JPH0711680B2 - Negative-type silver halide photographic light-sensitive material with improved temporal stability and image quality - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material, and more specifically, the raw film has excellent stability over time (particularly moisture resistance) and has improved graininess and sharpness at the same time. And a silver halide photographic light-sensitive material (hereinafter, simply referred to as light-sensitive material).

[Background of the Invention]

The silver halide photographic light-sensitive material, especially the silver halide photographic light-sensitive material for photography, is a small format screen and a large format screen as the negative photography format is reduced due to the spread of small cameras that are convenient to carry in recent years. From now on, the same image quality as when the image is stretched is desired. That is, there is a strong demand for the development of a silver halide photographic light-sensitive material that does not impair the granularity and sharpness even when the enlargement factor during printing increases.

On the other hand, even if the photosensitive material has high sensitivity and high image quality, if the performance of the raw film deteriorates during storage over time, the original performance of the photosensitive material cannot be brought out and the quality of the material cannot be improved. The variation of the value becomes large and it cannot meet the needs of users.

It is well known that one of the means for improving the graininess is to improve the image quality by incorporating silver iodide in a silver halide composition, especially in silver halide grains, and utilizing the development inhibiting effect of iodine ions released during development. Technology.

For example, a silver halide emulsion generally used for a black and white light-sensitive material contains 2 mol% or more of silver iodide, and the above-mentioned technique can be used for adjusting the above-mentioned image quality. The material generally has a silver iodide content of 4 mol% or more, and the above-mentioned technique can be utilized more effectively. However, increasing the content of silver iodide in this way means graininess. However, on the other hand, silver iodide cannot suppress the sulfur sensitizing reaction or the developing reaction during the chemical ripening, and therefore is not necessarily a preferable means for improving the sensitivity.

The desensitization resulting from the inhibitory action that occurs during the above chemical ripening or development can be considerably recovered, for example, by adding an increased amount of a sulfur sensitizer or a gold sensitizer during the chemical ripening,
At the same time, the emulsion coating solution and the light-sensitive material are deteriorated in stability over time, and fog is likely to occur.

On the other hand, most conventional silver halide emulsions have a wide grain size distribution and a non-uniform crystal habit, and therefore, it is said that the optimum chemical sensitization is performed on any grain during chemical sensitization. Hard to say. Therefore, at present, the sensitivity that each particle originally has has not been sufficiently extracted.

Therefore, in recent years, a monodisperse emulsion (that is, a silver halide emulsion having a narrow grain size distribution and a uniform crystal habit) has been attracting attention.

On the other hand, based on the study of the growth mechanism of silver halide crystals, the next-stage precipitation was sequentially laminated on the crystal nuclei of the preceding silver halide, and the composition or progress environment of each precipitate was intentionally controlled (core / shell) emulsion. Is also well known.

A photographic emulsion composed of core / shell type silver halide grains, which is substantially monodisperse and has a higher silver iodide content in the core portion than in the shell portion, is excellent in sensitivity and graininess. It is expected that it will be the most suitable for producing a light-sensitive material.

However, even if such a core / shell type silver halide grain is used, the graininess is improved, but the sharpness is not sufficiently improved.

As a means of improving sharpness, it is known that the grain size of silver halide grains is coarsened to a region where light scattering is small, or the amount of coated silver is significantly reduced to suppress light scattering in an emulsion film. However, according to this technique, the development active points are reduced due to the coarsening of the particles and the like, which causes the deterioration of the graininess.

Further, there is known a method of improving sharpness by an irradiation prevention effect and an antihalation effect by using a dye in order to reduce light scattering of an emulsion film. It leads to a loss of balance.

[Object of the Invention]

The purpose of the present invention is to stabilize the raw film over time (especially moisture resistance).
And to provide a light-sensitive material which is excellent in graininess and sharpness at the same time.

[Structure of Invention]

The present inventor has studied various materials based on the above technical background. As a result, at least one of the photosensitive silver halide emulsion layers on the support has a silver iodide content of 6 to 40 mol%. Core / shell type core / shell type silver halide grains having a layer or phase, the outermost surface layer having a silver iodide content of less than 6 mol% and an average silver iodide content of 4 to 20 mol%. Diffusive resistance which is combined with a layer containing the silver halide grains and / or a silver halide emulsion layer having a color sensitivity different from that of the layer to react with an oxidized product of a developing agent to form a dye. -Containing coupler, which further forms an unsharp positive image, reacts with the oxidant of the developing agent, and diffuses moderately during the development processing, and the above-mentioned diffusion-resistant coupler reacts with the oxidant of the developing agent. It has the main absorption in the main absorption wavelength range of the formed dye. Presence layer of resistant diffusible coupler colored compounds or has been found that the objects of the present application is achieved by incorporating in the adjacent layer.

[Specific Description of the Invention]

The silver halide grain having a layer or phase having a large silver iodide content (hereinafter, simply referred to as core / shell type silver halide grain) according to the present invention is conceptually a silver iodide content. The grain structure is composed of two or more different layers, and the layer having the highest silver iodide content (hereinafter referred to as the core) is other than the outermost surface layer (hereinafter referred to as the shell). Is a silver halide grain consisting essentially of silver iodobromide. The inner layer having the highest silver iodide content or the phase (core) silver iodide content of 6 to 40 mol% can be used, but preferably 8 to 30 mol%, more preferably 10 to 10 mol%.
It is 20 mol%. The silver iodide content of the outermost surface layer is preferably less than 6 mol%, more preferably 0 to 4.0 mol%.

The proportion of the shell portion of the core / shell type silver halide grains is 10 to 80%, preferably 15 to 70%, more preferably
20-60%.

The ratio of the core portion is preferably 10 to 80% of the total particles, and more preferably 20 to 50%.

In the present invention, the difference in content between the core portion having a high silver iodide content and the shell portion having a low content of the silver halide grains may have a sharp boundary, and the boundary is not always clear and continuous. It may change. Further, those having an intermediate layer having a silver iodide content intermediate between the core portion and the shell portion between the core and the shell are also preferably used.

In the case of core / shell type silver halide grains having the above-mentioned intermediate layer, the volume of the intermediate layer is 5 to 60% of the total amount of the grains and further 20
~ 55% is good. The difference in silver iodide content between the shell and the intermediate layer and between the intermediate layer and the core is preferably 3 mol% or more, and the difference in silver iodide content between the shell and the core is preferably 6 mol% or more.

In the present invention, the average silver iodide content of the core / shell type silver halide grains is preferably 4 to 20 mol%, more preferably 5 to 15 mol%. Further, silver chloride may be contained within a range that does not impair the effects of the present invention.

The core / shell type emulsion of the present invention is disclosed in JP-A-59-177535 and JP-A-6-177535.
It can be produced by a known method disclosed in, for example, 0-138538, 59-52238, 60-143331, 60-35726 and 60-258536.

When a core / shell type silver halide emulsion is grown starting from seed grains as in the method described in Examples, it may have a halogen composition region different from the core in the grain central portion. It is possible. In such a case, the halogen composition of the seed grains may be of any composition such as silver bromide, silver iodobromide, silver chloroiodobromide, silver chlorobromide, silver chloride, etc. Silver iodobromide or silver bromide at 10 mol% or less is preferable.

Further, the proportion of the total silver halide in the seed emulsion is preferably 50% or less, particularly preferably 10% or less.

The distribution state of silver iodide in the above core / shell type silver halide grains can be detected by various physical measurement methods, and is described in, for example, Abstracts of the Annual Meeting of the Photographic Society of Japan, 1981. As described above, it can be investigated by measuring luminescence at a low temperature or by an X-ray diffraction method.

The core / shell type silver halide grains of the present invention are cubic, 14
It may be a normal crystal such as a tetrahedron or octahedron, may be composed of twin crystals, or may be a mixture thereof, but a normal crystal is preferable.

The particle size distribution of the core / shell type silver halide grains in the present invention may be either polydisperse or monodisperse.
The coefficient of variation of the grain size distribution is preferably 20% or less, and the variation coefficient is preferably 15% or less. This coefficient of variation is Is a measure of monodispersity.

The core / shell type silver halide grains of the present invention preferably have a grain size (defined as the length of one side of a cube having the same volume as the silver halide grains) of 0.1 to 3.0 μm.

The compound capable of forming a means for forming an unsharp positive image in combination with the silver halide emulsion layer according to the present invention is a colored compound, and reacts with an oxidant of a developing agent to moderately develop during the development processing. It is a compound characterized by diffusing. Here, the term "appropriately diffusing" means that, in an image forming process using the photographic material of the present invention, it diffuses more than a diffusion resistant coupler used in combination, especially in a developing process. After completion of the above, at least 30 wt% or more of the added amount remains in the photographic material.

The compound of the present invention which is a colored compound which reacts with an oxidized product of a developing agent and which diffuses appropriately during development processing (hereinafter, referred to as the compound of the present invention) is a compound which has the above-mentioned diffusion resistant coupler as a color developing agent. It is a colored compound having a main absorption in the main absorption wavelength range of a dye produced by the reaction with an oxidant. And
Reaction with the oxidant of the developing agent produces a colored or colorless product. When the reaction product has an undesired color tone in image formation, the reaction product flows out of the photographic material. Therefore, in the area where a color image is produced by the reaction between the oxidized product of the color developing agent and the diffusion-resistant coupler, the compound of the present invention also reacts with the oxidized product of the developing agent to produce a compound that is colorless or flows out of the system. The main absorption wavelength does not substantially change, and it is resistant to diffusion. Further, the compound of the present invention remains unreacted in the area where no color image is formed by the diffusion resistant coupler. As a result, the color image formed by the diffusion-resistant coupler and the compound of the present invention have an inverse relationship with each other, or a seemingly no image, that is, when the former is a negative image, the latter forms a positive image or a seemingly no image. It will be. Moreover, since the compound of the present invention has an appropriate diffusivity, an unsharp image,
That is, an unsharp mask image is formed.

Of the above, the compound of the present invention is not the image of the inverse relationship,
When forming a seemingly no image, the image of only the compound of the present invention causes almost no density change macroscopically, but a high degree of diffusion occurs at the edge part (boundary part where the intensity of irradiation light changes). And the resistance to diffusion after the reaction cause a micro concentration change (edge effect).

The compound of the present invention may be a so-called shift compound. That is, a color compound having a desired absorption may be discolored during the development process, and the degree of discoloration is preferably such that the change in the maximum absorption wavelength is 10 nm or more.
As such a discoloration mechanism, a mechanism in which the color tone is changed by subjecting the compound of the present invention to hydrolysis is preferably mentioned.

Examples of the compound of the present invention include compounds represented by the following general formula [I].

General formula [I] A-Link-B In the formula, A is an organic residue capable of reacting with an oxidized product of a developing agent to release the Link-B portion according to the amount of the oxidized product of a developing agent, and Link is A and B. Is a group that binds to, and B represents an organic residue.

Further, the compound represented by the general formula [I] is a colored compound which diffuses in the photographic material appropriately during the development processing, and the product generated due to A and Link-B after the reaction has a desirable color tone in image formation. In the case of the compound represented, the hydrophilic region is provided with a substituent having a lipophilic balance so that the product flows out of the photographic material after the reaction.

Examples of A in the general formula [I] include a residue of a coupler which produces a colored or colorless product by a coupling reaction with an oxidized product of a color developing agent, or a moiety which undergoes a cross oxidation reaction with an oxidized product of a developing agent. To be

Specific examples of the former include, for example, phenols, naphthols, 5-pyrazolones, pyrazocotriazoles,
Pyrazolobenzimidazoles, indazolones, acylacetanilides, RCOCH ₃ (R is alkyl,
Aryl, heterocyclic group) (Z is a group of atoms that completes, for example, a 5- to 8-membered saturated or unsaturated alicyclic ring or heterocyclic ring, and R'represents an aryl residue.).

Specific examples of the latter include, for example, an alkali after being oxidized.
B-SO as Link-B by cleavage₂NH Emitting fe
Knols, naphthols, indanones, indole
, Hydroquinone residues, after being oxidized, closed intramolecularly
Received ring reaction and B-SO as Link-B₂ Emit
Enols (see U.S. Pat. Nos. 3,443,939 and 3,44
Nos. 3,940 and 3,443,941. ) Is
Can be mentioned.

The Link, for example, -N = N -, - O - , - S -, - NH-SO 2 -, - SO 2 -NH
-, And so on.

here, Is a nitrogen-containing heterocyclic residue, such as imidoyl succinate,
Imidoyl phthalate, pyridoyl, imidazolyl imidazoloneyl, benzimidazolyl, hydantoyl, thiohydantoyl triazolyl, benztriazolyl, urazolyl, 2,4-dioxyoxazolyl, 2,4-dioxothiazolyl, There are thiadiazo reel and tetrazo reel. R is an alkyl which may have a substituent,
Aryl and the like.

As B, when Link is a chromophore such as -N = N-, -CH =, it is, for example, an aryl group or a heterocyclic group, and preferably an organic residue having an auxochrome or a dye residue. It may be. When Link is not a chromophore, it is preferably a dye (eg, azo, anthraquinone, azomethine, indophenol, indoaniline, etc.) residue.
The compound represented by the general formula [I] having such a structure is represented by B
It may be a colored compound as a part or as a whole A-Link-B.

To give the compound represented by the general formula [I] a property of moderately diffusing during the development process and a diffusing property for allowing an undesirable product after the reaction to flow out of the system, for example, a carboxyl group is used. , An alkali-soluble group such as a sulfo group, a hydroxyl group, and a sulfamoyl group, and a group such as an alkyl group that reduces diffusibility may be appropriately introduced to balance the diffusivity before and after the reaction.

When the compounds of the present invention are classified according to their properties, for example, the following classifications can be mentioned.

CLASS I: Coloring dye forming type In the compounds belonging to this class, the A part of the general formula [I] is a coupler residue and the Link part is bonded to the active site of the coupler. However, when Link is —NHSO ₂ — (a nitrogen atom is bonded to the Coup part), it may be adjacent to the active site.

The photographic material preferably has an alkali-soluble group and, for example, an alkyl group having 16 or less carbon atoms so as to have appropriate diffusion. If the color-forming dye formed by coupling the A-part with the oxidation product of the color-developing agent is not desirable for image formation, should an alkali-soluble group be present in the A-part so that the color-forming dye will flow out of the system during processing. As the color developing agent, it is preferable to use one having an alkali-soluble group.

When the B portion forms a dye, the B portion preferably has an alkali-soluble group so that the B portion after the reaction flows out of the system.

In the exposed part, the compound A belonging to this class produces a negative colored dye image in the exposed part, but flows out of the system, and when the part B is a dye, the part B also flows out of the system after leaving the part A. Therefore, a positive image is formed with the compound represented by the general formula [I] remaining in the unexposed area. Moreover, the compound has a moderate diffusivity so that it will migrate slightly into the layer during the development process to form an unsharp positive image. Further, among these types, the following two types are preferable.

(Type A): Colored coupler type [II] Coup-Link _2- Ar Coup-of the general formula [II] is preferably a coupler residue having an alkali-soluble group, and the dye produced by the color development reaction is a photographic material. It leaks out of the system.

Ar is preferably an aryl group which may have a substituent, for example, a benzene type or naphthalene type, and a heterocyclic group which may have a substituent, for example, isoxazole and the like, and a compound of the general formula [II] is photographed. Since it moves slightly in the material, it preferably has a semi-diffusion preventing group, and particularly preferably has an Ar portion. Link ₂ is -N = N- or -CH =. Some of these compounds have already been used as colored couplers, for example, U.S. Patents 2,449,969, 2,688,538 and 2,706,684.
No. 2,808,329, 3,005,712, Belgian patent 570,
It is known for example in No. 271 and Japanese Patent Publication No. 44-32461.

However, the present invention and these prior arts are completely different in the use method of the compound and the purpose of use, and the effects obtained are completely different. That is, in the above-mentioned prior art, since the hue generated by the Coup portion or coupler portion represented by the general formula [II] is the main absorption for image formation, it is a principle that the dye generated from this portion does not move, The hue of the compound represented by the formula [II] is a secondary absorption portion different from the above main absorption wavelength region. According to the present invention, it is essential that the dye generated from the Coup portion is taken out of the system, and that the general formula [I
The hue of the compound represented by I] is the same as the main absorption of the image forming layer. That is, the light-sensitive wavelength range of the silver halide layer combined with the compound of the present invention is the complementary color of the compound hue in the case of a conventional negative photographic material. Specifically, for example, with respect to a green-sensitive negative layer, prior art colored couplers use a yellow compound in this layer, whereas the present invention uses a magenta compound.
These differences will be easily understood because they will be described in detail in the examples.

(Type B): Active site substitution type General formula [III] Coup-Link _3- Dye Coup is the same as general formula [II]. Link ₃ has the same meaning as Link of the general formula [I], and similar ones are exemplified, and preferably a group which produces alkali solubility after the coupling reaction, for example, —O—, —SO ₂ —NH—, —NHSO. _2- is preferable. Dye represents a dye moiety and preferably has an alkali-soluble group, but it is not essential depending on the type of Link ₃ . Since the compound represented by the general formula [III] is adjusted to slightly diffuse in the photographic material, it preferably has a semi-diffusion preventing group.

The group is preferably attached to one of the coloring dyes and Link _3- Dye, which has a better diffusibility. Compounds belonging to this class are disclosed in U.S. Pat.Nos. 3,227,550 and 3,476,563, but these prior arts have completely different usages similar to Type A, and the concept of the present invention is included. It is not. That is, a part of the present invention is obviously different from the aspect of the present invention in the case where it is used for the same color correction as the color coupler like Type A and the case where the Dye portion which is diffused and transferred and flows out is used for an image.

Next, a compound group that does not produce a color image after the color reaction is described.

CLASS II: colorless coupling body-forming type Compounds belonging to this class are CLAS for A part of general formula [I].
It reacts similarly to the compound of SI, but since the reaction product is colorless, it may remain in the layer after the coupling reaction.

(Type C): Weiss coupler type general formula [IV] Wcoup-Link _4- Dye Wcoup is, for example, R ₂ COCH _2- (R ₂ is alkyl, aryl, or a heterocyclic group having alkyl having 16 or less carbon atoms) , (Z is an atomic group that completes a 5- to 8-membered alicyclic ring, condensed ring or heterocyclic ring, and R ₃ represents an aryl residue).

Link ₄ is -O -, - S- or -SO ₂ - shows a.

Dye is a dye residue that preferably has an alkali-soluble group and is L
ink _4- Dye flows out of the layer.

Further, this compound preferably has a semi-diffusion preventing group so that the compound itself slightly diffuses in the layer in cooperation with an alkali-soluble group which may be present in the Dye portion, and particularly in the W-coup portion. Preferably there is.

CLASS III: Redox reaction type Compounds belonging to this class do not undergo coupling reaction such as CLASS I or II. Instead, it reacts with an oxidized product of a developing agent to form a quinone, a quinimide, etc., but this product releases a dye only when it reacts with an alkali in a developing solution or an intramolecular ring closure reaction.

(Type D): DRR compound type General formula [V] FUN-Link _5- Dye FUN shows a redox mother nucleus, and is 2-, 3- or 4-phenol, 4-α-naphthol, 1-β-naphthol, 2 -Hydroquinone, 3-indole, 4-pyrazolone-5 residue, Link ₅ is -NHSO _2- (nitrogen atom is bonded to FUN part),
_{-O -, - SO 2 -,} - S- and the like, Dye is a dye residue, preferably has an alkali-soluble group.

When a semi-diffusion preventing group that cooperates with an alkali-soluble group which may be present in the Dye portion is used to allow the compound of the general formula [V] to slightly diffuse in the layer, it is preferably attached to the FUN portion. .

A dye or a precursor thereof, which itself forms a diffusion-resistant dye by a reaction with an oxidant of a color developing agent, may form a new dye portion by the reaction. However, the dye portion may not be newly formed, and the dye portion before the reaction or the precursor portion thereof may be made diffusion resistant as the dye portion after the development processing step. Regarding this type of compound, Japanese Patent Application No. 60-1665
It is described in detail in the specification of No. 44.

Next, the compounds of the present invention are specifically exemplified, but the present invention is not limited to these compounds.

The above-mentioned positive compounds are synthesized according to a general synthetic method, but there are roughly two main routes. That is, one is a method in which a dye moiety is pre-synthesized and finally the dye moiety is combined with another moiety having an amino group as sulfochloride or acid chloride by a suitable acid chloride agent such as phosphorus oxychloride or thionyl chloride. The other synthetic method is to obtain a dye moiety by diazo coupling in the final step.

In the case of a dye precursor, it can be obtained by, for example, acylating the auxochrome after forming the dye.

The positive compound is contained in a silver halide emulsion layer containing the above-mentioned diffusion-resistant coupler and / or in a photographic constituent layer separate from the silver halide emulsion layer.

The other photographic constituent layer need not be adjacent to the silver halide emulsion layer, but is preferably adjacent to it.
Further, when the positive compound itself has a main absorption in the main light-sensitive wavelength region of the emulsion layer, it is necessary to position it on the side opposite to the light incident side at the time of exposure with respect to the silver halide emulsion layer to lower the sensitivity. It is preferable for preventing Further, the other photographic constituent layer may be a light-sensitive silver halide emulsion layer having the same color sensitivity as that of the light-sensitive silver halide emulsion layer or a non-light-sensitive layer.

Further, the diffusion resistant positive compound is preferably contained in a non-photosensitive manner.

When the positive compound is contained in the non-photosensitive layer, the positive compound reacts with the oxidized product of the developing agent generated by the development of the photosensitive silver halide emulsion layer, which has diffused into the non-photosensitive layer. As a result, an unsharp positive image is formed.

The amount of the positive compound used is preferably 0.01 to 1.00 mol, and particularly preferably 0.05 to 0.60 mol, per mol of the diffusion resistant coupler used in combination with the compound. Further, as a method of adding the same, a method similar to that of the diffusion resistant coupler described later can be used.

When the light-sensitive material of the present invention is a multi-layer color light-sensitive material comprising three light-sensitive layers of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer, the silver halide grains of the present invention are contained in at least the green-sensitive layer and / or It is desirable to include it in the red-sensitive layer.

The photographic materials of this invention have a diffusion-resistant coupler and a compound of this invention in combination with a light-sensitive silver halide emulsion as described above.

Here, the diffusion resistant coupler is preferably incorporated in the photosensitive silver halide emulsion layer. Further, the compound of the present invention is contained in the silver halide emulsion layer and / or in a photographic constituent layer different from the silver halide emulsion layer.

The other photographic constituent layer need not be adjacent to the silver halide emulsion layer, but is preferably adjacent to it.
Further, it is preferable to position the silver halide emulsion layer on the side opposite to the light incident side at the time of exposure in order to prevent a decrease in sensitivity. Further, the other photographic constituent layer may be a light-sensitive silver halide emulsion layer having the same color sensitivity as that of the light-sensitive silver halide emulsion layer or a non-light-sensitive layer. When the compound of the present invention is contained in the non-photosensitive layer, the compound of the present invention reacts with the developing agent generated by the development in the above-mentioned photosensitive silver halide emulsion layer, which has diffused in the non-photosensitive layer. Then, an unsharp mask image is formed.

The amount of the compound of the present invention used is preferably 0.01 to 1.00 mol, and more preferably 0.05 to 0.60 mol, per mol of the diffusion resistant coupler used in combination with the compound. Further, as a method of adding the same, a method similar to that of the diffusion resistant coupler described later can be used.

The light-sensitive material of the present invention achieves the object of the present invention only by containing the silver halide grains of the present invention and the compound of the present invention. The light-sensitive material of the present invention contains other known silver halide emulsions. You may use together.

Examples of such silver halide emulsions include ordinary silver halide emulsions such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide and silver chloride as silver halides. Any of those used in can be used, especially silver bromide,
Silver iodobromide and silver chloroiodobromide are preferred.

The silver halide grains used in the silver halide emulsion may be those obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after forming seed grains. The method of forming seed particles and the method of growing seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed at the same time, or the other may be mixed in a liquid containing either one. Alternatively, it may be produced by sequentially adding halide ions and silver ions simultaneously while controlling the pH and pAg in the mixing vessel while considering the critical growth rate of silver halide crystals. By this method, silver halide grains having a regular crystal form and a substantially uniform grain size can be obtained. The conversion may be used at any step in the formation of AgX to change the halogen composition of the grains.

A known silver halide solvent such as ammonia, thioether or thiourea can be present during the growth of silver halide grains.

The silver halide grains are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium salt (including complex salt) and iron salt (in the process of forming and / or growing the grain). Metal ions are added using at least one selected from the group consisting of complex salts)
Alternatively, these metal elements can be contained on the grain surface, and reduction sensitizing nuclei can be imparted to the inside of the grain and / or the grain surface by placing in a suitable reducing atmosphere.

In the silver halide emulsion, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or may be contained. When removing the salts, Research Disclosure (RD)
It can be carried out based on the method described in Item 17643, Item II.

The silver halide grain may be a grain in which a latent image is mainly formed on the surface, or may be a grain in which a latent image is mainly formed inside the grain.

The silver halide grain may have a regular crystal form such as a cube, an octahedron or a tetradecahedron, or may have an irregular crystal form such as a sphere or a plate. In these grains, any ratio of {100} plane to {111} plane can be used. Further, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed.

The size of silver halide grains may be 0.05 to 30 μm, preferably 0.1 to 20 μm.

The silver halide emulsion may have any grain size distribution. An emulsion having a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion having a narrow grain size distribution (referred to as a monodisperse emulsion. The monodisperse emulsion referred to here is the standard deviation of the grain size distribution. When divided by the average grain size, the value is 0.20 or less, where the grain size is the diameter in the case of spherical silver halide and the projected image in the case of grains other than spherical. The diameter when converted to a circular image of the same area is shown).
Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used.

As the silver halide emulsion, two or more kinds of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion can be chemically sensitized by a conventional method. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
The noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

The silver halide emulsion can be optically sensitized to a desired wavelength range by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. A dye that does not have a spectral sensitizing action by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, and that contains a supersensitizer that enhances the sensitizing action of the sensitizing dye in the emulsion. Good.

As the sensitizing dye, a cyanine dye, a merocyanine dye,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes and hemioxanol dyes are used.

Particularly useful dyes are cyanine dyes, merocyanine dyes,
And a complex merocyanine dye.

Silver halide emulsion, during the manufacturing process of the light-sensitive material, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, during chemical ripening, at the end of chemical ripening, and / or after the completion of chemical ripening, before coating a silver halide emulsion, Compounds known in the art as antifoggants or stabilizers can be added.

As the binder (or protective colloid) of the silver halide emulsion, it is advantageous to use gelatin, but gelatin derivatives, graft polymers of gelatin and other macromolecules, other proteins, sugar derivatives, cellulose derivatives, single Alternatively, a hydrophilic colloid such as a synthetic hydrophilic polymer substance such as a copolymer can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of a light-sensitive material using the silver halide emulsion of the present invention crosslink binder (or protective colloid) molecules, and one or more hardeners for enhancing film strength. By using it, a dura mater can be obtained. The hardener can be added in such an amount that the photosensitive material can be hardened to the extent that it is not necessary to add the hardener to the processing liquid.
It is also possible to add a hardening agent to the processing liquid.

For example, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5 -Triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol and the like), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine and the like), mucohalogen acids (mucochloric acid, Mucophenoxycyclo acid, etc.) can be used alone or in combination.

A plasticizer may be added to the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material for the purpose of enhancing flexibility. Preferred plasticizers are the compounds described in A of RD17643, section XII.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or these and acrylic acid, A polymer having a monomer component of a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid and the like can be used.

In the color development processing, the emulsion layer of the light-sensitive material forms a dye by a coupling reaction with an oxidant of an aromatic primary amine developer (eg, p-phenylenediamine derivative, aminophenol derivative). A coupler is used. The dye-forming couplers are usually selected so that a dye that absorbs the light of the light-sensitive spectrum of the emulsion layer is formed for each emulsion layer. A magenta dye forming coupler is used in the sensitive emulsion layer and a cyan dye forming coupler is used in the red sensitive emulsion layer. However, a silver halide color photographic light-sensitive material may be prepared by a method different from the above combination depending on the purpose.

It is desirable that these dye-forming couplers have a group called a ballast group, which has a carbon number of 8 or more, which makes the coupler non-diffusible. Also, these dye-forming couplers need only reduce 4 molecules of silver ion in order to form 1 molecule of dye, but they need only reduce 2 molecules of silver ion even if they are 4 equivalence. Either of two equivalence may be used. The dye-forming coupler has a color-correcting effect and is coupled with a colored coupler and an oxidant of a developing agent to develop a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent. , Hardeners, antifoggants, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizing compounds that release photographically useful fragments. Among these, a coupler which releases a development inhibitor with development and improves the sharpness of images and the graininess of images is called a DIR coupler. Instead of the DIR coupler, a DIR compound which releases a development inhibitor at the same time as producing a colorless compound by coupling reaction with an oxidized product of a developing agent may be used.

The DIR coupler and the DIR compound used are those in which the inhibitor is directly bonded to the coupling position, and those in which the inhibitor is bonded to the coupling position via a divalent group and which are separated by the coupling reaction. Intramolecular nucleophilic reaction, intramolecular electron transfer reaction and the like so that the inhibitor is released (referred to as timing DIR coupler and timing DIR compound) are included. Further, as the inhibitor, one that is diffusible after withdrawal and one that is not so diffusible can be used alone or in combination depending on the application. Aromatic first
Coupling reaction with the oxidation product of the primary amine developer,
A colorless coupler that does not form a dye (also called a competing coupler) can be used in combination with the dye-forming coupler.

As the yellow dye-forming coupler, a known acylacetanilide type coupler can be preferably used.
Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous. Specific examples of yellow color forming couplers that can be used include, for example, U.S. Pat.
No. 7, No. 3,265,506, No. 3,408,194, No. 3,551,1
No. 55, No. 3,582,322, No. 3,725,072, No. 3,891,
No. 445, West German patent 1,547,868, West German application published 2,219,91
No. 7, No. 2,261,361, No. 2,414,006, British Patent No. 1,42
5,020, JP-B-51-10783, JP-A-47-26133, 4
8-73147, 50-6341, 50-87650, 50-123
342, 50-130442, 51-21827, 51-102636
No. 52-82424, No. 52-115219, No. 58-95346 and the like.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indazolone couplers and the like can be used. Specific examples of magenta color couplers that can be used include, for example, U.S. Pat.Nos. 2,600,788 and 2,983,608.
No. 3, No. 3,062,653, No. 3,127,269, No. 3,311,47
No. 6, No. 3,419,391, No. 3,519,429, No. 3,558,3
No. 19, No. 3,582,322, No. 3,615,506, No. 3,834,
908, 3,891,445, West German patent 1,810,464, West German patent application (OLS) 2,408,665, 2,417,945, 2,41
No. 8,959, No. 2,424,467, Japanese Patent Publication No. 40-6031, Japanese Patent Laid-Open No. 49
-74027, 49-74028, 49-129538, 50-60
No. 233, No. 50-159336, No. 51-20826, No. 51-26541
No. 52-42121, No. 52-58922, No. 53-55122,
Examples include those described in Japanese Patent Application No. 55-110943.

As the cyan dye forming coupler, a phenol or naphthol type coupler is generally used. Specific examples of cyan color forming couplers that can be used include, for example, U.S. Pat.
No. 0, No. 2,474,293, No. 2,801,171, No. 2,895,8
No. 26, No. 3,476,563, No. 3,737,326, No. 3,758,
No. 308, No. 3,893,044 specification, JP-A-47-37425,
50-10135, 50-25228, 50-112038, 50
The couplers described in JP-A-117422 and JP-A-50-130441 and the couplers described in JP-A-58-98731 are preferable.

Among the dye-forming couplers, colored couplers, DIR couplers, DIR compounds, image stabilizers, antifoggants, UV absorbers, and fluorescent brighteners that do not need to be adsorbed on the surface of silver halide crystals, hydrophobic compounds are Various methods such as a solid dispersion method, a latex dispersion method and an oil-in-water emulsion dispersion method can be used, which can be appropriately selected according to the chemical structure of the hydrophobic compound such as a coupler. The oil-in-water emulsion dispersion method can be applied by a conventionally known method of dispersing a hydrophobic additive such as a coupler, and usually has a low boiling point of about 150 ° C. or higher and a high boiling point organic solvent, and / or an aqueous solution. Dissolve in a hydrophilic organic solvent together, and emulsify and disperse using a surfactant in a hydrophilic binder such as gelatin aqueous solution, using a dispersing means such as stirrer, homogenizer, colloid mill, flowgit mixer, ultrasonic device, etc. After that, it may be added to the desired hydrophilic colloid solution. A step of removing the low boiling point organic solvent may be added at the same time as the dispersion or dispersion.

As a high boiling point solvent, organic compounds with a boiling point of 150 ° C or higher, such as phenol derivatives, alkyl phthalates, phosphates, citrates, benzoates, alkylamides, fatty acid esters, trimesic acid esters that do not react with the oxidized product of the developing agent. A solvent is used.

A low boiling or water soluble organic solvent can be used with or in place of the high boiling solvent. Examples of the organic solvent having a low boiling point and substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane and benzene.

Dye forming coupler, DIR coupler, Colored coupler, D
When the IR compound, the image stabilizer, the antifoggant, the ultraviolet absorber, the brightening agent and the like have an acid group such as carboxylic acid and sulfonic acid, they may be introduced into the hydrophilic colloid as an alkaline aqueous solution. it can.

Dissolving a hydrophobic compound in a solvent having a low boiling point solvent alone or in combination with a high boiling point solvent, as a dispersion aid when dispersed in water using mechanical or ultrasonic waves, an anionic surfactant, a nonionic surfactant, Cationic and amphoteric surfactants can be used.

Between the emulsion layers of the light-sensitive material (same color-sensitive layer and / or different color-sensitive layer), the oxidant of the developing agent or the electron transfer agent moves to cause color turbidity, deterioration of sharpness, and graininess. An antifoggant can be used to prevent the property from being conspicuous.

The color antifoggant may be contained in the emulsion layer itself,
An intermediate layer may be provided between adjacent emulsion layers and contained in the intermediate layer.

An image stabilizer that prevents deterioration of a dye image can be used in the light-sensitive material. Compounds which can be preferably used are those described in RD17643, item VII J.

The hydrophilic colloid layers such as the protective layer and the intermediate layer of the photosensitive material may contain an ultraviolet absorber in order to prevent fogging due to discharge caused by charging of the photosensitive material due to friction and the like and to prevent deterioration of the image by ultraviolet rays. Good.

A formalin scavenger can be used in the light-sensitive material in order to prevent deterioration of the magenta dye-forming coupler and the like due to formalin during storage of the light-sensitive material.

When the hydrophilic colloid layer of the light-sensitive material contains a dye, an ultraviolet absorber or the like, they may be mordanted with a mordant such as a cationic polymer.

To the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material, a compound such as a development accelerator or a development retarder which changes the developability and a bleaching accelerator can be added. The compound which can be preferably used as the development accelerator is the compound described in Item XXI to D of RD17643, and the development retarder is 1
The compound is described in Item XXI, Item E of 7643. A black and white developing agent and / or its precursor may be used for the purpose of promoting development and other purposes.

The emulsion layer of the photographic light-sensitive material comprises a polyalkylene oxide or a derivative thereof such as an ether, ester or amine, a thioether compound, a thiomorpholine compound, a quaternary ammonium compound or a urethane derivative for the purpose of increasing sensitivity, increasing contrast or promoting development. It may include a urea derivative, an imidazole derivative and the like.

A fluorescent whitening agent can be used in the light-sensitive material for the purpose of emphasizing the whiteness of the white background and making the coloring of the white background inconspicuous. Compounds which can be preferably used as the fluorescent whitening agent are described in RD17643, item V.

The light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and an irradiation prevention layer. In these layers and / or in the emulsion layers, dyes which are bleached or bleached from the light-sensitive material during the development processing may be contained. Examples of such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes.

Improvement of low gloss of the light-sensitive material and writing property on the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material,
A matting agent can be added for the purpose of preventing sticking of the photosensitive materials to each other.

Any matting agent may be used, for example, silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, polymers of acrylic acid and methacrylic acid and their esters, polyvinyl resins, polycarbonate and styrene. And the copolymers thereof. The matting agent preferably has a particle size of 0.05 μ to 10 μ.
The amount to be added is preferably 1 to 300 mg / m ² .

A lubricant may be added to the light-sensitive material to reduce sliding friction.

An antistatic agent for the purpose of antistatic can be added to the light-sensitive material. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and may be a protective colloid layer other than the emulsion layer and / or the emulsion layer on the side of the support on which the emulsion layer is laminated. May be used for. Antistatic agents preferably used are the compounds described in RD17643 XIII.

For the photographic emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material, coating property improvement, antistatic property, slipperiness improvement, emulsion dispersion,
Various surfactants can be used for the purpose of preventing adhesion, improving photographic properties (acceleration of development, hardening, sensitization, etc.).

The support used in the light-sensitive material of the present invention includes an α-olefin polymer (for example, polyethylene, polypropylene,
Flexible reflective support such as paper laminated with ethylene / butene copolymer), synthetic paper, etc., semi-synthetic or synthetic polymer such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate and polyamide. And a flexible support in which a reflective layer is provided on these films, glass, metal, pottery, and the like.

The photosensitive material is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support, if necessary, and then directly or on the surface of the support, antistatic property, dimensional stability, abrasion resistance, hardness,
It may be applied via one or more subbing layers to improve antihalation properties, friction properties, and / or other properties.

At the time of applying the light-sensitive material, a thickener may be used to improve the coatability. For a hardener such as a hardener that causes gelation before coating when it is added to the coating solution in advance because it has a high reactivity, it is recommended to mix it with a static mixer or the like immediately before coating. preferable.

As the coating method, extrusion coating and curtain coating capable of simultaneously coating two or more layers are particularly useful, but packet coating is also used depending on the purpose. Further, the coating speed can be arbitrarily selected.

The surfactant is not particularly limited, and examples thereof include natural surfactants such as saponin, nonionic surfactants such as alkylene oxide-based, glycerin-based, glycidol-based, higher alkylamines, quaternary ammonyl salts, pyridine and the like. Heterocycles, cation surfactants such as phosphonium or sulfonium, carboxylic acids, sulfonic acids,
Anionic surfactants containing an acidic group such as phosphoric acid, sulfuric acid ester and phosphoric acid ester, and amphoteric surface active agents such as amino acids, aminosulfonic acids and sulfuric acid or phosphoric acid esters of amino alcohol may be added. Further, it is also possible to use a fluorine-based surfactant for the same purpose.

To obtain a dye image using the light-sensitive material of the present invention, after exposure,
Perform color photo processing. Color processing includes a color development processing step, a bleaching processing step, a fixing processing step, a water washing processing step and a stabilization processing step if necessary, but instead of a processing step using a bleaching solution and a processing step using a fixing solution. In addition, the bleach-fixing treatment step can be carried out using the 1-bath bleach-fixing solution, and the mono-bath processing step using the 1-bath development bleach-fixing solution capable of performing color development, bleaching and fixing in a single bath You can also do

In combination with these treatment steps, a pre-hardening treatment step, a neutralizing step thereof, a stop fixing treatment step, a post-hardening treatment step and the like may be performed. In these processes, instead of the color development processing step, a color developing agent, or a precursor thereof may be contained in the material, and an activator processing step in which the development processing is carried out with an activator solution may be performed, or an activator for the monobath processing. Treatments can be applied. Among these treatments, typical treatments are shown below (these treatments include the washing treatment step, the washing treatment step and the stabilizing treatment step as the final step).

Color development process-bleaching process-fixing process-Color development process-bleaching fixing process-Pre-hardening process-coloring development process-stop fixing process-washing process-bleaching process-fixing process Process-Washing process-Post-hardening process-Color development process-Water washing process-Supplemental color development process-Stopping process-Bleaching process-Fixing process-Activator process-Bleaching fixing process-Activation Beta treatment process-bleaching treatment process-fixing treatment process-monobath treatment process The treatment temperature is usually selected in the range of 10 ° C to 65 ° C, but 65 ° C.
The temperature may be higher than that. It is preferably treated at 25 ° C to 45 ° C.

The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, and includes aminophenol-based and p-phenylenediamine-based derivatives. These color developing agents can be used as salts of organic acids and inorganic acids, for example, salt acid, sulfate, p-toluenesulfonate, sulfite, oxalate, benzenesulfonate and the like. it can.

These compounds generally account for about 0.1 for Color Developer 1.
It is used in a concentration of -30 g, more preferably in a concentration of about 1-15 g for color developer 1. If the amount added is less than 0.1 g, sufficient color density cannot be obtained.

Examples of the aminophenol-based developer include o-aminophenol, p-aminophenol, 5-amino-
2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene and the like are included.

Particularly useful primary aromatic amine-based color developing agents are N, N-dialkyl-p-phenylenediamine-based compounds, in which the alkyl and phenyl groups may or may not be substituted. Among them, particularly useful compound examples are NN-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N, N-dimethyl-p-phenylenediamine hydrochloride,
2-amino-5- (N-ethyl-N-dodecylamino)
-Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N
-Ethyl-N-β-hydroxyethylaminoaniline,
4-amino-3-methyl-N, N-diethylaniline, 4
-Amino-N- (2-methoxyethyl) -N-ethyl-
Examples thereof include 3-methylaniline-p-toluenesulfonate.

The color developing agents may be used alone or in combination of two or more kinds. Furthermore, the color developing agent may be incorporated in a color photographic material. In this case, it is also possible to treat the silver halide color photographic light-sensitive material with an alkaline solution (activator solution) instead of the color developing solution,
After the alkaline solution treatment, a bleach-fixing treatment is carried out immediately.

The color developing solution used in the present invention may contain an alkaline agent usually used in a developing solution, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate or borax. And various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, or a development modifier such as citrazinic acid, and a preservative such as hydroxylamine or sulfite. You may. Further, various antifoaming agents and surfactants, and an organic solvent such as methanol, dimethylformamide or dimethylsulfoxide, etc. may be appropriately contained.

The pH of the color developer used in the present invention is usually 7 or higher, preferably about 9-13.

In the color developing solution used in the present invention, if necessary, diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, an aromatic secondary alcohol, hydroxamic acid, bentose or an antioxidant is used. Hexose, pyrogallol-1,3
-Dimethyl ether and the like may be contained.

In the color developing solution used in the present invention, various chelating agents can be used together as a sequestering agent. For example, as the chelating agent, an amine polycarboxylic acid such as ethylenediaminetetraacetic acid or diethylenetriaminopentaacetic acid, 1
-Organophosphonic acid such as hydroxyethylidene-1,1'-diphosphonic acid, aminopolyphosphonic acid such as aminotri (methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acid such as citric acid or gluconic acid, 2-phosphonobutane 1, Examples thereof include phosphonocarboxylic acid such as 2,4-tricarboxylic acid, polyphosphoric acid such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compound.

The bleaching process may be performed simultaneously with the fixing process as described above, or may be performed individually. As the bleaching agent, a metal complex salt of an organic acid is used, and for example, an organic acid such as polycarboxylic acid, aminopolycarboxylic acid or oxalic acid, citric acid, etc., in which metal ions such as iron, cobalt, copper are coordinated are used. . Among the above-mentioned organic acids, the most preferable organic acid includes polycarboxylic acid or aminopolycarboxylic acid. Specific examples of these include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β-oxyethyl) -N, N ′, N ′.
-Triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine citric acid (or tartaric acid), ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediamine Tetraacetic acid etc. can be mentioned.

These polycarboxylic acid alkali metal salts, ammonium salts or water-soluble amine salts may be used. These bleaching agents are used at 5-450 g /, more preferably 20-250 g /.

As the bleaching solution, in addition to the bleaching agent as described above, a solution having a composition containing sulfite as a preservative is applied if necessary.
Further, it may be a bleaching solution having a composition containing an ethylenediaminetetraacetic acid iron (III) complex salt bleaching agent and adding a large amount of a halide such as ammonium bromide. As the halide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may be used in addition to ammonium bromide. it can.

The bleaching solution used in the present invention includes JP-A-46-280, JP-B-45-8506, JP-A-46-556, and Belgian Patent No. 770,910.
No. 5, Japanese Patent Publication No. 45-8836, No. 53-9854, JP-A-54-7163
Various bleaching accelerators described in No. 4 and No. 49-42349 can be added.

The bleaching solution is used at a pH of 2.0 or higher, but generally 4.0 to 9.
Used in 5, preferably used in 4.5-8.0, most preferably 5.0-7.0.

The fixer may have a commonly used composition. As the fixing agent, a compound which reacts with silver halide to form a water-soluble complex salt as used in a usual fixing process, for example, thiosulfate such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, potassium thiocyanate. Typical examples thereof include thiocyanates such as sodium thiocyanate and ammonium thiocyanate, thiourea and thioether. Those fixatives are
It is used in an amount in which it can be dissolved at 5 g / or more, but is generally used at 70 to 250 g /. A part of the fixing agent can be contained in the bleaching tank, and conversely, a part of the bleaching agent can be contained in the fixing tank.

The bleaching solution and / or the fixing solution are various pH buffers such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide. The agents can be contained alone or in combination of two or more. Further, various fluorescent whitening agents, antifoaming agents or surfactants may be contained. Further, hydroxylamine, hydrazine, preservatives such as bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids or stabilizers such as nitroalcohol and nitrates, hardening agents such as water-soluble aluminum salts, methanol,
An organic solvent such as dimethyl sulfamide or dimethyl sulfoxide can be appropriately contained.

The fixer is used at a pH of 3.0 or above, but generally 4.5-10
Is used, preferably 5 to 9.5, and most preferably 6 to 9.

Examples of the bleaching agent used in the bleach-fixing solution include the metal complex salts of organic acids described in the bleaching treatment step, and preferable compounds and concentrations in the processing solution are the same as in the bleaching treatment step.

As the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the above-mentioned bleaching agent and, if necessary, a sulfite as a preservative is applied. Further, a bleach-fixing solution having a composition in which a small amount of an ethylenediaminetetraacetic acid iron (III) complex bleach and a halide such as ammonium bromide other than the above silver halide fixing agent are added in a small amount, or conversely, a halide such as ammonium bromide A bleach-fix solution composed of a large amount of iron, and further ethylenediaminetetraacetate iron (II
I) A special bleach-fixing solution having a composition comprising a combination of a complex salt bleaching agent and a large amount of a halide such as ammonium bromide can also be used. As the halide,
Hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide and the like can be used in addition to ammonium bromide.

Examples of the silver halide fixing agent that can be contained in the bleach-fixing agent include the fixing agents described in the fixing processing step. The concentration of the fixing agent and the pH buffering agent and other additives that can be contained in the bleach-fixing solution are the same as those in the fixing processing step.

The pH of the bleach-fix solution is 4.0 or higher, but it is generally 5.0.
~ 9.5, preferably 6.0-8.5, most preferably 6.5-8.5.

〔Example〕

Hereinafter, examples of the present invention will be shown.
It is not limited.

Example-1 A. Preparation of silver halide emulsion In a reaction kettle in which seed grains of silver halide and an aqueous gelatin solution have been charged in advance, while controlling pAg and pH in the reaction kettle, an aqueous ammoniacal silver nitrate solution and an iodine solution are controlled. Increasing the surface area during grain growth of an aqueous potassium bromide solution (1) and an aqueous potassium iodobromide solution (2-1) or an aqueous potassium bromide solution (2-2) having a lower potassium iodide content than the solution (1). Was added in proportion to the solution (2-1) or the solution (2-2) to the solution (1) at an appropriate particle size, and the solution was continuously added. Solution (2) for solution (1)
In some cases, the addition ratio of -1) or solution (2-2) was increased in two stages. Then, Kao Atlas's Demol N aqueous solution and magnesium sulfate aqueous solution were added, precipitation desalting was performed, and gelatin was added to pAg 7.8, pH 6.
An emulsion of 0 was obtained. Furthermore, sodium thiosulfate, metal chloride and ammonium rhodanate are added, and chemical aging is carried out.
4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 6-nitrobenzimidazole were added, and further gelatin was added to obtain a core / shell type silver iodobromide emulsion.

Here, the solution (1) and the solution (2-1) or the solution (2-
Solution (1) during silver halide grain growth by changing the addition ratio of 2) to change the mol% of silver iodide, and changing the addition amounts of ammoniacal silver nitrate and potassium halide to change the grain size. And solution (2-1)
Alternatively, the outermost grain thickness and the intermediate grain thickness are changed by changing the particle diameter when the addition ratio of the solution (2-2) is changed, and further, the crystal habit is changed by changing the pAg during the reaction, Core / shell type silver iodobromide emulsion samples EM-1-1 to EM-7-2 as shown in Table 1 were prepared.

It was found by electron microscope observation that each emulsion sample shown in Table 1 was a monodisperse emulsion having the average grain size and the variation coefficient of grain size distribution shown in the table.

B. Preparation of multilayer color photographic elements In all of the following examples, the addition amount in a silver halide photographic light-sensitive material is per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver.

A multilayer color photographic element test 1 was prepared by sequentially forming each layer having the composition shown below from the support side on a triacetyl cellulose film support.

Sample-1 (Comparison) First layer: Antihalation layer (HC-1) Gelatin layer containing black colloidal silver.

Second layer: intermediate layer (IL) A gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Third layer: low-sensitivity red-sensitive silver halide emulsion layer (RL-1) Silver halide emulsion (emulsion number EM1-1) ... Silver coating amount 1.8 g / m ² Sensitizing dye I ... with respect to 1 mol of silver 6 × 10 ⁻⁵ mol Sensitizing dye II …… 1.0 × 10 ⁻⁵ mol to 1 mol silver Cyan coupler (C-1) …… 0.06 mol to 1 mol silver Colored cyan coupler (CC-1) ... 0.003 mol per mol of silver Fourth layer: high-sensitivity red-sensitive silver halide emulsion layer (RH-1) Silver halide emulsion (emulsion number EM1-2) ... Silver coating amount 1.3 g / m ² sensitizing dye I: 3 × 10 ^-5 mol per 1 mol of silver Sensitizing dye II: 1.0 × 10 ^-5 mol per 1 mol of silver Cyan coupler (C-1): 0.02 mol per 1 mol of silver Colored cyan coupler (CC-1): 0.0015 mol per mol of silver Compound A (W-1) 0.01 mol per mol of silver Fifth layer; Intermediate layer (IL) Same as the second layer, Z Chin layer.

6th layer; low-density green-sensitive silver halide emulsion layer (GL-1) Emulsion number EM1-1 ... Coating amount of silver 1.5 g / m ² Sensitizing dye III: 2.5 × 10 ^-5 per mol of silver Molar Sensitizing Dye IV …… 1.2 × 10 ^-5 mol for 1 mol silver Magenta coupler (M-1) …… 0.050 mol for 1 mol silver Colored magenta coupler (CM-1) …… for 1 mol silver 0.009 mol 7th layer; high-sensitivity green-sensitive silver halide emulsion layer (GH-1) Emulsion number EM1-2 …… coated silver amount 1.4 g / m ² Sensitizing dye III …… 1.5 per mol silver × 10 ^-5 mol Sensitizing dye IV …… 1.0 × 10 ^-5 mol magenta coupler (M-1) for 1 mol of silver …… 0.020 mol color magenta coupler (CM-1) for 1 mol of silver …… 0.002 mol per mol of silver Compound A (W-1) 0.01 mol per mol of silver Eighth layer; Yellow filter layer (YC-1) Yellow colloidal silver and 2.5-di-t Gelatin layer containing emulsified dispersion of octyl hydroquinone.

Ninth layer: low-sensitivity blue-sensitive silver halide emulsion layer (BL-1) Monodisperse emulsion consisting of AgBrI containing 0.48 μm average grain size and 6 mol% AgI ... Silver coating amount 0.9 g / m ² Sensitizing dye V .... 1.3 × 10 ⁻⁵ mol to 1 mol of silver Yellow coupler (Y-1) ... 0.34 mol to 1 mol of silver 10th layer; high-sensitivity blue-sensitive emulsion layer (BH-1) Average particle size 0.8 μm, Monodisperse emulsion consisting of AgBrI containing 15 mol% AgI Silver coating amount 0.5 g / m ² Sensitizing dye V …… 1.0 × 10 ^-5 mol per 1 mol silver Yellow coupler (Y-1) …… 1 mol silver To 0.13 mol 11th layer; 1st protective layer (Pro-1) Silver iodobromide (AgI 1 mol% average particle size 0.07 μm) Silver coating amount 0.5 g / m ² UV absorber UV-1, UV-2 A gelatin layer containing.

Twelfth layer; Second protective layer (Pro-2) Gelatin layer containing polymethylmethacrylate particles (diameter 1.5 μm) and formalin scavenger (HS-1) Each layer contains a gelatin hardener (H −
1) (H-2) and a surfactant were added.

The compounds contained in each layer of Sample 1 are as follows.

Sensitizing dye I; anhydro 5,5'-dichloro-9-ethyl-
3,3'-Di- (3-sulfopropyl) thiacarbocyanine hydroxide Sensitizing dye II; Anhydro 9-ethyl-3,3'-di- (3-
Sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide Sensitizing dye III; Anhydro 5,5'-diphenyl-9-ethyl-3,3'-di- (3-sulfopropyl) Oxacarbocyanine hydroxide Sensitizing dye IV; Anhydro 9-ethyl-3,3'-di- (3-
Sulfopropyl) -5,6,5 ', 6'-dibenzooxacarbocyanine hydroxide Sensitizing dye V; Anhydro 3,3'-di- (3-sulfopropyl) -4,5-benzo-5'-methoxy Thiacyanin H-2 _{[(CH 2 = CHSO 2 CH 2} ) 3 CCH 2 SO 2 CH 2 CH 2 ] ₂ NCH ₂ CH ₂ SO ₃ H was prepared sample -1 Thus, the sixth layer and seventh
Sample-2 to Sample-12 were prepared by replacing the silver halide of the layer or by adding the compound of the present invention (the contents of the prepared samples are shown in Table 2).

Each sample thus obtained was left at 40 ° C. and 80% relative humidity for 3 weeks, then exposed to white light through a wedge by the usual method, and then the following development process was performed to measure the green density. did.

Treatment process (38 ℃) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying The composition of the treatment solution used in each processing step is as follows. Is the street.

[Color developer]

4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline ・ sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine ・ 1/2 sulfate 2.0g anhydrous potassium carbonate 37.5g sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 1.

[Bleaching solution]

Ethylenediaminetetraacetic acid iron ammonium salt 100.g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water to make 1 and adjust the pH to 6.0 with ammonia water.

[Fixing solution] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 and pH is adjusted to 6.0 using acetic acid.

[Stabilizer]

 Formalin (37% aqueous solution) 1.5 ml Conidax (Konishi Rokusha Kogyo Co., Ltd.) 7.5 ml Add water to make 1.

Next, the sensitivity, graininess, and sharpness of the color images formed on the above samples were measured. The results are shown in Table 3.

Here, the evaluation of the humidity resistance is a ratio of the relative sensitivity (Sp) of the green photosensitive layer of the sample which has been subjected to the treatment at 40 ° C. and the relative humidity of 80% for 3 weeks to the relative sensitivity (So) of the sample which has not been treated. Sp / S
o × 100 (%) was calculated. The closer the ratio is to 100 (%), the better the moisture resistance is.

Further, the graininess of the color image forming unit layer in the table is a measurement value when green exposure is given, and the graininess (RMS) is a density value generated when scanning with a microdensitometer having a circular scanning aperture of 2.5 μm. It is expressed as 1000 times the standard deviation of fluctuation.

Image sharpness is evaluated by MTF (Modulation Transfer Functio).
n) was calculated and the size of the MTF at a spatial frequency of 50 lines / mm was calculated.

As is clear from Table 3, the samples according to the present invention are clearly excellent in sensitivity, graininess, sharpness and moisture resistance.

Example-2 Samples 13 to 21 were prepared by changing the silver halides of the third and fourth layers or adding the compound of the present invention to the sample-1 of Example-1. The contents of the prepared samples are shown in Table 4.).

The sample thus obtained was allowed to stand in the same atmosphere as in Example-1 and then developed to measure the red density.

Further, the relative sensitivity, graininess, sharpness and moisture resistance were evaluated in the same manner as in Example-1 (however, in Example-2, the evaluation values were for the red photosensitive layer).

The results are shown in Table 5.

As is clear from Table 5, it is clear that the sample of the present invention is excellent in graininess, sharpness and moisture resistance.

Claims (1)

[Claims] 1. At least one light-sensitive silver halide emulsion layer on a support has therein a layer or phase having a silver iodide content of 6 to 40 mol%, and the silver iodide of the outermost surface layer. Content is 6 mol%
Less than the average silver iodide content of 4 to 20 mol% and containing a core / shell type silver halide grain, and a layer containing the silver halide grain and / or a color sensitivity different from that layer. Containing a diffusion resistant coupler that reacts with an oxidized form of a developing agent in combination with a silver halide emulsion layer having to form a dye, and further forms an unsharp positive image, reacts with an oxidized form of a developing agent, A colored compound which is appropriately diffused during development and has a main absorption in the main absorption wavelength range of the dye formed by the reaction of the diffusion resistant coupler with the oxidized product of the developing agent is present in the diffusion resistant coupler. Alternatively, a negative-type silver halide photographic light-sensitive material is contained in the adjacent layer.