g nitrilotriacetic acid / trisodium salt 1.5 g Water is added to make up to 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or aqueous ammonia.

The sample obtained by the development was subjected to PDA-65.
Using a densitometer (manufactured by Konica Corporation), measure the blue density,
A characteristic curve was obtained by plotting against the amount of exposure. Dmax of this sample was 2.30. The sensitivity is Dmin + 0.
The reciprocal of the exposure amount giving a density of 5 × (Dmax−Dmin) was calculated, and expressed as a logarithm of the relative sensitivity with respect to the sample 101. In addition, the effective sensitivity range is Dmax-0.1 and Dm
Sample 101 for the reciprocal of the exposure dose giving in-0.1
The value was expressed as a relative value based on the reciprocal of the exposure amount giving the sensitivity. The blue-sensitive emulsion (Em-B10
The sensitivity and effective sensitivity range of 1) were determined. Blue-sensitive emulsion (Em
-B101), the amounts of sodium thiosulfate and chloroauric acid to be added were adjusted, and a blue-sensitive emulsion (Em-B1) was prepared.
02) to (Em-B107). A sample was prepared in the same manner as Sample 101 except that the blue-sensitive emulsion (Em-B101) was changed to the blue-sensitive emulsions (Em-B102) to (Em-B107). The concentrations of these samples were measured in the same manner to determine the sensitivity and the effective sensitivity range. The results are shown in Table 2.

[0101]

[Table 2]

Example 2 In the preparation of the sample 101 of Example 1, in addition to the first layer, the coating liquids of the second to seventh layers were the same as those of the first layer of Example 1, as shown in Tables 3 and 4. Each coating solution was prepared so as to have a coating amount. (H-1) and (H-2) were added as hardeners. Surfactants (SU-2), (S
U-3) was added to adjust the surface tension. In addition, F
Total amount -1 was added in an amount of 0.04 g / ^{m 2.}

[0103]

[Table 3]

[0104]

[Table 4]

DOP: dioctyl phthalate DIDP: di-i-decyl phthalate PVP: polyvinylpyrrolidone H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-2: 2,5-disecdodecyl Hydroquinone HQ-3: 2,5-disec-tetradecylhydroquinone HQ-4: 2-secdodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di (1,1-dimethyl-4-hexyloxycarbonyl ) Butyl hydroquinone

[0106]

Embedded image

[0107]

Embedded image

[0108]

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(Preparation of Green-Sensitive Silver Halide Emulsion) In the preparation of the blue-sensitive emulsion (Em-B101) of Example 1,
(Solution A) and (solution B) addition time and (solution C) and (solution D)
A monodisperse cubic emulsion EMP-2 having an average particle size of 0.40 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% was obtained in the same manner as in EMP-1, except that the addition time was changed. Next, a monodispersed cubic emulsion EMP-2B having an average particle size of 0.50 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% was obtained.

The above-mentioned EMP-2 was optimally subjected to chemical sensitization at 55 ° C. using the following compounds. Also EMP-2B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-2 and EMP-2B were mixed at a silver amount of 1: 1 to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX

(Preparation of Red-Sensitive Silver Halide Emulsion) In the preparation of the blue-sensitive emulsion (Em-B101) of Example 1,
(Solution A) and (solution B) addition time and (solution C) and (solution D)
A monodisperse cubic emulsion EMP-3 having an average particle size of 0.40 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% was obtained in the same manner as in EMP-1, except that the addition time was changed. A monodispersed cubic emulsion EMP-3B having an average particle size of 0.38 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% was obtained.

The above-mentioned EMP-3 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also EMP-3B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-3 and EMP-3B were mixed at a silver ratio of 1: 1 to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 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 , SS-1 was added in an amount of 2.0 × 10 ⁻³ per mol of silver halide.

[0115]

Embedded image

Thus, a sample 201 was obtained. In the preparation of this sample 201, the emulsion (Em
Samples 202 to 211 were obtained in the same manner except that -B101) was changed as shown in Table 5.

[0117]

[Table 5]

These samples were exposed through Konica Color JX-400, which had been photographed and developed, and were subjected to development processing in development processing step A of Example 1 and development processing steps B and C described below. Developing process B Processing process Processing temperature Time Replenishment amount Color development 37.0 ± 0.3 ° C 45 seconds 80ml Bleaching and fixing 35.0 ± 0.5 ° C 45 seconds 120ml Stabilization 30-34 ° C 60 seconds 150ml Drying 60-80 ℃ 30 seconds Development processing step C Processing step Processing temperature Time Replenishment amount Color development 40.0 ± 0.3 ℃ 25 seconds 80ml Bleaching and fixing 35.0 ± 0.5 ℃ 45 seconds 120ml Stabilization 30-34 ° C 60 seconds 150ml Drying 60-80 ° C 30 seconds

The tank liquids in the development processing steps B and C were obtained in Example 1.
The same processing as in the developing step A was carried out until the replenishing solution for color development was replenished in an amount three times the tank capacity of the color developing solution. The replenishers for the development processing steps B and C are the same as those in the development processing step A of the first embodiment. The prints of the landscape scene and the portrait scene obtained in this way were evaluated sensory by five persons on a five-point scale. This 10
Table 6 shows the average scores of humans.

[0120]

[Table 6]

As can be seen from the above, the silver halide light-sensitive material using the emulsion of the present invention has excellent gradation from highlight to shadow in both scenes of scenes and portraits, and as a result it is preferable. You can see that it is finished. In addition, it can be seen that the gradation processing is not lost even in the rapid processing and the low replenishment processing, so that a preferable finish is obtained.

Example 3 A sample was prepared by replacing the first layer of the sample 101 of Example 1 with a specific silver halide emulsion layer, and the sensitivity and the effective sensitivity range of the silver halide emulsion of Example 1 were determined. The sensitivity and effective sensitivity range of a specific silver halide emulsion layer were determined in the same manner.
The first layer of the sample 101 is referred to as a silver halide emulsion layer 301. Blue-sensitive emulsion of silver halide emulsion layer 301 (Em-B
101) replacing the blue-sensitive emulsion used in Example 1,
Alternatively, silver halide emulsion layers 302 to 311 were prepared by substituting STAB-1 with a plurality of silver halide emulsion layers. Table 7 shows the sensitivity and the effective sensitivity range of these silver halide emulsion layers.
Shown in

[0123]

[Table 7]

Example 4 Samples 401 to 408 were prepared in the same manner as in the preparation of Sample 201 of Example 2 except that the layers shown in Table 8 were applied instead of the first layer.
Was prepared.

[0125]

[Table 8]

These samples were exposed and developed through Konica Color JX-400, which had been photographed and developed, in the same manner as in Example 2, and the resulting scenery and portrait scene prints were evaluated organoleptically by five persons on a five-point scale. did. Table 9 shows the average scores of the ten persons.

[0127]

[Table 9]

As is apparent from the results, the silver halide light-sensitive material using the silver halide emulsion layer of the present invention has the following properties.
It can be seen that in both the scenery scene and the portrait scene, the gradation from the highlight to the shadow portion is excellent, and a favorable finish is obtained. In addition, it can be seen that the gradation processing is not lost even in the rapid processing and the low replenishment processing, so that a preferable finish is obtained.

[0129]

According to the present invention, the gradation is excellent, and a natural and high descriptive power is obtained from the highlight portion to the shadow portion.
It is possible to provide a silver halide emulsion, a silver halide photographic material, and an image forming method which maintain excellent gradation even in rapid processing and low replenishment processing.

Claims (10)

[Claims] An effective sensitivity range of 0% to 95% of an emulsion having a low sensitivity of an emulsion having a close sensitivity overlaps an effective sensitivity range of an emulsion having a high sensitivity and 5% of an effective sensitivity range of an emulsion having a high sensitivity.
0% or more and 100% or less overlap the effective sensitivity range of the low-sensitivity emulsion, and at least one of the overlaps of the effective sensitivity range of the emulsion has a sensitivity of less than 50% or more than 95%. A silver halide emulsion characterized by containing. 2. A silver halide photographic material having a silver halide emulsion layer containing at least two or more dye image-forming couplers of substantially the same hue on a support, wherein the silver halide emulsion has a similar sensitivity. 0% to 95% of the effective sensitivity range of the silver halide emulsion layer having a low sensitivity of the silver emulsion layer overlaps the effective sensitivity range of the silver halide emulsion layer having a high sensitivity, and the effective sensitivity range of the silver halide emulsion layer having a high sensitivity is effective. 50% or more and 100% or less of the sensitivity range overlap with the effective sensitivity range of the silver halide emulsion layer having low sensitivity, and at least one of the overlaps of the effective sensitivity range of the silver halide emulsion layer is less than 50% or 95%. A silver halide photographic material having a plurality of silver halide emulsion layers having different sensitivities. 3. The halogen of an emulsion having a high sensitivity, wherein 0% to 95% of the effective sensitivity range of a silver halide grain of an emulsion having a low sensitivity of an emulsion having a close sensitivity overlaps the effective sensitivity range of an emulsion having a high sensitivity. 50% or more of the effective sensitivity range of silver halide grains 100
% Or less overlaps with the effective sensitivity range of the silver halide grains of the low-sensitivity emulsion, and at least one of the overlaps of the effective sensitivity range of the silver halide grains of the emulsion has a different sensitivity of less than 50% or more than 95%. A silver halide emulsion comprising a silver halide emulsion of the formula (1). 4. An effective sensitivity range of 0 to 95% of an effective sensitivity range of a low sensitivity emulsion of an emulsion having a close sensitivity overlaps an effective sensitivity range of a high sensitivity emulsion, and 5% of an effective sensitivity range of a high sensitivity emulsion.
It is characterized in that 0% or more and 100% or less overlap the effective sensitivity range of the low-sensitivity emulsion, and at least one of the overlaps of the effective sensitivity range of the emulsion is less than 50% or more than 95%, characterized by chemical sensitization and / or spectroscopy. A silver halide emulsion containing a plurality of silver halide emulsions having different sensitivities provided by sensitization. 5. A silver halide photographic light-sensitive material having at least two or more silver halide emulsion layers containing dye image-forming couplers of substantially the same hue on a support, wherein silver halides having similar sensitivity are used. 0% to 95% of the effective sensitivity range of the silver halide emulsion layer having a low sensitivity of the emulsion layer overlaps with the effective sensitivity range of the silver halide emulsion layer having a high sensitivity,
And an effective sensitivity range of 50 for the silver halide emulsion layer having high sensitivity.
% To 100% overlap the effective sensitivity range of the silver halide emulsion layer having low sensitivity, and at least one of the overlaps of the effective sensitivity range of the silver halide emulsion layer is less than 50% or more than 95%. A silver halide photographic material provided by a dye image forming coupler contained in a silver halide emulsion layer. 6. A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion according to claim 1 is contained in the silver halide emulsion layer. Characteristic silver halide photographic material. 7. A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion according to claim 1 is contained in the silver halide emulsion layer closest to the support. A silver halide photographic light-sensitive material characterized in that: 8. A silver halide photographic material having at least one silver halide emulsion layer on a support, characterized in that the silver halide emulsion according to claim 1 is contained in a yellow color emulsion layer. Silver halide photographic material. 9. An image forming method wherein the silver halide photographic light-sensitive material according to claim 2 or 3 is processed with a color developing solution in which the replenishment amount of the color developing solution is 120 ml or less per 1 m ^{2 of the} light-sensitive material. . 10. An image forming method, wherein the silver halide photographic light-sensitive material according to claim 2 is processed in a color development processing time of 30 seconds or less.