JPH10282614A - Silver halide photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve fluctuation of sensitivity due to fluctuation of amplification development processing conditions and fluctuation of time length from exposure to the amplification development by forming a color image forming layer on a support and providing the contained photosensitive silver halide grains with a specific condition. SOLUTION: This silver halide photographic sensitive material is provided on a support with at least one color image forming layer containing photosensitive silver halide grains having a silver chloride content of >=80 mol% and a dye donor and satisfying the expression; S/V>=17.0, in which S in the average grain surface (μm<2> ) of the silver halide grains in this image forming layer, and V is the average grain volume (μm<3> ) of the silver halide grains, thus permitting sensitivity fluctuation due to the amplification development processing conditions and fluctuation of a time length from the exposure to the amplification development to be improved.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material and an image forming method which have improved sensitivity fluctuations due to fluctuations in amplification development processing conditions and fluctuations in the time from exposure to amplification development.

[0002]

2. Description of the Related Art Silver halide photographic materials (hereinafter, also simply referred to as "photosensitive materials") have extremely excellent characteristics, such as high sensitivity and excellent gradation, as compared with other printing materials. It has been widely used today. The silver halide photographic light-sensitive material has the features described above. Further, the amount of photosensitive silver halide in the light-sensitive material can be reduced, the time required for desilvering processing can be shortened or omitted, and halogen is a preferable means in terms of effective use of resources. A method of forming an image by subjecting a silver halide photographic light-sensitive material to amplification and development processing has been known for a long time. As an example of the amplification development processing, there is a method in which an oxidized color developing agent is generated with an oxidizing agent such as hydrogen peroxide / cobalt (III) complex using developed silver as a catalyst, and then an image dye is formed by reaction with a coupler. . Among them, a method using hydrogen peroxide as an oxidizing agent for amplification and development is preferable because it has high amplification efficiency and can greatly reduce the burden on the environment. In an amplification development method using hydrogen peroxide as an oxidizing agent, iodide ions or bromide ions are known to significantly reduce the amplification effect and become so-called catalyst poisons. A light-sensitive material using silver halide grains having a high silver content or an image forming method using the same is disclosed in, for example, JP-A-58-15484.
No. 0, No. 64-44938, JP-A-5-346647.
And No. 6-301128.

However, silver halide grains having a high silver chloride content tend to have a large sensitivity variation due to a variation in time from exposure to amplification and development. In amplification development, since processing is performed in the coexistence of a developing agent as a reducing agent and an oxidizing agent for amplification development, the stability of the processing solution is easily lost, and the processing solution conditions during amplification development are liable to fluctuate.

In addition, since the oxidizing agent for amplification and development affects a weak latent image, in the amplification and development processing of a photosensitive material using silver halide particles having a high silver chloride content, the processing solution conditions at the time of amplification and development are limited. When the concentration of the oxidizing agent fluctuates, or when the latent image state changes due to a change in the time from exposure to amplification and development, the sensitivity tends to change more easily. Further, in amplification development, there is a problem that the minimum density tends to increase when the sensitivity changes in the sensitizing direction, and improvement thereof has been desired.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material and an image forming method which have improved sensitivity fluctuations due to fluctuations in amplification processing conditions and fluctuations in the time from exposure to amplification development. To provide.

[0006]

The above object of the present invention is attained by the following constitutions.

[0007] 1. A support having at least one color image-forming layer containing photosensitive silver halide grains having a silver chloride content of 80 mol% or more and a dye-donor substance; Wherein the photosensitive silver halide grains satisfy the following formula (1).

(Formula 1) S / V ≧ 17.0 In the formula 1, S represents the average grain surface area (unit: μm ² ) of the photosensitive silver halide grains in the color image forming layer;
V represents the average grain volume (unit: μm ³ ) of the photosensitive silver halide grains in the color image forming layer.

[0009] 2. 2. The halogen according to the item 1, wherein 50% or more of the photosensitive area of the photosensitive silver halide grains contained in the color image forming layer is tabular silver halide grains having an aspect ratio of 2.0 or more. Silver halide photographic material.

[0010] 3. The silver content of the photosensitive silver halide grains contained in the color image forming layer is 0.001 g / m 2 in terms of silver.
^{2 or} 0.1 g / m ² or 1 or 2
3. The silver halide photographic light-sensitive material described in 1. above.

4. 4. The silver halide photographic material as described in any one of the items 1 to 3, wherein the color image forming layer is a magenta image forming layer.

5. A yellow image-forming layer, a magenta image-forming layer and a cyan image-forming layer each containing at least one layer of a photosensitive silver halide having a silver chloride content of 80 mol% or more and a dye-donor substance are provided on the support. And the photosensitive silver halide grains in each color image forming layer are represented by the following (formula 2)
A silver halide photographic light-sensitive material, characterized by satisfying the following relationship:

(Formula 2) S / V ≧ 17.0 In Formula 2, S represents the average grain surface area (unit: μm ² ) of the photosensitive silver halide grains in each color image forming layer.
Represents the average grain volume (unit: μm ³ ) of the photosensitive silver halide grains in each color image forming layer.

6. The halogen according to the above item 5, wherein 50% or more of the projected area ratio of the photosensitive silver halide grains contained in the color image forming layers are tabular silver halide grains having an aspect ratio of 2.0 or more. Silver halide photographic material.

[0015] 7. The amount of silver in the photosensitive silver halide grains contained in each of the image forming layers is 0.001 g / silver equivalent.
7. The silver halide photographic material as described in the above item 5 or 6, wherein the photographic material is m ^{2 to} 0.1 g / m ² .

8. 8. The silver halide photographic material as described in any one of 1 to 7, wherein the photographic layer of the silver halide photographic material has a coating pH of 4.5 to 6.5.

9. 9. An image forming method, comprising subjecting the silver halide photographic light-sensitive material according to any one of the above items 1 to 8 to amplification development processing.

10. 10. The image forming method according to the item 9, wherein the amplification and development processing is performed in the presence of a black and white developing agent.

11. PH at the time of the amplification development processing is 10.
The image forming method according to the above item 9 or 10, wherein the number is from 5 to 12.0.

Hereinafter, the present invention will be described in more detail.

In the present invention, the average grain surface area (S: μ) of photosensitive silver halide grains having a silver chloride content of 80 mol% or more is used.
m ² ) and the average particle volume (V: μm ³ ) ratio (S / V) is 1
It is characterized by being 7.0 or more, and when this condition is satisfied, the fluctuation of the amplification and development processing and the fluctuation of the sensitivity due to the fluctuation of the time from exposure to amplification and development are improved.

In the present invention, the grain surface area and grain volume of the photosensitive silver halide grains can be measured by various methods generally used in the art. As a representative method, there may be mentioned Loveland's “Particle Size Analysis Method” (ASTM Symposium on Right Microscopy, pp. 94-122, 1955) or “Theory of Photographic Process, No. 3. Edition "(co-authored by Mies and James, Chapter 2, published by Macmillan, 1966).

In the present invention, when the silver halide grains are cubic, the grain size of the silver halide grains is one of the following.
The length of the side is used as the particle size of the silver halide grains. Further, silver halide grains other than cubic (for example, tabular,
In the case of a tetrahedron, an octahedron, etc., it is expressed using the diameter of a circle having the same projected area as the projected area of the particle. The aspect ratio is defined as a value obtained by dividing the particle size by the thickness of the particle.

Although the mechanism of action of the present invention is not clear, it is known that the interstitial silver ion concentration is higher at the surface of the silver halide grains, and the interstitial is increased by increasing the specific surface area of the silver halide grains. Increases silver ion concentration, is relatively stable even in the presence of oxidizing agent for amplification development, and has small sensitivity fluctuation even when fluctuations in the time from exposure to amplification development and processing solution conditions during amplification development change It is estimated that a latent image that can be suppressed to the level can be formed.

In the present invention, the ratio (S / S) of the average grain surface area (S: μm ² ) and the average grain volume (V: μm ³ ) of the photosensitive silver halide grains having a silver chloride content of 80 mol% or more.
V) is 17.0 or more, and S /
The case where V is 22.0 or more is preferable because the effect of the present invention is particularly remarkable. Further, since the solubility of silver halide grains having a high silver chloride content is relatively large as compared with silver iodobromide or the like, when the value of S / V is too large, the production stability of silver halide grains is maintained. Load increases. Therefore, in the present invention, it is particularly preferable that the value of S / V is 22.0 or more and 50.0 or less.

In the light-sensitive material according to the present invention, the composition of the silver halide grains contained in the color image forming layer satisfying the conditions of the present invention has a silver chloride content of 80 mol% or more.
The higher the silver chloride content, the more remarkable the fluctuation in sensitivity due to fluctuations in amplification and development processing conditions and fluctuations in the time from exposure to amplification and development, making the present invention particularly useful.

As the silver halide emulsion used in the light-sensitive material according to the present invention, a silver halide emulsion having a portion containing silver bromide at a high concentration can be preferably used.
In this case, the portion containing a high concentration of silver bromide may be a so-called core / shell emulsion in which a complete layer is formed, or a region in which the complete layer is not formed and the composition is merely partially present. In this case, what is called an epitaxy junction may be used. Further, the composition may change continuously or discontinuously. It is particularly preferable that the portion where silver bromide is present at a high concentration is present at the top of silver halide grains.

The photosensitive silver halide grains according to the present invention can also contain heavy metal ions for the purpose of improving various photographic properties. As heavy metal ions,
Eighth to tenth such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, and cobalt
Examples include Group 12 metals, 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 can be contained in the silver halide grains in the form of a salt or a complex salt.

When the heavy metal ion forms a complex, the ligand may be a cyanide ion, thiocyanate ion, isothiocyanate ion, cyanate ion, or the like.
Examples include chloride ion, bromide ion, iodide ion, carbonyl, nitrosyl, thionitrosyl, and ammonia. Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion,
Preferred are bromide ion, nitrosyl, thionitrosyl, carbonyl and the like.

In the present invention, the photosensitive silver halide grains contain at least one metal selected from Groups 5 to 10 in the periodic table and at least one ligand selected from nitrosyl, thionitrosyl and carbonyl ligands. When containing a metal complex having a species, particularly when exposed to high illuminance in a short time,
The effect of improving the sensitivity fluctuation due to the fluctuation of the time from exposure to amplification and development is remarkable, which is preferable.

Specific examples of the metal complex that can be used in the present invention are shown below, but the present invention is not limited thereto.

(I-1) FeCl ₂ (I-2) FeCl ₃ (I-3) (NH ₄ ) Fe (SO ₄ ) ₂ (I-4) K ₃ [Fe (CN) ₆ ] (I-5 ) K ₄ [Fe (CN) ₆ ] (I-6) K ₂ [IrCl ₆ ] (I-7) K ₃ [IrCl ₆ ] (I-8) K ₂ [PtCl ₆ ] (I-9) K ₂ [Pt (SCN) ₄ ] (I-10) K ₂ [NiCl ₄ ] (I-11) K ₂ [PdCl ₆ ] (I-12) K ₃ [RdCl ₆ ] (I-13) K ₂ [IrBr ₆ ] (I-14) K ₃ [IrBr _6] (I-15) K ₃ [Re (CNO) _6] (I-16) K ₃ [Mo (OCN) _6] (I-17) K ₄ [Fe ( (CNO) ₆ ] (I-18) K ₄ [Ru (CNO) ₆ ] (I-19) K ₂ [Ni (CN) ₄ ] (I-20) K ₂ [Pt (CNO) ₄ ] (I-21) ) K ₃ [C (NH _{3) 6]} (I-22) K ₅ [Co ₂ (CNO) _11] (I-23) K ₃ [Re (CNO) _6] (I-24) K ₄ [Os (CNO) _6] ( II-1) Cs ₂ [Os (NO) Cl ₅ ] (II-2) K ₂ [Ru (NO) Cl ₅ ] (II-3) K ₂ [Ru (CO) Cl ₅ ] (II-4) Cs ₂ [Os (CO) Cl _5] (II-5) K ₂ [Fe (NO) (CN) _5] (II-6) K ₂ [Ru (NO) Br _5] (II-7) K ₂ [Ru (NO) I ₅ ] (II-8) K ₂ [Re (NO) (CN) ₅ ] (II-9) K ₂ [Re (NO) Cl ₅ ] (II-10) K ₂ [Ir (NO) Cl _5] (II-11) K ₂ [Ru (NS) Cl _5] (II-12) K ₂ [Os (NS) Br _5] (II-13) K ₂ [Ru (NS) (CN) _5] (II-14) K ₂ [Ru (NS) (SCN) _5] this onset In order to contain a metal complex in the photosensitive silver halide grains according to the present invention, the metal complex before the formation of silver halide grains, during the formation of silver halide grains, during physical ripening after the formation of silver halide grains It may be added at any place in each step. To obtain a silver halide emulsion satisfying the above conditions,
The metal complex can be dissolved together with the halide salt and added continuously over the whole or a part of the grain formation process. Further, a method of adding fine silver halide grains containing a metal complex can also be preferably used.

The amount of the metal complex added to the silver halide grains is preferably 1 × 10 ⁻⁹ mol or more, more preferably 1 × 10 ⁻² mol or less, per 1 mol of silver halide.
In particular, it is preferably from 1 × 10 ⁻⁸ mol to 5 × 10 ⁻⁵ mol.

The silver halide grains used in the light-sensitive material according to the present invention may have any shape.
One preferable example is a cube having a {100} plane as a crystal surface. No. 4,183,756.
No. 4,225,666, JP-A-55-26589.
No. 55-42737 and the Journal of Photographic Science (J. Photo
gr. Sci. ) Particles having shapes such as octahedron, tetrahedron, and dodecahedron can be prepared and used by methods described in documents such as 21, 39 (1973). Further, particles having a twin plane may be used.

As the silver halide grains used in the light-sensitive material of the present invention, grains having a single shape are preferably used, but it is also preferable to add two or more monodispersed silver halide emulsions to the same layer. .

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

The silver halide grains used in the light-sensitive material of 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 a 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.

Also, 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 disposed in a reaction mother liquor, and a water-soluble silver described in DE-A-2,921,164. 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.

As the silver halide grains used in the light-sensitive material according to the present invention, so-called tabular silver halide grains (hereinafter, also simply referred to as tabular grains) are used in order to increase sensitivity and control gradation balance. Particularly preferably used. As tabular grains containing silver chloride at a high concentration, grains having a {111} major plane and grains having a {100} major plane are known. Particles having a flat surface are particularly preferably used.

It is preferred that 50% or more of the photosensitive silver halide grains contained in the color image forming layer satisfying the conditions of the present invention be tabular silver halide grains having an aspect ratio of 2.0 or more. The effect of the present invention is that the fluctuation of the time from the exposure to the amplification development and the fluctuation of the processing solution during the amplification development can be suppressed to a small level even when the processing solution conditions fluctuate. It is preferable because silver halide grains can be obtained.

The silver halide emulsion used in the light-sensitive material 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.

As a chalcogen sensitizer applied to the silver halide emulsion used in the light-sensitive material according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, and the like can be used. Sensitizers are preferred.

The silver halide emulsion used in the light-sensitive material according to the present invention prevents fogging that occurs during the preparation of the light-sensitive material, reduces performance fluctuations during storage, and prevents fogging that occurs during development. For the purpose, known antifoggants and stabilizers can be used as long as the effects of the present invention are not impaired. Preferred examples of the compound that can be used for such a purpose include a compound represented by the general formula (II) described in the lower section of page 7 of JP-A-2-14636. These compounds are added according to the purpose in a step of preparing a silver halide emulsion, a step of chemical sensitization, at the end of the step of chemical sensitization, a step of preparing a coating solution and the like.

In the light-sensitive material according to the present invention, it is sufficient that the silver halide particles are present in an amount necessary to produce developed silver which serves as a catalyst during amplification development. For example, the silver halide particles are required for coupling with a coupler. The amount of silver halide can be greatly reduced as compared with a normal color developing method in which an oxidized form of a color developing agent is produced by a redox reaction between a silver halide and a developing agent.

In the light-sensitive material according to the present invention, the silver content of the photosensitive silver halide grains contained in the color image forming layer satisfying the conditions of the present invention is 0.001 g / m ^{2 to} 0.
It is preferably 1 g / m ² . When the silver content is in the above range, the load on the desilvering treatment is small, which is preferable.

When the light-sensitive material according to the present invention has a plurality of color image forming layers for forming color images having mutually different hues, when the light-sensitive silver halide particles contained in the light-sensitive material are used. The total amount of silver is 0.3 g / m in terms of silver
It is preferably ² or less. Further, the silver amount of the preferred light-sensitive silver halide grains of each color image forming layer are each 0.001 to 0.1 g / m ² in terms of silver, more preferably 0.01~0.08g / m ² Range. When the silver content is in the above range, the so-called interimage effect, in which the development reaction in the own layer is affected by the development reaction in the other layer, is small, and the stability of gradation reproduction is improved, which is preferable.

In general, human vision is particularly sensitive to magenta images, and fluctuations in photographic performance in the magenta image forming layer greatly affect the finish of a printed image even if slight. Therefore, when the magenta image forming layer is a color image forming layer that satisfies the conditions of the present invention, a stable and beautiful print can be obtained by improving the fluctuation in amplification processing conditions and the fluctuation in sensitivity due to the fluctuation in time from exposure to amplification development. The effect of obtaining an image is great, and this is a preferred embodiment of the present invention.

The pH of the film of the light-sensitive material according to the present invention is as follows:
It is preferably from 5 to 6.5.

In the present invention, the film pH of the photosensitive material is
This is the pH of the photographic layer obtained by applying a coating solution used for preparing a light-sensitive material on a support, and does not always coincide with the pH of the coating solution. The pH of the film was measured using 0.05 m of pure water on 1 cm ² of the exposed surface of the photosensitive material.
After dripping for 1 minute and allowing to stand for 3 minutes, it can be determined by measuring with a flat electrode (such as GST5313F manufactured by Toa Denpa Kogyo KK). When the coating pH is 4.5 or more and 6.5 or less, it is considered that the balance between the oxidizing agent used for amplification development and the diffusion rate of hydroxide ions in the coating is good,
The effects of the present invention are particularly high, and the stability of gradation reproduction is good, which is preferable.

As a method for adjusting the coating pH, the pH of the coating solution is adjusted.
H can be adjusted by appropriately adjusting H with an acid (such as citric acid or sulfuric acid) or an alkali (such as potassium hydroxide or sodium hydroxide).

Next, couplers preferred as the dye-providing substance of the present invention will be described.

The coupler preferably used in the present invention includes a coupler which undergoes a coupling reaction with an oxidized form of a color developing agent.
Any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 40 nm can be used. Particularly, a typical coupler has a spectral absorption maximum wavelength in a wavelength region of 350 to 500 nm. Representative examples include a yellow dye-forming coupler, a magenta dye-forming coupler having a spectral absorption maximum wavelength in the wavelength range of 500 to 600 nm, and a cyan dye-forming coupler having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm.

As the cyan coupler which can be preferably used in the present invention, Japanese Patent Application Laid-Open No. 4-114154,
Couplers represented by general formulas (CI) and (C-II) described in the lower left column of the page, and general formulas (Ia), (Ib), and (Ib) described in the lower left column of page 4 of JP-A-2-23556. I
c) a cyan coupler represented by JP-A-1-2476;
No. 1, JP-A No. 1-page 6 lower right to page 7 upper left column, general formulas (IIα) to (VIIIα) and page 7 lower right to page 8 upper left column, general formulas (IIβ) to (VIIIβ) Cyan couplers. In particular, cyan couplers represented by the general formulas (IIα) to (VIIIα) and (IIβ) to (VIIIβ) are preferable because they have sharp image dye absorption and excellent color reproducibility.

The magenta couplers which can be preferably used in the present invention include the general formulas (MI) and (M-II) described in the upper right column on page 4 of JP-A-4-114154.
And a coupler represented by the following formula: More preferred among the above magenta couplers are couplers represented by the general formula (MI) described in the upper right column on page 4 of the publication, wherein the RM of the general formula (MI) is a tertiary alkyl. The coupler which is a group is excellent in light resistance and particularly preferable.

As the yellow coupler which can be preferably used in the present invention, a coupler represented by the general formula (YI) described in the upper right column of page 3 of JP-A-4-114154 can be exemplified. Of these, couplers of the formula (Y-1) in which RY1 is an alkoxy group or couplers of the formula [I] described in JP-A-6-67388 can reproduce yellow having a preferable color tone and are preferable. The most preferred compounds are compounds represented by the formula (Y-1) described in JP-A-4-81847, page 1 and pages 11 to 17 of the same.

When the oil-in-water emulsion dispersion method is used to add the couplers and other organic compounds preferably used in the present invention, they are usually added to a high-boiling organic solvent and, if necessary, to a low-boiling and / or organic solvent. It is dissolved together with a water-soluble organic solvent, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. The high-boiling organic solvent that can be used for dissolving and dispersing the coupler 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.

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. 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 after the addition are preferably 10 hours each. Preferably within 3 hours, more preferably within 20 minutes.

The coupler includes light of the formed dye image,
In order to prevent discoloration due to heat, humidity and the like, it is preferable to use a discoloration inhibitor in combination. Particularly preferred compounds include compounds represented by the general formula I described on page 3 of JP-A-2-66541.
Phenyl ether compounds represented by II, JP-A-3-1
A phenolic compound represented by the general formula IIIB described in JP-A-74150, an amine-based compound represented by the general formula A described in JP-A-64-90445, and JP-A-62-182.
Metal complexes represented by general formulas XII, XIII, XIV and XV described in JP-A-741 are particularly preferable 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 preferred 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'-1) described in the lower left column of page 10 of JP-A-4-114154 are disclosed. And the like. In addition, the fluorescent dye releasing compounds described in U.S. Pat. No. 4,774,187 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.

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. Particularly preferred compounds are compounds represented by the formula III-3 described in JP-A-1-250944, and JP-A-64-6664.
6, a compound represented by the general formula III,
UV-1L to UV-27 described in 3-187240
L, 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.

In the 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, dyes having absorption in the visible region include those described in JP-A-3-25184.
The dyes of AI-1 to 11 described in JP-A No. 308, page 308 and the dyes described in JP-A-6-3770 are preferably used. As the infrared absorbing dye, JP-A 1-28075 is used.
No. 0, page 2, lower left column, formulas (I) and (I)
The compounds represented by I) and (III) have preferable spectral characteristics, and do not affect the photographic characteristics of the silver halide photographic emulsion.
It is also preferable because there is no contamination due to residual color.

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

As the spectral sensitizing dye, any of the known compounds can be used. As the blue-sensitive sensitizing dye, BS-1 to 8 described in JP-A-3-251840, page 28, can be used alone. Or in combination. As the green photosensitive sensitizing dye, the same publication 28
GS-1 to GS-5 described on the page are preferably used. As the red-sensitive sensitizing dye, RS described on page 29 of the same publication is used.
-1 to 8 are preferably used. 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 in JP-A-4-285950, pp. 8-9, and JP-A-5-6.
Compound S-1 described in No. 6515, pages 15 to 17
It is preferable to use a combination of -S-17.

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

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

It is advantageous to use gelatin as a binder in the light-sensitive material according to the present invention. If necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, A hydrophilic colloid such as a sugar derivative, a cellulose derivative, or a synthetic hydrophilic polymer such as a homopolymer or a copolymer 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.
It is preferable to use the compounds described in JP-A Nos. 054 and 61-245153. Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 in the colloid layer in order to prevent the growth of mold and bacteria which adversely affect the photographic performance and image storability. Further, in order to improve the physical properties of the surface of the light-sensitive material or the processed sample, a protective layer is disclosed in
It is preferable to add a slip agent or a matting agent described in JP-A-118543 and JP-A-2-73250.

As the support used in the light-sensitive material according to the present invention, any material may be used, such as paper coated with polyethylene or polyethylene terephthalate, a paper support made of natural pulp or synthetic pulp, a vinyl chloride sheet, For example, polypropylene, polyethylene terephthalate support, baryta paper, etc. which may contain a white 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.

It is more preferred that the value of the center plane average roughness (SRa) of the support is 0.15 μm or less, more preferably 0.12 μm or less, because the effect of good gloss is 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 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, antistatic property on the support surface, It may be applied via one or more undercoat layers for improving dimensional stability, friction resistance, hardness, antihalation property, frictional properties and / or other properties.

At the time of coating the light-sensitive material according to the present invention, 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 photosensitive material according to the present invention, the image recorded on the negative may be optically formed on the photosensitive material to be printed and printed. Also, the image may be once converted into digital information, then the image may be formed on a CRT (cathode ray tube), and this image may be formed on a photosensitive material to be printed and printed. The printing may be performed by scanning while changing the light intensity or the irradiation time.

In particular, when the exposure time per pixel is 10 ^-3 seconds or less (so-called high-illuminance short-time exposure), the effects of the present invention are remarkable and the present invention can be used effectively. is there. In the case of flash exposure, the term “exposure time” here means that, when the light intensity changes over time, the light intensity reaches 1/2 of its maximum value and then attenuates to 1/2 of that maximum value. In the case of scanning exposure by laser light, the time when the light intensity becomes 1/2 of the maximum value in the spatial change of the light intensity is defined as the outer edge of the light beam, and the scanning line When the distance between two points where the line passing through the point where the light intensity is maximum and the outer edge of the light beam intersects is the diameter of the light beam, the exposure time is defined as the value obtained by dividing the diameter of the light beam by the scanning speed. I do. Scanning exposure using an array of light sources may be considered in the same manner as the above-described scanning exposure using laser light.

Examples of the exposure apparatus applicable to the image forming method of the present invention include, for example, JP-A-55-4071 and JP-A-55-4071.
9-11062, JP-B-56-14963, JP-B-56-40822, and European Patent 77410.
No., IEICE Technical Report Vol. 24
4 and Movie Television Technology 1984/6 (382), 34-
And those described on page 36 and the like.

The image forming method of the present invention is particularly preferably applied to a photosensitive material for forming an image for direct viewing. For example, color paper, color reversal paper, a photosensitive material for directly 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.

Next, the amplification and development processing will be described.

In the present invention, the term “amplification development processing” means that a latent image generated by exposure of a photosensitive material is developed with a color or black-and-white developer to form developed silver, and a chemical reaction using the developed silver as a catalyst is utilized. Is defined as a method of forming or releasing image dyes by, for example, a method of forming image dyes by a coupling reaction of a coupler with an oxidized developing agent formed by a redox reaction of a developing agent and an oxidizing agent using a developed silver catalyst as a catalyst, and the like. Is raised.

Examples of the oxidizing agent include compounds that give hydrogen peroxide such as hydrogen peroxide, salts of hydrogen peroxide, and adducts of hydrogen peroxide, peroxo compounds such as peroxoborates and peroxocarbonates, and cobalt hexaammine complexes. Cobalt (III) complexes, halogenous acids such as chlorite, etc.
And periodic acid. Among them, a method using a compound that gives hydrogen peroxide such as hydrogen peroxide, a salt of hydrogen peroxide, and an addition compound of hydrogen peroxide as an oxidizing agent is advantageous because the amplification effect is high and the load on the environment is reduced. It is.

In the amplification development processing according to the present invention, a combination of an aromatic primary amine developing agent and hydrogen peroxide is preferably used, and as the aromatic primary amine developing agent,
N, N-diethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, 2-amino-5
(N-ethyl-N-laurylamino) toluene, 4-
(N-ethyl-N- (β-hydroxyethyl) amino)
Aniline, 2-methyl-4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline, 4-amino-3
-Methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) -aniline, N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide,
N, N-dimethyl-p-phenylenediamine, 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline, 4-amino-3-methyl-N-ethyl-N- (β
-Ethoxyethyl) aniline, 4-amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline and the like.

Further, in addition to the aromatic primary amine developing agents, for example, European Patents 565,165 and 572,054
And 593110, JP-A-8-202002, JP-A-8-227131, and JP-A-8-234390, etc., can also be preferably used as the sulfonylhydrazide and carbonylhydrazide developing agents.

In the present invention, it is possible to supply the processing solution containing the color developing agent and the oxidizing agent for amplification development to the photographic material as a co-existing processing solution. A liquid containing the agent is divided into a plurality and prepared,
It is also possible to supply to a photosensitive material.

The image forming method according to the present invention is described, for example, in JP-A-52-13335 and JP-A-55-127555.
As described in JP-A-61-77851 and the like, a developing agent and an oxidizing agent are present in the same processing bath (developing / amplifying solution) to produce developed silver as a catalyst and the subsequent amplification development processing. A method performed in the same bath, JP-A-5-216192,
As described in JP-A-5-346647 and the like, a method in which a developing bath containing a developing agent and an amplification bath containing an oxidizing agent are separated, silver is formed in the developing bath, and the developing agent is brought into the amplification bath and amplified and developed. Or JP-A-61-88259,
As described in Japanese Patent Application Laid-Open No. 7-077788, a method of forming a developed silver by processing in a developing bath containing a developing agent, followed by amplifying and developing in a processing bath containing a developing agent and an oxidizing agent is exemplified. Further, as a processing method without using a processing bath, for example, a method of spraying a developing solution, an amplifying solution, or an amplifying developing solution in a mist onto a silver halide photosensitive material as described in JP-A-61-80150, etc. Can be used.

When the developing bath and the amplification bath are separated, the preferred amount of the developing agent in the developing solution is 0.2 to 10 g / l, particularly preferably 1 to 5 g / l. The amount of hydrogen peroxide (30% solution) in the amplification solution is 0.1 to 100 ml / l.

When processing is carried out in a single bath of a developing bath and an amplification bath, the preferred amount of the developing agent in the developing / amplifying solution is 0.5 to
15 g / l, more preferably 1 to 7 g / l, and the preferred amount of hydrogen peroxide (30% solution) is 0.1 to 30 ml
/ L, more preferably 1 to 5 ml / l.

In the present invention, the above-mentioned developer, amplifying solution,
Although the developing / amplifying solution can be used in any pH range, it is preferably pH 9.0 to 12.5, more preferably pH 10.5 to 1 from the viewpoint of rapid processing and stability of the processing solution.
It is used in the range of 2.0.

In the present invention, the pH at the time of amplification development refers to the pH of the development / amplification solution when processing is performed using a development / amplification solution in which a developing agent and an oxidizing agent for amplification development coexist.
When the processing is performed by separating the developing bath and the amplification bath, the pH refers to the pH of the amplification solution in the amplification bath. When the developing solution and the amplifying solution are supplied to the photosensitive material independently of each other, the pH of the solution in which the developing solution and the amplifying solution are preliminarily mixed at a ratio supplied to the photosensitive material is defined as the pH at the time of the amplification development. In the present invention, the pH at the time of amplification development is from pH 9.0 to 12.5 from the viewpoint of rapid processing.
It is more preferable that the pH is 10.5 to 12.0.
Is more preferable.

The temperature of the amplification and development processing according to the present invention is 20
The temperature is preferably not less than 60 ° C and not less than 60 ° 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, it is preferable that the temperature is not too high.

The amplification and development processing time varies depending on the type of photosensitive material, processing temperature, activity of the processing solution and the like, but is preferably within 180 seconds, more preferably within 90 seconds in the present invention.

To the developing solution, the amplifying solution, and the developing / amplifying solution, known developing solution component compounds can be added in addition to the above-described color developing agent and oxidizing agent. Usually, a development inhibitor such as a pH buffer, a chloride ion, and benzotriazole, a preservative, and a chelating agent are used.

As the pH buffer, known buffers can be used. Among them, buffers composed of a combination of carbonate and / or phosphate are preferable because they can reduce the cost.

In the present invention, the use of the above-described color developing agent and black-and-white developing agent in combination in the amplification developing processing solution further improves the stability of gradation reproduction and the amplification processing time in addition to the effects of the present invention. This can be shortened, which is preferable.

In the present invention, black-and-white developing agents that can be used include dihydroxybenzenes, 3-pyrazolidones, pyrogallols, glycines, hydroxylamines, hydrazines, aminophenols, reductones (for example, ascorbic acid) (Including salts), erythorbic acid (including salts)), 3-aminopyrazolines, transition metal complex salts (Ti, Cr, Mn, Fe, Co, Ni, C
and a complex salt of a transition metal such as u. These may be in a form having a reducing power to be used as a developer.
^3+, V ^2+, Cr ^2+, take the form of a complex salt of Fe ²⁺ and the like, as a ligand ethylenediaminetetraacetic acid (EDTA), amino-polycarboxylic acids and their salts such as diethylenetriaminepentaacetic acid (DTPA), Phosphoric acids such as hexametapolyphosphoric acid and tetrapolyphosphoric acid and salts thereof). Among them, dihydroxybenzenes, 3-pyrazolidones, hydroxylamines, and reductones (for example, ascorbic acid (including salts) and erythorbic acid (including salts)) are preferred. The amount of the black-and-white developing agent is 0.1% by mole relative to the color developing agent.
-3.0, particularly preferably 0.25-
2.0.

In the image forming method of the present invention, after the amplification and development, bleaching and fixing may be performed as necessary. The bleaching process may be performed simultaneously with the fixing process.
After the fixing process, a water washing process is usually performed. Also,
As an alternative to the water washing treatment, a stabilization treatment may be performed.

The processing apparatus used in the image forming method of the present invention may be a roller transport type in which the photosensitive material is transported between rollers disposed in a processing bath, or may be transported with the photosensitive material fixed to a belt. An endless belt method may be used, but a processing bath is formed in a slit shape, and a processing method for supplying a processing liquid to the processing bath and transporting the photosensitive material, and a spray method for spraying the processing liquid,
A web method by contact with a carrier impregnated with the processing solution,
A method using a viscous treatment liquid can also be used.

[0102]

Next, the present invention will be described based on examples, but embodiments of the present invention are not limited to these examples.

(Blue-sensitive silver halide emulsion (Em-B
Preparation of 1) pAg = (A1 solution) and (B1 solution) below in 1 liter of a 2% aqueous gelatin solution kept at 40 ° C.
7.3, pH = 3.0 were added simultaneously while controlling, and the following (solution C1) and (solution D1) were further pAg = 8.0, pH =
Simultaneous addition was performed while controlling to 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437.
The pH was controlled using sulfuric acid or an aqueous sodium hydroxide solution.

(Solution A1) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B1) Silver nitrate 10 g Water was added to 200 ml (Solution C1) Sodium chloride 102.7 g Potassium bromide 1.0 g Water 600 ml (D1 solution) Silver nitrate 300 g Water was added and 600 ml was added. After completion of the addition, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas Co. and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution. Average particle size 0.50μ
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-1A was obtained. The above-mentioned EMP-1A was optimally subjected to chemical sensitization at 60 ° C. using the following compounds to give a blue-sensitive silver halide emulsion (Em-B
1) was obtained.

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 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 BS-1 4 × 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

[0106]

Embedded image

In the preparation of the silver halide emulsion EMP-1A, the procedure was the same except that the addition times of the (A1 solution) and the (B1 solution) and the (C1 solution) and the (D1 solution) were changed. Monodisperse cubic emulsions EMP-2A to EMP-6A having different average grain sizes and a silver chloride content of 99.5 mol% were obtained. The above-mentioned EMP-2A to EMP-6A were optimally subjected to spectral chemical sensitization in the same manner as in the preparation of the blue-sensitive silver halide emulsion (Em-B1) to perform blue-sensitive silver halide emulsion (Em-B1).
B2) to (Em-B6) were prepared.

(Preparation of photosensitive materials (101) to (106)) 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 on which the emulsion layer was coated, a molten polyethylene containing anatase-type titanium oxide having a surface treatment dispersed therein at a content of 15% by weight was laminated. After the reflective support was subjected to corona discharge treatment, a gelatin undercoat layer was provided, and each layer having the following constitution was further applied thereon, to prepare silver halide photographic light-sensitive materials (101) to (106). In the preparation of the photosensitive material, each coating solution was prepared so as to have the following coating amount, and (H-1) and (H-2) were added as hardening agents. Surfactants (SU-1) and (S
U-2) and (SU-3) were added to adjust the surface tension. Further, (F-1) was added to each layer so that the total amount became 0.04 g / m ² .

The coating amount of each layer is shown below.

Layer composition Addition amount (g / m ² ) Second layer (protective layer) Gelatin 1.00 DIDP 0.002 DBP 0.002 Silicon dioxide 0.003 First layer (blue-sensitive layer) Gelatin 1. 30 Blue-sensitive emulsion (Em-B1) 0.03 Magenta coupler (M-1) 0.20 Dye image stabilizer (ST-3) 0.20 Dye image stabilizer (ST-4) 0.17 DIDP 0.13 DBP 0.13 Support polyethylene-laminated paper The amount of silver halide was shown in terms of silver.

SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sodium sulfosuccinate sodium salt SU-3: di (2,2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) sodium salt H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium DBP: dibutyl phthalate DIDP: diisodecyl phthalate

[0112]

Embedded image

The photosensitive material (10
Each of 1) to (106) was exposed to white wedge light for 0.5 seconds using a light wedge, allowed to stand for 30 minutes after exposure, and then subjected to the following processing step 1. The obtained sample was used as a densitometer PDA-65.
The reflection density was measured using Konica Corporation. Also,
The same processing and measurement were performed except that the time from exposure to amplification and development was changed to 5 minutes and 1 minute. Here, the reciprocal of the exposure amount that gives a reflection density of 0.75 is defined as the sensitivity, and the sensitivity (S30) when the time from exposure to amplification and development is 30 minutes for each sample is 100, and the time from exposure to amplification and development is 100. The sensitivity (S5) when was 5 minutes and the sensitivity (S1) when the time from exposure to amplification and development was 1 minute were represented by relative values. The closer the values of S5 and S1 are to 100, the smaller the change in sensitivity is, which is preferable, even if the time from exposure to amplification and development varies.

Further, the sample left standing for 30 minutes after exposure was processed and measured in the same manner except that the amount of aqueous hydrogen peroxide in the amplification developer (CDA-1) was changed to 50 ml. The sensitivity (So) when the amount of the hydrogen peroxide solution was 50 ml was represented by a relative value, with the sensitivity of 100 as 100. S
The closer the value of o is to 100, the smaller the change in sensitivity is, which is preferable, even if the concentration of the oxidizing agent in the amplification developer changes. Table 1 shows the results.

Processing Step 1 Processing Temperature Time Amplification Developer (CDA-1) 35.0 ± 0.5 ° C. 50 seconds Bleach-Fix Solution (BF-1) 30.0 ± 0.5 ° C. 45 seconds Stabilization Liquid 30 to 34 ° C for 60 seconds Drying 60 to 80 ° C for 30 seconds The composition of the treatment liquid is shown below.

Amplification developer (CDA-1) Pure water 800 ml Potassium bromide 0.001 g Potassium chloride 0.35 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 4.0 g N, N-diethylhydroxylamine 4.7 g hydroxylamine sulfate 1.0 g diethylenetriaminepentaacetic acid pentasodium salt 2.0 g 1-hydroxyethylidene-1,1'-diphosphonic acid 0.35 g fluorescent whitening agent (4 2,4'-diaminostilbene disulfonic acid derivative) 2.0 g Disodium hydrogen phosphate 10 g Potassium carbonate 20 g Hydrogen peroxide solution (5.99%) 25 ml The pH was adjusted to 11.0 with potassium hydroxide or sulfuric acid. In addition, make the total volume 1 liter.

Bleach-fixing solution (BF-1) Pure water 700 ml Diethylenetriaminepentaacetate ammonium ferric dihydrate 65 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4 -Thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Add water to make the total volume 1 liter, and adjust the pH to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing solution Pure water 800 ml 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 0.0 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 (polyvinylpyrrolidone) 1.0 g ammonia water (25% aqueous solution of ammonium hydroxide) 2.5 g nitrilotriacetic acid / trisodium salt 1.5 g Water was added to make the total volume 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or ammonia water. .

[0119]

[Table 1]

Example 1 relates to a light-sensitive material using a cubic silver halide emulsion. From the results in Table 1,
The light-sensitive materials (103) to (106) of the present invention have a small sensitivity fluctuation when the time from exposure to amplification development varies, and also have a small oxidizing agent concentration variation in the amplification developer.
It can be seen that sensitivity fluctuation is small and preferable. Above all, S / V
Materials (105) and (10) each having a value of 22.0 or more.
6) shows that the variation in sensitivity is particularly small and is a particularly preferred embodiment of the present invention.

Example 2 (Blue-sensitive silver halide emulsions (Em-B21) to (Em-B21)
Preparation of B25)) The following (solution A4) and (solution B4) were placed in 2 liters of a 3.5% gelatin aqueous solution (containing 0.654 g of sodium chloride and 0.050 g of potassium iodide) kept at 40 ° C. for 30 seconds. After simultaneous addition and aging for 20 minutes, the following (solution C4) and (solution D4) were further added with pCl = 2.
It was added simultaneously while controlling to 32.

(A4 solution) Sodium chloride 3.49 g Potassium iodide 0.05 g Water was added and 30 ml (B4 solution) Silver nitrate 10.2 g Water was added and 30 ml (C4 solution) Sodium chloride 54.9 g Water was added and 1880 ml (D4 solution) 159.7 g of silver nitrate 1880 ml of water was added, and after the addition was completed, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution. Redistributed. Thus, a silver halide grain having an {100} plane having an average grain size of 0.66 μm and an average thickness of 0.11 μm (average aspect ratio (AR) 6.0) as a principal plane and having an aspect ratio of 2.0 or more is projected. Silver chloroiodide emulsion EMP- containing 75% by area
7A was obtained.

In contrast to EMP-7A, E
A blue-sensitive silver halide emulsion (Em-B21) was obtained by optimally performing chemical sensitization similarly to MP-1A.

In the preparation of the silver halide emulsion EMP-7A, the same procedure was followed except that the addition times of the (A4 solution) and (B4 solution) and the (C4 solution) and (D4 solution) were changed. Silver chloroiodide emulsions EMP-8A to EMP-11A having different average particle diameters and average aspect ratios were obtained (in addition,
It was confirmed that EMP-8A to EMP-11A all contained silver halide grains having an aspect ratio of 2.0 or more in a projected area ratio of 50% or more). The above EMP-8A ~
For EMP-11A, a blue-sensitive silver halide emulsion (E
m-B21), and then spectrally sensitized optimally in the same manner as in the preparation of m-B21) to give blue-sensitive silver halide emulsions (Em-B22) to (Em-
B25) was prepared.

(Preparation of photosensitive materials (201) to (205)) Except that the blue-sensitive silver halide emulsion was changed as shown in Table 2 in preparation of the photosensitive material (101) in Example 1, the same procedure was carried out. And photosensitive materials (201) to (205).

The photosensitive material (20
For 1) to (205), the same processing and evaluation as in Example 1 were performed. The results are shown in Table 2.

[0127]

[Table 2]

Example 2 relates to a light-sensitive material using a tabular silver halide emulsion. From the results in Table 2, it can be seen that even when a tabular silver halide emulsion was used, the photosensitive material of the present invention showed a small change in sensitivity when the time from exposure to amplification development was changed, It can be seen that sensitivity fluctuation is small with respect to concentration fluctuation of the agent, which is preferable. Further, a light-sensitive material (20) using a silver halide emulsion in which silver halide grains having an aspect ratio of 2.0 or more account for 50% or more of the projected area ratio of the silver halide grains.
1) to (205) show that, even when the value of S / V is smaller than that of the photosensitive material (106) using a cubic silver halide emulsion, the sensitivity fluctuation when the time from exposure to amplification and development is small is small. It turns out that this is a particularly preferred embodiment of the present invention.

Example 3 (Preparation of photosensitive materials (301) to (309)) In the preparation of the photosensitive materials (101), (103) and (106) of Example 1, the pH of the coating solution for the second layer was adjusted to sulfuric acid or The composition was adjusted with sodium hydroxide to prepare photosensitive materials (301) to (309) whose coating pH was as shown in Table 3. The photosensitive materials (301) to (309) thus produced were subjected to the same processing and evaluation as in Example 1.

Further, the gradation (γS) of the light-sensitive material of the present invention was determined. The gradation was defined as the average gradient of the characteristic curve with respect to the exposure amount between the reflection density of 0.75 and the reflection density of 1.75. The gradation when the amount of hydrogen peroxide is 25 ml is γS, and the gradation when the amount of hydrogen peroxide is 50 ml is γ.
O, the value of the ratio of γO to γS (γO / γS) is determined as a value representing the change in gradation when the concentration of the oxidizing agent changes,
Using this value, the stability of gradation reproduction was evaluated. γO / γ
The closer the value of S is to 1, the smaller the gradation fluctuation when the concentration of the oxidizing agent fluctuates, which is preferable. The results are shown in Table 3.

[0131]

[Table 3]

In Example 3, samples in which the film pH of the photosensitive material was different were prepared and evaluated. From the results shown in Table 3, among the photographic materials of the present invention using the same silver halide emulsion, the photographic materials having a coating pH of 4.5 or more and 6.5 or less fluctuate the time from exposure to amplification and development, and increase the amplification. The variation in sensitivity is particularly small with respect to the variation in the concentration of the oxidizing agent in the developer, and further, the variation in gradation when the concentration of the oxidizing agent varies is small, indicating that this is a particularly preferred embodiment of the present invention.

Example 4 (Blue-sensitive silver halide emulsions (Em-B41) to (Em-B41)
Preparation of B44)) The silver halide emulsion of Example 1 (EMP
-3A) In the preparation of silver halide emulsions (EMP-B41) to (EMP-B44), except that a metal complex as shown in Table 4 was added to the liquid C1,
Further, the blue-sensitive silver halide emulsion of Example 1 (Em-B
The same chemical sensitization as in the preparation of 3) was performed to prepare blue-sensitive silver halide emulsions (Em-B41) to (Em-B44).

(Preparation of photosensitive materials (401) to (404)) The preparation of the photosensitive material (103) in Example 1 was repeated except that the blue-sensitive silver halide emulsion was changed as shown in Table 4. And photosensitive materials (401) to (404).

The thus prepared photosensitive material (40)
1) to (404) were processed and evaluated in the same manner as in Example 1.

Further, processing and evaluation were performed in the same manner except that the exposure time was changed to 10 ^-5 seconds. The results are shown in Table 4.

[0137]

[Table 4]

From the results shown in Table 4, among the photosensitive materials of the present invention, the photosensitive materials (402) and (402) containing a metal complex having a nitrosyl ligand of a metal selected from Groups 5 to 10 in the periodic table. In 403), the phenomenon that the change width of the relative sensitivity slightly increases when exposure of 10 ^-5 seconds is performed is reduced, and the effect of improving the sensitivity fluctuation due to the fluctuation of the time from exposure to amplification development regardless of the exposure time is reduced. Is remarkable,
It turns out that this is a preferred embodiment of the present invention.

Example 5 (Preparation of photosensitive materials (501) to (506)) After a corona discharge treatment was applied to the reflective support prepared in Example 1, a gelatin subbing layer was provided, and each layer having the following constitution was further applied. It was coated to prepare silver halide photographic light-sensitive materials (501) to (506). In the preparation of the photosensitive material, each coating solution was prepared so as to have the following coating amount, and (H-
1) and (H-2) were added. Surfactants (SU-1), (SU-2) and (SU-3) were added as coating aids to adjust the surface tension. Further, (F-1) was added to each layer so that the total amount became 0.04 g / m ² .

The coating amount of each layer is shown below.

Layer composition Addition amount (g / m ² ) Second layer (protective layer) Gelatin 1.00 DIDP 0.002 DBP 0.002 Silicon dioxide 0.003 First layer (blue photosensitive layer) Gelatin 1. 30 Blue photosensitive emulsion Table 5 Cyan coupler (C-2) 0.30 Color developing agent (HCD-1) 0.12 Color developing agent (HCD-2) 0.10 Dye image stabilizer (ST-1) ) 0.10 Stain inhibitor (HQ-1) 0.004 DBP 0.30 DOP 0.60 Support polyethylene laminated paper The amount of silver halide is shown in terms of silver.

DOP: dioctyl phthalate HQ-1: 2,5-di-t-octyl hydroquinone

[0143]

Embedded image

The light-sensitive material (50
With respect to 1) to (506), the same processing and evaluation were performed except that the processing step 1 of Example 1 was changed to the following processing step 2. Table 5 shows the results.

Processing Step 2 Processing Temperature Temperature Amplification Developer (CDA-2) 35.0 ± 0.5 ° C. 50 seconds Bleach-fixer (BF-1) 30.0 ± 0.5 ° C. 45 seconds Stabilization Liquid 30 to 34 ° C for 60 seconds Alkaline liquid (AL-1) 30 to 34 ° C for 30 seconds Drying 60 to 80 ° C for 30 seconds The composition of the treatment liquid is shown below.

Amplification developer (CDA-2) Pure water 800 ml Potassium bromide 0.001 g Potassium chloride 1.0 g N, N-diethylhydroxylamine 4.7 g Hydroxylamine sulfate 1.0 g Diethylenetriaminepentaacetic acid pentasodium salt 0 g 1-hydroxyethylidene-1,1'-diphosphonic acid 0.35 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g Disodium hydrogen phosphate 10 g Potassium carbonate 20 g Hydrogen peroxide (5 .99%) 25 ml Adjust the pH to 12.0 with potassium hydroxide or sulfuric acid, and add water to make the total volume 1 liter.

Alkaline solution (AL-1) Pure water 800 ml Disodium hydrogen phosphate 10 g Potassium carbonate 20 g Adjust the pH to 10.0 with potassium hydroxide or sulfuric acid, and add water to make the total volume 1 liter.

[0148]

[Table 5]

Example 5 relates to a photosensitive material in which a color developing agent is incorporated in advance. From the results shown in Table 5, the light-sensitive materials (503) to (506) of the present invention have a small sensitivity fluctuation when the time from exposure to amplification development is changed, and are sensitive to the oxidizing agent concentration fluctuation in the amplification developer. Therefore, it can be seen that sensitivity fluctuation is small and preferable. Among them, the value of S / V is 2
The light-sensitive materials (505) and (506) which are 2.0 or more are
It can be seen that the sensitivity fluctuation is particularly small, which is a particularly preferred embodiment of the present invention.

Example 6 (Preparation of silver halide emulsions (Em-G1) to (Em-R2)) The silver halide emulsion EMP-1 prepared in Example 1
A, EMP-3A, and EMP-7 prepared in Example 2.
A was optimally subjected to chemical sensitization at 60 ° C. using the following compound to give a green photosensitive silver halide emulsion (Em-G1),
(Em-G3) and (Em-G7) were obtained.

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX 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 Further, the following compound was used at 60 ° C. for EMP-1A, EMP-3A and EMP-7A. For optimal chemical sensitization, a red-sensitive silver halide emulsion (Em-R1), (Em-R1)
-R3) and (Em-R7).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-2 1 × 10 ⁻⁴ mol / mol AgX SS-1 2.0 × 10 ⁻³ mol / mol AgX 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

[0153]

Embedded image

(Silver halide photographic light-sensitive material (601))
(Preparation of (603)) After subjecting the reflective support used in Example 1 to 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. . In the preparation of the photosensitive material, each coating solution was prepared so as to have the following coating amount, and (H-
1) and (H-2) were added. Surfactants (SU-1), (SU-2) and (SU-3) were added as coating aids to adjust the surface tension. Further, (F-1) was added to each layer so that the total amount became 0.04 g / m ² .

The coating amount of each layer is shown below.

Layer composition Addition amount (g / m ² ) 7th layer (protective layer) Gelatin 1.00 DIDP 0.002 DBP 0.002 Silicon dioxide 0.003 6th layer (UV absorbing layer) Gelatin 0.40 AI-1 0.01 UV absorber (UV-1) 0.12 UV absorber (UV-2) 0.04 UV absorber (UV-3) 0.16 Stain inhibitor (HQ-5) 0.04 PVP 0.03 Fifth layer (red-sensitive layer) Gelatin 1.30 Red-sensitive emulsion 0.025 Cyan coupler (C-1) 0.28 Dye image stabilizer (ST-1) 0.10 Stain inhibitor (HQ-1) 0.004 DBP 0.10 DOP 0.20 Fourth layer (ultraviolet absorbing layer) Gelatin 0.94 Ultraviolet absorbing agent (UV-1) 0.28 Ultraviolet absorbing agent (UV-2) 0.09 UV absorber (UV-3 ) 0.38 AI-1 0.02 Stain inhibitor (HQ-5) 0.10 Third layer (green-sensitive layer) Gelatin 1.30 AI-2 0.01 Green-sensitive emulsion 0.025 Magenta coupler ( M-1) 0.20 Dye image stabilizer (ST-3) 0.20 Dye image stabilizer (ST-4) 0.17 DIDP 0.13 DBP 0.13 Second layer (intermediate layer) Gelatin 1 .20 AI-3 0.01 Stain inhibitor (HQ-2) 0.03 Stain inhibitor (HQ-3) 0.03 Stain inhibitor (HQ-4) 0.05 Stain inhibitor (HQ-5) 0 .23 DIDP 0.04 DBP 0.02 Fluorescent whitening agent (W-1) 0.10 First layer (blue-sensitive layer) Gelatin 1.20 Blue-sensitive emulsion 0.055 Yellow coupler (Y-1) 0 .70 dye image stabilizer (ST-1) .10 Dye image stabilizer (ST-2) 0.10 Dye image stabilizer (ST-5) 0.10 Stain inhibitor (HQ-1) 0.01 Image stabilizer A 0.15 DBP 0.10 DNP 0.05 support polyethylene-laminated paper The silver halide coating amount was shown in terms of silver.

DNP: dinonyl phthalate PVP: polyvinylpyrrolidone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2,5-di-sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl -5-sec-tetradecylhydroquinone HQ-5: 2,5-di (1,1-dimethyl-4-hexyloxycarbonyl) butylhydroquinone Image stabilizer A: pt-octylphenol

[0158]

Embedded image

[0159]

Embedded image

[0160]

Embedded image

The light-sensitive material (60
For 1) to (603), light wedge exposure was performed for 0.5 seconds with white light, and the same processing and evaluation as in Example 1 were performed. Table 6 also shows the results.

[0162]

[Table 6]

From the results in Table 6, it can be seen that the light-sensitive material of the present invention (60
It can be seen that 2) and (603) are preferable because the sensitivity fluctuation when the time from exposure to amplification development fluctuates and the sensitivity fluctuation with respect to the concentration fluctuation of the oxidizing agent in the amplification developer is small. The photosensitive material (603) using a silver halide emulsion in which silver halide grains having an average aspect ratio of 2.0 or more occupy 50% or more has a small sensitivity variation when the time from exposure to amplification development varies. It can be seen that this is a particularly preferred embodiment of the present invention.

Further, the photosensitive materials (601) to (603) were subjected to photographing and development processing by Konica Color LV400.
After performing image exposure through a color negative film, processing was performed by changing the time from exposure to amplification and development processing as described above, and the resulting print image was observed. As a result, the light-sensitive materials (602) and (60)
3), when the time from exposure to amplification and development is shorter than that of the photosensitive material (601) of the comparative example, and also when the oxidizing agent concentration in the amplification developer is high and amplification development is active, An increase in the density of the white background and a change in the density were small, and a beautiful print was obtained.

[0165]

The silver halide photographic light-sensitive material and the image forming method according to the present invention have an excellent effect of improving the sensitivity fluctuation due to fluctuations in amplification processing conditions and fluctuations in the time from exposure to amplification development.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] May 19, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0112

[Correction method] Change

[Correction contents]

[0112]

Embedded image

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0119

[Correction method] Change

[Correction contents]

[0119]

[Table 1]

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0127

[Correction method] Change

[Correction contents]

[0127]

[Table 2]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 1/76 501 G03C 1/76 501 7/407 501 7/407 501

Claims (11)

[Claims] 1. A support having at least one color image-forming layer containing photosensitive silver halide grains having a silver chloride content of 80 mol% or more and a dye-providing substance, and
A silver halide photographic material, wherein the photosensitive silver halide grains in the color image forming layer satisfy the following formula (1). (Formula 1) S / V ≧ 17.0 [In Formula 1, S represents the average grain surface area (unit: μm ² ) of the photosensitive silver halide grains in the color image forming layer, and V represents the color image formation. Represents the average grain volume (unit: μm ³ ) of photosensitive silver halide grains in the layer. ] 2. The method according to claim 1, wherein 50% or more of the photosensitive silver halide grains contained in the color image forming layer are tabular silver halide grains having an aspect ratio of 2.0 or more. Item 6. The silver halide photographic material according to Item 1. 3. The photosensitive silver halide grains contained in the color image forming layer have a silver content of 0.001 g / m ^{2 in} terms of silver.
3. The silver halide photographic light-sensitive material according to claim 1, wherein the amount is from 0.1 to 0.1 g / m < ² >. 4. The silver halide photographic material according to claim 1, wherein the color image forming layer is a magenta image forming layer. 5. A yellow image-forming layer, a magenta image-forming layer, and cyan comprising at least one layer each containing a photosensitive silver halide having a silver chloride content of 80 mol% or more and a dye-donor substance on a support. A silver halide photographic material having an image forming layer, wherein the photosensitive silver halide grains in each color image forming layer satisfy the following formula (2). (Formula 2) S / V ≧ 17.0 [In Formula 2, S represents the average grain surface area (unit: μm ² ) of the photosensitive silver halide grains in each color image forming layer, and V represents the color image formation. Represents the average grain volume (unit: μm ³ ) of photosensitive silver halide grains in the layer. ] 6. A tabular silver halide grain having an aspect ratio of 2.0 or more in a projected area ratio of at least 50% of a photosensitive silver halide grain contained in each color image forming layer. Item 6. A silver halide photographic material according to item 5. 7. The photosensitive silver halide grains contained in each color image forming layer have a silver content of 0.001 g / m 2 in terms of silver.
The silver halide photographic material as claimed in claim 5 or 6, characterized in that a ^{2 ~0.1g} / m ^2. 8. The silver halide photographic material according to claim 1, wherein the photographic layer of the silver halide photographic light-sensitive material has a coating pH of 4.5 to 6.5. Photosensitive material. 9. An image forming method, comprising subjecting the silver halide photographic material according to claim 1 to amplification development processing. 10. The image forming method according to claim 9, wherein the amplification and development processing is performed in the presence of a black-and-white developing agent. 11. The pH during the amplification and development processing is 10.5.
11. The image forming method according to claim 9, wherein