JP2001092066A - Silver halide emulsion and silver halide photographic sensitive material using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide emulsion excellent in latent image stability and reciprocity failure while having high sensitivity and gradation suitable for silver halide color photographic printing paper and excellent also in gradation in high illuminance exposure and to obtain a silver halide photographic sensitive material using the emulsion. SOLUTION: The silver halide emulsion is a silver chlorobromide emulsion having >=90 mol% silver chloride content and comprises silver chlorobromide grains each having a region whose silver bromide content is higher than that of the other region and containing at least one compound (B) selected from (b1) a compound having the effect of reducing the intensity of a microwave photoconductive signal, (b2) a compound having the effect of shortening the attenuation time of the intensity of a microwave photoconductive signal, (b3) a compound having a de-photosensitizing effect, (b4) a compound forming a deep trap level by which trapped electrons are retained for >=5 sec, (b5) a compound forming a deeper electron trap level than the following compounds (C) and (b6) a compound having a deeper electron trap level than 0.6 eV. The compounds C are an Ir-containing compound and an Ir-containing complex. The compound (B) does not belong to the compound (C).

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 for color photography and a silver halide photographic light-sensitive material (hereinafter, also referred to as a "light-sensitive material"). The present invention relates to a silver halide (for color photography) emulsion which has excellent characteristics and gives good gradation even at high illuminance exposure, and a silver halide photosensitive material using the same.

[0002]

2. Description of the Related Art With the development of minilabs and the like, silver halide color photographic paper has been handled in various places, and with this, exposure for printing has been performed under various conditions and environments. Was. In recent years, development processing has been accelerated, and a large amount of color photographic paper has been rapidly processed. Accelerated development is a very strong demand in the color photographic industry, with numerous improvements being made and new rapid systems being developed every few years.

Although silver halide having a high silver chloride content has been widely used for the purpose of speeding up the above development processing, silver halide emulsions having a high silver chloride content are important properties of color photographic paper. It is known that it is difficult to obtain such a hard gradation, and that there is a defect that the so-called reciprocity failure characteristic is deteriorated such that the sensitivity to the change of the exposure illuminance and the gradation change become large.

[0004] Techniques for improving this disadvantage include, for example, Japanese Patent Publication No. 43-4935 and US Patent No. 4,997,75.
As described in No. 1, it is described that an Ir compound is effective for improving reciprocity failure property.
-It provides an appropriately hard gradation in the LogE characteristic curve. However, Ir compounds are described in Journal of Photography Science, Vol.
As disclosed on page 1, there is a disadvantage that the stability of the latent image is deteriorated in the initial stage after exposure.

On the other hand, JP-A-64-26837 discloses a high silver chloride emulsion having a region having a high silver bromide content near the apex of silver halide grains, and JP-A-1-105940 discloses a high silver chloride emulsion. It has been shown that by selectively doping Ir in a localized region of silver, a high silver chloride emulsion having excellent latent image stability and reciprocity failure characteristics can be provided. US Patent 5,
No. 627,020 discloses a method of forming a localized region of silver bromide by using Ir-doped silver bromide fine particles, but any of these methods is intended to improve the stability of a latent image at the initial stage after exposure. That was not enough.

Japanese Patent Application Laid-Open No. 10-307357 discloses that a high permanent contrast characteristic peculiar to a bright room light-sensitive material is introduced by introducing a deep permanent electron trap satisfying a specific formula into a silver halide grain in a light-room light-sensitive material. It is disclosed that it can be obtained.

In recent years, digital processing of images has rapidly progressed, and the need for image formation by scanning exposure with a high-intensity light source such as a light emitting diode or a semiconductor laser has rapidly increased. There is a strong demand for silver halide photosensitive materials to have further improved suitability for high illuminance and short time exposure.

That is, there is a strong demand for the appearance of a photosensitive material capable of obtaining a good image in both conventional photographic image formation and image formation by short-time scanning exposure using high-intensity light.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide high sensitivity and excellent gradation characteristics suitable for silver halide color photographic paper, as well as excellent latent image stability and reciprocity failure characteristics. An object of the present invention is to provide a silver halide emulsion and a silver halide photographic light-sensitive material which are excellent in gradation stability in high-illuminance short-time exposure.

[0010]

The above object of the present invention is achieved by the following constitution.

1. A silver chlorobromide emulsion having a silver chloride content of 90 mol% or more, which has a region where the silver bromide content is higher than the others and contains at least one of the following compounds (B): A silver halide emulsion comprising silver halide grains.

Compound (B): a compound corresponding to at least one of the following (b1) to (b6).

However, compounds belonging to the following compound (C) are excluded.

(B1): a compound having an effect of decreasing the intensity of the microwave photoconductive signal (b2): a compound having an effect of shortening the decay time of the intensity of the microwave photoconductive signal (b3): having a desensitizing effect of photographic sensitivity Compound (b4): a compound that forms a deep electron trap level that holds the trapped electrons for 5 seconds or more (b5): a compound that forms a deeper electron trap level than the following compound (C) (b6): 0.6 eV A compound that forms a deeper electron trap level.

Compound (C): Ir-containing compound and complex.

2. The silver chlorobromide particles are the following compound (A)
2. The silver halide emulsion according to the above item 1, wherein the silver halide emulsion contains both at least one compound of the formula (I) and at least one compound (C).

Compound (A): a compound corresponding to at least one of the following (a1) to (a6).

However, compounds belonging to compound (C) are excluded.

(A1): a compound having an effect of increasing the intensity of the microwave photoconductive signal (a2): a compound having an effect of increasing the decay time of the intensity of the microwave photoconductive signal (a3): having a sensitizing effect of photographic sensitivity Compound (a4): Compound that forms a shallow electron trap level that releases trapped electrons in less than 50 ns (a5): Compound that forms a shallower electron trap level than compound (C) (a6): 0.03 to A compound that forms an electron trap level having a depth of 0.3 eV.

3. 3. The silver halide emulsion according to the above item 2, wherein the compound (C) is present in a silver bromide high content region, and the Ir content in the region is the highest in the silver halide grains.

4. 4. The silver halide emulsion according to any one of the above items 1 to 3, wherein silver halide fine particles having a smaller particle size than the silver chlorobromide particles and having a silver bromide content of 15% or more are added. A silver halide emulsion characterized in that a silver bromide-rich region is formed.

5. Chemical sensitization is performed at a molar ratio of chalcogen sensitizer to gold sensitizer of 0.5 or less, and from 60 minutes before the addition of the chemical sensitizer to immediately before the addition of the chemical sensitizer,
5. The silver halide emulsion according to the item 4, wherein fine silver halide grains are added.

6. The proportion of the added silver halide fine grains is 0.1 mol% or more and 5 mol% or less with respect to the total silver content of the finally obtained silver halide emulsion grains, and 90% or more of the total silver bromide. Br mole% of silver halide fine particles based on the total silver amount and Ir mole / Ag mole present when silver halide fine particles are added satisfy the following formulas [1] and [2]. 6. The silver halide emulsion according to the above item 4 or 5, wherein

Formula [1] Ir> 2 × 10 ⁻⁹ (138.63 × Br mol%) Formula [2] Ir <6 × 10 ⁻⁷ (434.67 × Br mol%) The compound (A) and the compound (B) are not substantially present on the surface of the silver halide grains, and the region containing the compound (B) is a region containing the compound (C). 7. The silver halide emulsion as described in any one of the above items 2 to 6, wherein the emulsion is located inside the silver halide grains.

8. The compound (A) and the compound (B) are not substantially present on the surface of the silver halide grains, and the region containing the compound (B) is a region containing the compound (A). Item 8. The silver halide emulsion according to any one of Items 2 to 7, wherein the silver halide emulsion is located inside the silver halide grains.

9. 9. A silver halide photographic material, wherein at least one layer contains the silver halide emulsion according to any one of the above items 1 to 8.

10. On the characteristic curve obtained with an exposure time of 0.5 seconds, the ratio of the density point γ showing a value of fog +1.8 to the density point γ on the characteristic curve obtained with an exposure time of 10 ⁻⁶ seconds The silver halide photographic light-sensitive material according to the above item 9, wherein is adjusted to 0.8 to 1.5.

Although the reason for the phenomenon caused by appropriately adjusting the decay time of the signal intensity in the excitation absorption of microwave photoconductivity according to the present invention has not been theoretically interpreted yet, such electronic conditions It is presumed that the adjustment of the value affects the manner in which the latent image is formed and the distribution of the latent image, thereby affecting how the latent image is bleached during development.

Hereinafter, the present invention will be described in detail.

Compounds (A) and (B) according to the present invention
The determination of compound (C) can be performed by the method described below.

The compounds (A) and (B) of the present invention can be discriminated by microwave photoconductivity measurement in the range of 10 ^-8 to 10 ^-4 mol / 1 mol Ag, and the compound to be evaluated is halogenated by a method known in the art. An emulsion obtained by uniformly doping silver halide grains was used as a measurement sample in accordance with JP-A-10-186558, and the microwave photoconductive signal intensity (hereinafter, also simply referred to as signal intensity) and the decay time of microwave photoconductive signal intensity (hereinafter simply referred to as "signal intensity") were measured. Decay time of the signal intensity).

Microwave photoconductivity measurement is a well-known method in the art for evaluating the physical properties of silver halide photographic emulsions. M. Kellogg, Photographic Science and Engineering, 18
The measurement can be carried out with reference to the method described in Vol. 378, page 1974 (1974). The detailed conditions of the microwave photoconductivity measurement performed in the present invention are described in JP-A-5-4575.
According to the description of No. 8.

In the present invention, the decay time of the photoconductivity signal intensity in the microwave photoconductivity measurement is defined as the time required to decay to half the peak intensity.

However, the silver halide grains contained in the silver halide emulsion at this time have a silver chloride content of 90 mol% or more, and when silver halide other than silver chloride is contained, the silver halide grains It is necessary to prepare so as to be uniformly distributed in the grains, and it is prepared without containing any compound other than silver chloride, silver bromide, silver iodide and one kind of the evaluation compound.

When the silver halide emulsion containing the above evaluation compound has a higher signal intensity or a longer decay time of the signal intensity than the silver halide emulsion containing no evaluation compound prepared under the same conditions, , Compound (A)
When the signal intensity is low or the decay time of the signal intensity is short, it can be determined that the compound (B).

The silver halide emulsion containing the above-mentioned evaluation compound can also be discriminated by optimally performing a chemical sensitization process using a gold or sulfur sensitizer known in the art. Optimum chemical sensitization with a chalcogen sensitizer and a noble metal sensitizer known in the art other than the gold and sulfur sensitizers can also be evaluated. The determination is made almost optimally for the emulsion that has undergone the chemical sensitization process. If the silver halide emulsion containing the evaluation compound is sensitized as compared with a silver halide emulsion which has not been contained and has been similarly chemically sensitized, the evaluation compound is compound (A); When desensitized, it can be determined that the compound is the compound (B).

The compound (A) is not particularly limited as long as it can increase the sensitivity by containing this compound, and a metal complex, a reduction sensitizer, a sensitizing dye and the like can be used.
Those having a large effect of increasing the sensitivity are more preferable, and the effects of the present invention can be obtained. In particular, a complex in which four or more cyanos are coordinated to iron, ruthenium, and osmium is more effective, and is more preferable.

Specific examples of the compound (A) are shown below, but the invention is not limited thereto.

(A1) K ₄ Fe (CN) ₆ (A2) CdCl ₂ (A3) K ₄ Ru (CN) ₆ (A4) K ₄ Os (CN) ₆ (A5) Ascorbic acid (A6) Sorbic acid (A7 Thiourea (A8) SnCl ₂ (A9) NH ₄ SCN Similarly, the compound (B) is not particularly limited as long as it can be desensitized by doping this compound. Metal complexes, desensitizing dyes, electron trapping agents Etc., but those having a large desensitizing effect are more preferable, and a metal complex in which rhodium, osmium, ruthenium is coordinated with four or more halogens is more preferable because a more effective effect is obtained, and particularly a complex is preferable. Are more preferred.

Specific examples of the compound (B) are shown below, but the invention is not limited thereto.

(B1) K ₃ [RhBr ₆ ] (B2) K ₂ [PdCl ₄ ] (B3) K ₂ [RuCl ₅ (NO)] (B4) K ₂ [OsCl ₆ ] (B5) K ₃ [Co ( CN) ₆ ] (B6) K ₂ [RuCl5H ₂ O] (B7) K ₃ [Ru ₂ Cl ₈ N (H ₂ O) ₂ ] (B8) K [OsO ₃ N] (B9) K ₃ [RhCl ₆ ] (B10) Phenosafranine (B11) Pinacryptol green The compound (C) is not particularly limited as long as it is an Ir compound, but a complex in which four or more halogen ligands are coordinated is more preferable.

The term "inside of the grain" as used in the present invention means that 10 grains or more of silver halide molecules are located inside the grain surface.

The "(b6) of the compound (B): a compound forming an electron trap level deeper than 0.6 eV" in the first aspect of the present invention is described in Tables 2 and 5 on page 38 of Fundamentals of Photographic Engineering. The Rh compound and the Pd compound described in (1) correspond to this. An electron trap level deeper than 0.6 eV is preferable, and the deeper it is, the more preferable. Compounds forming an electron trap level shallower than 0.3 eV are classified as compound (A) (a6).

The compound (B) (b4) of the compound (B), which is a compound forming a deep electron trap level holding the trapped electrons for 5 seconds or more, referred to in claim 1 of the present invention. The “deep electron trap level to be held” means that the effect of the present invention cannot be obtained if the level is held for less than 5 seconds.

In the compound (A) of the present invention, "(a6) of the compound (A): a compound forming an electron trap level having a depth of 0.03 to 0.3 eV" is referred to as "0.0.
“(A6) of compound (A), which is a compound that forms an electron trap level having a depth of 3 to 0.3 eV”, includes Pb, Cd, and Pb described in Tables 2 and 5 of the Fundamentals of Photographic Engineering. C
N ligand metals, divalent metal ions, and the like correspond. 0.
When an electron trap level shallower than 03 eV is formed, the effect of the present invention is hardly obtained.

In the compound (A) of the present invention, "(a4) of the compound (A): a compound forming a shallow electron trap level which releases a trapped electron in less than 50 ns" The “shallow electron trap level emitted by” is because the effect of the present invention cannot be obtained when the electron trap level is 50 ns or more.

The amount of the compound (A) to be added to the silver halide emulsion of the present invention is such that the microwave photoconductive signal intensity, the decay time of the microwave photoconductive signal intensity or the photographic sensitivity of the silver halide emulsion do not contain the compound (A). 2
It is preferable to dope and contain an amount that is twice or more.

The amount of the compound (B) to be added to the silver halide emulsion of the present invention depends on the microwave photoconductive signal intensity, the decay time of the microwave photoconductive signal intensity or the photographic sensitivity of the silver halide emulsion when the compound (B) is not contained. Of 1
/ 2 or less is preferably doped and contained.

In the silver halide emulsion of the present invention, it is preferable that the region containing the compound (C) and the region containing the compound (B) are adjacent or intersecting inside the silver halide grains. It is preferable that the region containing A) and the region containing compound (C) are adjacent to or cross each other inside the silver halide grains.

The expression that the regions containing the compounds are adjacent or cross each other inside the silver halide means that they are adjacent inside the silver halide, or a part or all of them overlap.

In the silver halide emulsion of the present invention, the compound (A) and the compound (B) are not substantially present on the surface of the silver halide grains, and the grain center of the region containing the compound (A) is not present. It is preferable that the boundary distant from is located 50% to 95% from the particle center on a line connecting the particle center and the point farthest from the particle center.

The term “particle surface” as used herein refers to a range containing 100 mol% of silver when the amount of silver added during the formation of the particles is represented by mol%.

The term "substantially absent" means that the compound does not substantially exhibit the effect, and the region containing the compound means a region containing the compound in an amount in which the compound exhibits a substantial effect. The amount at which the compound (A) substantially exerts the effect is 1 × 10 ⁻⁸ to 10 ⁻³ mol / 1 mol Ag, and the amount of the compound (B) is 1 × 10 ⁻¹⁰ to 10 ⁻⁶ mol. / 1 mol Ag.

The phrase "the region containing the compound (B) is located on the inside of the silver halide grains relative to the region containing the compound (C) or (A)" according to claim 7 or 8 of the present invention. Means that at least a part of the region containing the compound (B) is located closer to the center of the particle than the region containing the compound (C) or (A). Further, the region containing the compound (B) and the region containing the compound (C) or (A) are preferably adjacent or crossing.

The regions containing the compounds (A), (B) and (C) are each located in a region of 20 mol% or less of Ag mol% of the silver halide grains. More preferably, it is 10 to 10 mol%. The silver halide emulsion of the present invention preferably has a region containing the compound (A) outside the region containing the compound (B).

The compounds (A) and (B) of the present invention are preferably metal complexes in terms of doping efficiency, but are not limited thereto. When the compounds (A) and (B) according to the present invention are metal complexes, they can be added to the silver halide emulsion in the form of salts or complex salts.

The chemical sensitization process referred to in the present invention is a chemical sensitization process using a chalcogen sensitizer or a noble metal sensitizer known in the art.

The point γ in the tenth aspect of the present invention is represented by a slope of a tangent at a density of fog + 1.8 on the HD characteristic curve, that is, dD / dH.

In order to incorporate the compound according to the present invention into the silver halide emulsion according to the present invention, the compound according to the present invention is added before forming the silver halide grains, during forming the silver halide grains,
It may be added at any place in each step during physical ripening after the formation of silver halide grains. In order to obtain a silver halide emulsion satisfying the above conditions, it is preferable that the compound of the present invention is dissolved together with a halide salt and added during the grain formation step.

When the compound according to the present invention is added to a silver halide emulsion, the amount is 1 × 10 5 per mol of silver halide.
^It is more preferably from ^-9 mol to 1 × 10 ⁻² mol, particularly preferably from 1 × 10 ⁻⁸ mol to 5 × 10 ⁻⁵ mol.

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a particle having a (100) plane as a crystal surface, and examples thereof include a cubic particle and a tabular particle. U.S. Pat.
183,756, 4,225,666, JP-A-55-26589, JP-B-55-42737, and The Journal of Photographic Science (J. Photogr. Sci.) 21, 39 (197
Particles having shapes such as octahedron, tetradecahedron, and dodecahedron can be produced by a method described in a document such as 3) 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.

The silver halide grains according to the present invention have a region where the silver bromide content is higher than the others, and the position of the silver bromide high content region can be selected according to the purpose. In order to achieve the above-mentioned object, it is preferable that the particles are located in the periphery including the point farthest from the center of the particle. The composition of the silver bromide high content region may change continuously or may change discontinuously. The silver bromide high content region may be epitaxially bonded on the silver halide host grains, and a composition region satisfying the above conditions without forming a complete phase may partially exist.

The compound (C) is present in the high silver bromide content region of the silver halide emulsion according to the third aspect of the present invention,
Preferably, 50% or more of the total amount of the compound (C) contained in the finally obtained silver halide grains is present in the region, more preferably, 75% or more.

The silver halide emulsion according to the present invention is preferably formed by adding silver halide fine grains having a smaller particle size than the host grains and a higher silver bromide content than the host grains. The amount of bromide in the silver halide fine grains depends on the total silver halide 1 in the finally obtained silver halide emulsion.
It is preferably from 0.1 to 3.0 mol%, more preferably from 0.2 to 2.0 mol%, based on mol. Further, the Br mol% of the finally obtained silver halide emulsion is preferably 0.1 to 3.0 mol% based on the total silver amount.

The silver halide fine particles used in the present invention are particularly preferably formed in the presence of the compound (C). In the present invention, the method of using silver halide fine particles formed in the presence of the compound (C) in combination with silver halide fine particles not containing the compound (C) prepares a preferable amount of the compound (C). It is effective when. That is, in the present invention, control of the amount of the compound (C) added to the host grains is an indispensable technique, and a certain amount of silver halide fine grains not containing the compound (C) can be adjusted by adding or subtracting as necessary. Can control the amount of various compounds (C) to be added to host grains with one kind of silver halide fine particles produced in the presence of the compound (C). This is an effective technique for improving the emulsion preparation efficiency of the present invention because the step of newly producing silver fine particles can be omitted.

The silver halide fine particles used in the present invention preferably include a step of removing water and a part of the water-soluble compound during the addition after the formation. The removal method can be conveniently selected as needed, such as ultrafiltration, electrodialysis, etc., but a method using an ultrafiltration membrane is preferably used, and among them, an ultrafiltration apparatus having a hollow membrane therein is used. It is preferably used, and can be conveniently selected as necessary.

The particle size of the silver halide fine particles used in the present invention is preferably 0.1 μm or less, more preferably 0.0 μm or less.
It is preferably 7 μm or less.

The grain size of the silver halide grains according to the present invention is not particularly limited. However, in consideration of other photographic properties such as rapid processing property, sensitivity and gradation, the diameter is preferably 0.1 to 0.1 in terms of volume sphere. 1.2 μm, more preferably 0.2 to 1.0 μm
m. The volume sphere conversion diameter indicates a diameter when the particle volume is converted into a sphere. There is no limitation on the shape of the silver halide grains according to the present invention. The grain size of the silver halide grains can be measured using the projected area of the grains or an approximate value of the diameter. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area.

The particle size distribution of the silver halide grains according to the present invention is preferably a monodisperse silver halide grain having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, and particularly preferably a coefficient of variation. 0.15 or less monodispersed emulsions are added to the same layer. The variation coefficient referred to here 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 grain size distribution, and R represents the average grain size). Various apparatuses and methods known in the art can be used for preparing silver halide emulsions. A method 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 and
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 disposed in a reaction mother liquor, and a water-soluble silver described in German Offenlegungsschrift 2,921,164, etc. A device for continuously adding a salt and an aqueous solution of a water-soluble halide salt while changing the concentration,
No. 501776, etc., a reaction mother liquor may be taken out of a reactor and concentrated by an ultrafiltration method to form grains while keeping the distance between silver halide grains constant.

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 of the present invention can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer.

The chalcogen sensitizer applied to the silver halide emulsion of the present invention includes a sulfur sensitizer, a selenium sensitizer,
A tellurium sensitizer can be used, but a sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, triethylthiourea, allylthiocarbamide thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, and inorganic sulfur.

As a gold sensitizer, 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 sensitizer used is not uniform depending on the type of silver halide emulsion, the type of compound used, ripening conditions, and the like.
It is preferably from 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ mol per mol. More preferably, 1 × 10 ⁻⁵ mol to 1 × 10
^-8 mol.

The addition ratio of the chalcogen sensitizer and the gold sensitizer to achieve the improvement in suitability for high illuminance short-time exposure intended by the present invention is 0.5 or less, and more preferably 0.3 to 0.3.
0.4 is preferred.

As a chemical sensitization method for the silver halide emulsion of the present invention, a reduction sensitization method may be used.

The silver halide emulsion of the present invention is used for the purpose of preventing fog generated during the process of preparing a silver halide photographic material, reducing performance fluctuation during storage, and preventing fog generated during development. Known antifoggants and stabilizers can be used. Examples of preferred compounds that can be used for such a purpose are described in JP-A-2-14603.
The compounds represented by the general formula (II) described in the lower column of page 7 of JP-A-6 can be mentioned. More preferred specific compounds are (IIa-
1) to (IIa-8), (IIb-1) to (IIb-7), 1- (3-methoxyphenyl) -5-mercaptotetrazole, 1- (4-ethoxyphenyl) -5
Compounds such as 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, it is preferably used in an amount of about 1 × 10 ⁻⁵ mol to 5 × 10 ⁻⁴ mol per mol of silver halide. When added at the end of chemical sensitization, 1 × 10 ^-6 mol to 1 mol per mol of silver halide is used.
An amount of about × 10 ⁻² mol is preferable, and 1 × 10 ⁻⁵ mol to 5
× 10 ^-3 mol is 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 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁵ mol. 1 × 10 ^-2 mol is more preferred. When added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 ^-9 mol to 1 × 10 ^-3 mol per 1 m ² .

The silver halide photographic light-sensitive material of the present invention includes:
Dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any known compounds can be used. In particular, dyes having absorption in the visible region include AI-1 described in JP-A-3-251840, page 308.
To 11 and the dyes described in JP-A-6-3770 are preferably used. Examples of the infrared absorbing dyes include general formulas (I) and (II) described in the lower left column of page 2 of JP-A-1-280750. , (III) have preferred spectral characteristics, have no effect on the photographic characteristics of the silver halide photographic emulsion, and are free from contamination by residual color.
As specific examples of preferred compounds, the exemplified compounds (1) to (4) listed in the lower left column of page 3 to the lower left column of page 5 of the publication are referred to.
5).

The amount of these dyes added is 680 nm for an unprocessed sample of a light-sensitive material for the purpose of improving sharpness.
Is preferably an amount that makes the spectral reflection density 0.7 or more, and more preferably 0.8 or more.

It is preferable to add a fluorescent whitening agent to the light-sensitive material of the present invention since whiteness 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 of the present invention is used as a color photographic light-sensitive material, a halogen 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 layer containing a silver halide emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

As the spectral sensitizing dye used in the silver halide emulsion of the present invention, any known compounds can be used.
BS-1 to 8 described in page 1 of JP 1840 can be preferably used alone or in combination. Examples of the green photosensitive sensitizing dye include G
S-1 to S-5 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 light-sensitive sensitizing dyes include supersensitizers SS-1 to SS-9 described on pages 8 to 9 of JP-A-4-285950 and JP-A-5-66515. It is preferable to use compounds S-1 to S-17 described on pages 15 to 17 in combination. These sensitizing dyes may be added at any time from the formation of silver halide grains to the end of chemical sensitization.

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

As the coupler used in the light-sensitive material of the present invention, any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength range longer than 340 nm by coupling reaction with an oxidized form of a color developing agent is used. Although it is also possible to use, 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 magenta dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, A typical example is a cyan dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm.

Cyan couplers which can be preferably used in the light-sensitive material according to the present invention are described in JP-A-4-114.
No. 154, page 5, lower left column, formula (C-
Couplers represented by I) and (C-II) can 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 in the same specification.

The magenta coupler which can be preferably used in the light-sensitive material according to the present invention is described in JP-A-4-11.
The general formula (M-
Couplers represented by I) and (M-II) can be mentioned. Specific compounds include those described as MC-1 to MC-11 in the lower left column of page 4 to the upper right column of page 5 of the publication. Among the above magenta couplers, a coupler represented by the general formula (MI) described in the upper right column on page 4 of the same publication is preferable, and among them, the RM of the general formula (MI) is tertiary. Couplers that are alkyl groups are particularly preferred because of their excellent light resistance. MC-8 to MC-11 described in the upper column on page 5 of the same publication are excellent in reproducing colors from blue to purple and red, and are also excellent in detail delineation power, and thus are preferable.

The yellow coupler which can be preferably used in the light-sensitive material according to the present invention is described in JP-A No. 4-11.
The general formula (Y-
The couplers represented by I) can be mentioned. Specific compounds are described in YC-1 to YC
What is described as C-9 can be mentioned. Of these, couplers in which RY1 in the general formula [Y-1] is an alkoxy group or couplers represented by the general formula [I] described in JP-A-6-67388 can reproduce yellow having a preferable color tone and are 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 N-type compounds described in pages 13 to 14 of JP-A-6-67388.
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 page 1 of JP-A-7 and page 11-17 of the same publication.

When the oil-in-water type emulsification dispersion method is used to add the coupler or other organic compound used in the light-sensitive material according to the present invention, it is usually added to a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or more. If necessary, a low-boiling point and / or water-soluble organic solvent is used in combination to dissolve, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As the dispersing means, for example, 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. As a high boiling organic solvent that can be used to dissolve and disperse the coupler, dioctyl phthalate,
Phthalates such as diisodecyl phthalate and dibutyl phthalate, and phosphates such as tricresyl phosphate and trioctyl phthalate are preferably used. The high-boiling organic solvent has a dielectric constant of 3.5 to 3.5.
It is preferably 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).

A preferred compound used as a surfactant for dispersing a photographic additive or adjusting the surface tension during coating contains a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule. To do. Specifically, A-1 to A-1 described in JP-A-64-26854.
1 is mentioned. 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, but it is better that the time until the addition to the coating solution after the dispersion and the time from the addition to the coating solution after the addition are short. Each is preferably within 10 hours, more preferably within 3 hours and 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, phenolic compounds represented by general formula IIIB described in JP-A-3-174150, and Amine compounds represented by the general formula A described in JP-A-64-90445;
General formulas XII, XIII, XIV, XV described in -182741
Are particularly preferred for magenta dyes. Further, compounds represented by the general formula I 'described in JP-A-1-19649 and compounds represented by the general formula II described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the coloring dye, compound (d-11) described in the lower left column of page 9 of JP-A-4-114154 and compound (A'-) described in the lower left column of page 10 of the same publication are disclosed. Compounds such as 1) can be used. In addition to this, U.S. Pat.
The fluorescent dye-releasing compound described in (1) can also be used.

In the 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 added to a silver halide emulsion layer. It is preferable to improve fog and the like. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkylhydroquinone such as 2,5-di-t-octylhydroquinone. Particularly preferred compounds are those represented by the general formula II described in JP-A-4-133056, and include compounds II-1 to II-14 described on pages 13 to 14 and compound 1 described on page 17 of the same publication. .

It is preferable to add an ultraviolet absorber to the light-sensitive material of the present invention to prevent static fog or to improve the light fastness of a dye image. Preferable ultraviolet absorbers include benzotriazoles, and particularly preferable compounds are those represented by the general formula described in JP-A-1-250944.
A compound represented by the formula III-3, a compound represented by the general formula III described in JP-A-64-66646,
UV-1L to UV-27L described in 187240,
Examples include compounds represented by the general formula I described in JP-A-4-1633, and compounds represented by the general formulas (I) and (II) described in JP-A-5-165144.

It is advantageous to use gelatin as a binder in the light-sensitive material of the present invention. If necessary, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives Alternatively, a hydrophilic colloid such as a single or copolymerized hydrophilic polymer can 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.

As the support used in the light-sensitive material of the present invention, any material may be used, such as paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, vinyl chloride sheet, white For example, polypropylene, polyethylene terephthalate support, baryta paper, etc. which may contain a pigment 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 was 13% by weight for improving sharpness.
The above is preferred, and more preferably 15% by weight.

The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support used in 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 as a coefficient of variation described in the above-mentioned publication,
More preferably, it is 15 or less.

The center surface average roughness (SRa) of the support is preferably 0.15 μm or less, more preferably 0.12 μm or less, because the effect of good gloss can be obtained, and it is more preferable. 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 light-sensitive material of the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support, if necessary, and then directly or undercoating (adhesion, antistatic property, size, It may be applied via one or more undercoat layers for improving degree stability, friction resistance, hardness, antihalation property, frictional properties and / or other properties.

In coating a light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. As an application method, an extrusion coating and a curtain coating, which can apply two or more kinds of layers at the same time, are particularly useful.

In order to form a photographic image using the photosensitive material of the present invention, the image recorded on the negative may be optically formed on the photosensitive material to be printed and printed. Is once converted into digital information, the image is formed on a CRT (cathode ray tube), and this image may be formed on a photosensitive material to be printed and printed, or a laser based on the digital information may be used. The printing may be performed by scanning while changing the light intensity.

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 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.

Known compounds can be used as the aromatic primary amine developing agent used in the present invention. 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 developer can be used in any pH range, but from the viewpoint of rapid processing, the pH is 9.5 to 13.0.
And more preferably pH 9.8-1.
It is used in the range of 2.0.

The processing temperature for color development is 35 ° C. or higher and 70 ° C.
C. or less is preferred. 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 40 seconds, more preferably within 25 seconds.

To the color developing solution, known developing component compounds can be added in addition to the above color developing agents. 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 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, a water washing process is usually 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 photosensitive material of the present invention may be a roller transport type in which the photosensitive material is transported between rollers arranged in a processing tank, or may be transported by fixing the photosensitive material to a belt. An endless belt method may be used, but a processing tank is formed in a slit shape, and a processing liquid is supplied to the processing tank and the photosensitive material is conveyed. A web system by contact with a carrier impregnated with, a system using a viscous treatment liquid, and the like can also be used. When processing in large quantities, it is usual to perform a running process using an automatic developing machine. At this time, the replenishment amount of the replenisher is preferably as small as possible. The most preferred method is to add a treating agent in the form of the method described in JP-A-94-16935.

[0117]

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 (Preparation of silver halide emulsion E-1)
(A solution) and (B)
Liquid) to 20 while controlling pAg = 7.3 and pH = 3.0.
At the same time, and then add the following (Solution C) and (Solution D)
Was added simultaneously over 120 minutes while controlling to pAg = 8.0 and pH = 5.5. At this time, the pAg is controlled by
The pH was controlled using a sulfuric acid or sodium hydroxide aqueous solution.

(Solution A) Sodium chloride 0.48 g Potassium bromide 0.004 g Water was added to 28 ml (Solution B) Silver nitrate 1.4 g Water was added to 28 ml (Solution C) Sodium chloride 129.4 g Potassium bromide 133 g of water and 661 ml (solution D) of silver nitrate 376.6 g of water and 661 ml after completion of addition and desalting using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., Ltd. 0.40μ average particle size by mixing with gelatin aqueous solution
m, coefficient of variation of particle size distribution 0.08, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion E-1 was obtained.

Next, in the step of preparing the silver halide emulsion E-1, except that the compound according to the present invention was added to each of the solution A and the solution C so that the total addition amount was as shown in Table 1, E-
In the same manner as in Example 1, silver halide emulsions E-2 to E-6 were prepared. When the compound changed or added at this time is the compound (A) of the present invention, 1 × 10 ⁻⁵ mol / A
g molar amount, and in the case of compounds (B) and (C), 1 × 1
A ^0-8 mole / Ag mole amount was added. E-1 to E obtained
Samples were prepared from the emulsions Nos. -6 and 6 by a measurement method as described in JP-A-10-186558, and the decay time of the photoconductivity signal intensity and the photoconductivity signal intensity were evaluated. The decay time of the photoconductivity signal intensity and the photoconductivity signal intensity of E-1 were each set to 100, and the other emulsions were evaluated in the same manner and evaluated as relative values.

Table 1 shows the results.

[0122]

[Table 1]

In the table, (A1) = K ₄ Fe (CN) ₆ , (A
2) = CdCl ₂ , (B1) = K ₃ [RhBr ₆ ], (B
2) = K ₂ [PdCl ₄ ], (C1) = K ₂ [IrCl ₆ ]
Represents

From the results of the photoconductivity signal intensity evaluation and the photoconductivity signal intensity decay time evaluation in Table 1, it can be seen that it is possible to determine which of the compounds of the present invention each compound corresponds to.

(Preparation of silver halide fine grain emulsion BI-0) 1.5 liters of a 3% gelatin aqueous solution kept at 30 ° C. was adjusted to pAg = 9.0 and pH = 2.0, and stirred at a high speed. 5N silver nitrate (solution b) over 10 minutes
2. Add 00 ml and keep pAg = 9.0.
5N potassium bromide (solution a) was added simultaneously. After completion of the addition, a commercially available ultrafiltration apparatus having a hollow particle membrane therein was used to obtain a silver bromide fine grain emulsion BI-0 having an average particle size of 0.05 μm, with the total volume being １ ／ of that at the end of the addition. Was.

(Preparation of silver halide fine grain emulsion BI-1) In the preparation of silver halide fine grain emulsion BI-0,
A silver bromide fine grain emulsion BI-1 was obtained in the same manner except that a solution (solution c) in which K ₂ IrCl ₆ was further added to solution a so as to be 1 × 10 ⁻³ mol / Ag mol was used. The average particle size of the obtained silver halide fine particles was 0.05 μm.

(Preparation of Green-Sensitive Silver Halide Emulsion E2-1) At 60 ° C., 0.5 mol% of silver bromide and 5 × 10 ^-7 mol of Ir based on the total amount of silver based on E-1. The silver halide fine grain emulsion BI-0 and the silver halide fine grain emulsion BI-1 were adjusted so as to be / Ag mole and added. 30 minutes later, the following additives were added, and then the stabilizer STAB-1 was added.
Was added to obtain an appropriate sensitivity, and an optimal chemical sensitization was performed to prepare a green-sensitive silver halide emulsion E2-1.

Similarly, each of the silver halide emulsions E-2 to E-6 was subjected to the same chemical sensitization as in the case of E-1.
2-2 to E2-6 green-sensitive silver halide emulsions were prepared.

Additives Addition amount 1. 1. Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX 2. chloroauric acid 2.4 mg mol / mol AgX 3. Sodium thiosulfate 30 mol% based on chloroauric acid Stabilizer STAB-1 STAB-1: 1- (3-acetamidophenyl) -5-mercaptotetrazole

[0130]

Embedded image

Preparation of Coated Samples Each layer shown in Table 2 was successively placed on a paper support on which polyethylene was laminated on one side and polyethylene containing titanium oxide was laminated on another side (the side on which the photographic constituent layer was coated). The sample was applied to prepare Sample 1.

[0132]

[Table 2]

As a hardener, H-1 was added to the second layer.

[0134]

Embedded image

ST-3: 1,4-dibutoxy-2,5
-Di-t-butylbenzene ST-4: 4- (4-hexyloxyphenyl) thiomorpholine-1-dioxide ST-5: 1,1-bis (2-methyl-4-hydroxyl-5-t-butyl Phenyl) butane TOP: trioctyl phosphate H-1: 2,4-dichloro-6-hydroxy-s-triazine sodium Sodium Then, instead of E2-1 of sample 1, E2-2 to E
Samples 2 to 6 were prepared in the same manner except that each of the silver halide emulsions 2 to 6 was used.

Next, except that the compounds to be added to Solution A and Solution C at the time of preparing E-2 were changed as shown in Table 3, E-2
E-7 to E-12 were prepared in the same manner as described above, and subjected to chemical sensitization in the same manner as in E-2 to obtain a green-sensitive silver halide emulsion E2-7 to E-2.
2-12 was obtained. At this time, the addition amount of the compounds (A), (B) and (C) according to the present invention is E2-2 to E2.
-6 was the same as the addition amount.

After the particles were formed during the preparation of E-10, before the desalting process using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., Ltd., 1% of the total silver was obtained. Mol% of the above (solution a), (solution c) and 1
E-13 was prepared in the same manner as E-10 except that mol% (solution b) was added, and then chemically sensitized in the same manner as E2-2 except that BI-0 and BI-1 were not added. go,
E2-13 was obtained.

Also, BI-0 and B in E2-10
Except that the addition of I-1 was not carried out,
2-14 was obtained.

Instead of E2-1 of Sample 1, E2-7 to E2-7
Samples 7-14 were prepared in the same manner except that 2-14 was used.

In the table, (A1) = K ₄ Fe (CN) ₆ , (A
2) = CdCl ₂ , (B1) = K ₃ [RhBr ₆ ], (B
2) = K ₂ [PdCl ₄ ], (C1) = K ₂ [IrCl ₆ ]
Represents

In the cubic silver halide emulsions E-1 to E-12 obtained above, the presence of a phase having a high silver bromide content was confirmed by X-ray analysis. The highest was confirmed.

The following evaluation was performed for each sample obtained as described above.

<Evaluation Method><Toneγ> Wedge exposure with white light for 0.05 seconds, color development according to the following processing steps, and then using an optical densitometer (Konica's PDA-65 type). The density was measured, and the gradation γ was determined by the following equation, and displayed as a relative gradation γ with the gradation γ of Sample 1 being 100.

Tone γ = 1 / [Log (exposure indicating fog + 0.8 density) −Log (exposure indicating fog + 1.8 density)] <Reciprocity failure characteristic> Wedge exposure is performed for 1 second, 10 seconds for low illuminance, and 0.03 seconds for high illuminance, and color development is performed according to the following processing steps. Then, the density is measured using an optical densitometer (Konica's PDA-65 type). , When the gradation (γ0) in the 0.1 second exposure is 100, the gradation (γL) in the 10 second exposure with low illuminance,
The difference (γL−γ0, γH−γ0) of the relative value of the gradation (γH) in 0.03 second exposure under high illuminance is shown. However,
γ0, γL and γH are measured points at 0.2% of the fog density.
The calculation was performed in the same manner as the gradation γ except that the density was changed to a high density and a 1.2 density.

<Latent Image Stability> A sample subjected to the following color development processing 10 seconds after exposure to white light and a sample subjected to the following color development processing 5 minutes after exposure to white light were subjected to density measurement using a Konica PDA-65 type.
It was expressed as the difference (Δγ) between γ1 when color development was performed 10 seconds after exposure and γ2 when color development was performed 5 minutes after exposure.

Δγ = γ1−γ2 where γ1 and γ2 are calculated in the same manner as the gradation γ, except that the measurement point is changed to a density 0.1 and 0.35 higher than the fog density. did.

<< Color Development Processing >> Processing Step Processing Temperature Time Replenishment Color Development 38.0 ± 0.3 ° C. 45 seconds 80 ml Bleaching and Fixing 35.0 ± 0.5 ° C. 45 seconds 120 ml Stabilization 30-34 ° C. 60 seconds 150 ml Drying 60-80 ° C. 30 seconds Composition of developing solution 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 Tri Ethanolamine 10.0g 10.0g Diethylenetriaminepentaacetic acid Thorium 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 Each was added with water to make the total volume 1 liter, and the tank solution was pH = 10.10 and the replenisher was adjusted to pH = 10.60.

Bleach-fix solution and replenisher solution 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 was added to make the total volume 1 liter, and the pH was 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 Optical brightener (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 ( Polyvinylpyrrolidone) 1.0 g Ammonia water (25% aqueous solution of ammonium hydroxide) 2.5 g Nitrilotriacetic acid / trisodium salt 1.5 g Add water to make the total volume 1 liter, and adjust the pH to 7.5 with sulfuric acid or ammonia water. It was adjusted.

Table 3 shows the results obtained as described above.

[0151]

[Table 3]

As is clear from Table 3, the samples according to the present invention exhibited favorable effects on high contrast, latent image stability and reciprocity failure characteristics. In particular, it can be seen that Samples 10 to 12 are preferable in terms of achieving both reciprocity failure characteristics and latent image preservation.

The samples 13 and 14 correspond to the sample 10
Since the reciprocity failure property and the stability of the latent image are slightly deteriorated as compared with the above, it is preferable that the formation of the silver bromide-rich region is preferably performed after the desalting process using a silver halide fine grain emulsion. found.

Example 2 A green-sensitive silver halide emulsion E2-15 was prepared in the same manner as in the green-sensitive silver halide emulsion E2-10 except that the amount of sodium thiosulfate was changed with respect to the amount of chloroauric acid as shown in Table 4.
To E2-17 were prepared, and E10 in Sample 10 of Example 1 was prepared.
Samples 15 to 17 were prepared in the same manner except that the silver halides E2-15 to E2-17 were used instead of 2-10, and the gradation in high-illuminance exposure was compared.

<Gradation Evaluation of High Illumination Exposure> Wedge exposure was performed by exposure for 10 ⁻⁶ seconds with a Xe flash, and the density was measured in the same manner as in Example 1. The gradation γ of the sample 15 at the time of high illuminance exposure is
00 and relative display. However, the gradation γ is the same as in the first embodiment.
Is the same as the method of measuring the gradation γ.

[0156]

[Table 4]

As is clear from Table 4, the high illuminance exposure characteristics aimed at by the present invention are as follows.
7, it was found that a high contrast was obtained, and further excellent gradation characteristics were exhibited.

Example 3 Table 5 shows the addition times of the silver halide fine particles BI-0 and BI-1 to the green-sensitive silver halide emulsion E2-10 based on the addition time of the chemical sensitizer. Green-sensitive silver halide emulsion E2
-18 to 21 were prepared. E2- of Sample 10 of Example 1
Samples 18 to 21 were prepared in the same manner except that Sample No. 10 was changed to the silver halides E2-18 to E2-21, and the sensitivity was measured in addition to the same evaluations as in Example 1.

<Measurement of Sensitivity> Wedge exposure was performed for 0.05 seconds with white light, color development was performed in accordance with the above-described processing steps, and then density was measured using an optical densitometer (PDA-65 manufactured by Konica). The sensitivity was expressed as the logarithm of the reciprocal of the exposure required to obtain a density 0.8 higher than the density. In addition, the sensitivity was represented by a relative sensitivity with the sensitivity of Sample 1 being 100.

Table 5 shows the results.

[0161]

[Table 5]

As is evident from Table 5, Sample 21 to which silver halide fine grains were added after the addition of the chemical sensitizer exhibited a large increase in fog without optimal chemical sensitization. The properties were not evaluated. In contrast, Samples 10, 19 and 20 to which silver halide fine grains were added within 60 minutes before the addition of the chemical sensitizer according to the present invention were Sample 1
As compared with No. 8, the effect is large and preferable with respect to the gradation γ, the reciprocity failure property and the latent image stability.

Example 4 The silver halide fine grains BI-0 and BI-1 were changed from the green-sensitive silver halide emulsion E2-10 so that the Br mole% and the Ir content shown in Table 6 were obtained. In the same manner, green-sensitive silver halide emulsions E2-22 to E2-25 were prepared, and E2-10 of Sample 10 of Example 1 was changed to the silver halides E2-22 to E2-25. Samples 22 to 25 were prepared. The obtained sample was obtained in Example 1.
In the same manner as above, the reciprocity law of high illuminance and the stability of the latent image were evaluated. The results are shown in Table 6.

[0164]

[Table 6]

As is clear from Table 6, the samples 10 and 24 satisfying the expressions [1] and [2] of claim 6 with respect to the amount of Br are the same as the samples 22, 23 and 25 not satisfying the conditions. By comparison, it can be seen that the effect of the present invention is great.

Example 5 In the green-sensitive silver halide emulsion E2-10, the addition positions of the respective compounds according to the present invention were adjusted so that the distribution shown in Table 7 was obtained by the added silver amount (%) during grain formation. Green-sensitive silver halide emulsions E2-26 to E2-2, except for the change
Sample Nos. 9 were prepared, and Samples 26 to 29 were prepared in the same manner as in Example 1 except that E2-10 of Sample 10 was changed to the silver halides E2-26 to E2-29. The amount of silver added was 10
0% indicates the particle surface.

In the same manner as in Example 1, the sensitivity, gradation γ, high illuminance reciprocity characteristic and latent image stability of each sample were evaluated. The obtained results are shown in Table 7. In addition, the value of fog was shown as a relative value with that of Sample 10 being 100.

[0168]

[Table 7]

As is clear from Table 7, the sample 27 in which the compound (B) was further arranged inside the silver halide than the compound (C) had the compound (B) and the compound (C) arranged at the same position. The sensitivity is higher than that of the sample 28, and the reciprocity failure property is also excellent. Compound (B) is compound (A)
The sample 27 disposed inside the silver halide grains rather than
The reciprocity failure property is superior to that of the sample 26 in which the compound (B) and the compound (A) are arranged at the same position. Further, the sample 26 in which the compounds (A) and (B) are not present on the surface of the silver halide grains has better fog and latent image stability than the sample 29 in which the compound is present on the surface. You can see that.

Example 6 A fine silver halide fine grain BI- having a preferable gradation in 0.5 second exposure to green-sensitive silver halide emulsion E2-10 and exhibiting a point γ as shown in Table 8 was obtained. 0
Similarly, green-sensitive silver halide emulsions E2-30 to E2-35 were prepared except that the addition amounts of BI-1 and BI-1 were adjusted, and E2-10 of Sample 10 of Example 1 was replaced with silver halide E2- Samples 30 to 35 were prepared in the same manner except that the samples were changed to 30 to E2-35. With respect to the obtained sample, the clarity of fine lines in high-intensity scanning exposure was measured according to the following method. The results are shown in Table 8.

<Evaluation of Fine Lines by High-Illuminance Scanning Exposure> An optical system using a helium / neon laser (about 544 nm) as a green light source has a beam diameter of about 80 μm, a polygon mirror, and a scanning speed of 160 m / sec. Under the condition that the exposure time is 5 × 10 ⁻⁷ seconds, the letter “A” is changed from Helvetica 4 points to 18 so that the density becomes 2.0.
Exposure was performed by changing the size to the point, and evaluated according to the following criteria.

◎: Gray fine lines can be clearly distinguished. ○: Gray fine lines can be clearly distinguished, but the outline is slightly blurred. Δ: Gray fine lines can be distinguished, but blur is noticeable. .

[0173]

[Table 8]

As is clear from Table 8, Sample 30 which is a comparative product having a low point γ ratio cannot have a preferable gradation in 0.5 second exposure. However, blur identification was difficult. On the other hand, the samples 32 to 34 having the point γ ratio of the present invention can maintain the preferable gradation in the 0.5 second exposure, and at the same time, are the photographic materials having good resolution performance in the high illuminance scanning exposure. all right.

[0175]

According to the present invention, a halogen having excellent latent image stability, reciprocity failure, and excellent gradation at high illuminance exposure while having high sensitivity and gradation suitable for silver halide color photographic paper. A silver halide emulsion and a silver halide photosensitive material could be provided.

Continuing on the front page (72) Inventor Koichiro Kuroda 1 Konica Corporation, Sakuracho, Hino-shi, Tokyo In-house F-term (reference) 2H016 AB00 AB02 AC00 BB00 BB04 BD00 2H023 BA00 BA02 BA05 CA02 CA04

Claims (10)

[Claims] 1. A silver chlorobromide emulsion having a silver chloride content of 90 mol% or more, having a region where the silver bromide content is higher than the others, and at least one of the following compounds (B): A silver halide emulsion comprising silver chlorobromide grains containing Compound (B): at least one of the following (b1) to (b6)
Compounds that fall under However, compounds belonging to the following compound (C) are excluded. (B1): a compound having an effect of reducing the intensity of the microwave photoconductive signal (b2): a compound having an effect of shortening the decay time of the intensity of the microwave photoconductive signal (b3): a compound having a desensitizing effect of photographic sensitivity (b4) ): Compound forming a deep electron trap level that holds the trapped electrons for 5 seconds or more. (B5): Compound forming a deeper electron trap level than the following compound (C). (B6): Deeper than 0.6 eV. A compound that forms an electron trap level. Compound (C): a compound and a complex containing Ir. 2. The silver halide emulsion according to claim 1, wherein the silver chlorobromide grains contain at least one of the following compounds (A) and at least one of the compounds (C). . Compound (A): at least one of the following (a1) to (a6)
Compounds that fall under However, compounds belonging to compound (C) are excluded. (A1): Compound having an effect of increasing microwave photoconductive signal intensity (a2): Compound having effect of increasing decay time of microwave photoconductive signal intensity (a3): Compound having sensitizing effect of photographic sensitivity (a4) ): Compound that forms a shallow electron trap level that releases trapped electrons in less than 50 ns (a5): Compound that forms a shallower electron trap level than compound (C) (a6): 0.03 to 0.3 eV That form an electron trap level at a depth of 3. The compound (C) in a high silver bromide content region.
3. The silver halide emulsion according to claim 2, wherein the content of Ir is the highest in the silver halide grains. 4. The silver halide emulsion according to claim 1, wherein the silver halide emulsion has a smaller grain size than the silver chlorobromide grains and a silver bromide content of 15% or more. A silver halide emulsion wherein silver fine particles are added to form a silver bromide-rich region. 5. The chemical sensitization is performed when the molar ratio of the chalcogen sensitizer to the gold sensitizer is 0.5 or less, and from 60 minutes before the addition of the chemical sensitizer to immediately before the addition of the chemical sensitizer. 5. The silver halide emulsion according to claim 4, wherein silver halide fine grains are added to said emulsion. 6. The ratio of fine silver halide grains to be added is 0.1 mol% or more and 5 mol% or less based on the total silver amount of the silver halide emulsion grains finally obtained, and the total silver bromide is added. Of the silver halide fine particles with respect to the total silver amount, and the moles / Ag mole of Ir present when the silver halide fine particles are added to the total silver amount are represented by the following formulas [1] and [1]. The silver halide emulsion according to claim 4 or 5, which satisfies [2]. Formula [1] Ir> 2 × 10 ⁻⁹ (138.63 × Br mol%) Formula [2] Ir <6 × 10 ⁻⁷ (434.67 × Br mol%) 7. The compound (A) and the compound (B) are not substantially present on the surface of the silver halide grains, and the region containing the compound (B) is the same as that of the compound (C). The silver halide emulsion according to any one of claims 2 to 6, wherein the silver halide emulsion is located on the inner side of the silver halide grains relative to the contained region. 8. The compound (A) and the compound (B) are not substantially present on the surface of the silver halide grains, and the region containing the compound (B) is The silver halide emulsion according to any one of claims 2 to 7, wherein the silver halide emulsion is located on the inner side of the silver halide grains relative to the contained region. 9. A silver halide photographic material, characterized in that at least one layer contains the silver halide emulsion according to claim 1. 10. On the characteristic curve obtained at an exposure time of 0.5 seconds, a density point γ showing a value of fog +1.8 and the density at a characteristic curve obtained at an exposure time of 10 ⁻⁶ seconds. 10. The silver halide photographic light-sensitive material according to claim 9, wherein the ratio of the point [gamma] is adjusted to 0.8 to 1.5.