JPS62206541A - Silver halide color photographic sensitive material with novel layer structure - Google Patents

Abstract

PURPOSE:To improve sharpness and graininess and to enhance image quality by forming >=2 silver halide color sensitive emulsion layers different in sensitivity, with higher sensitivity for a layer nearer to a support than for a farther layer, and containing silver halide grains each having a layer or a phase (core) high in silver iodide content. CONSTITUTION:The 2 or more color sensitive silver halide emulsion layers different in sensitivity are formed, and at least one of said layers nearer to the support is higher in sensitivity than the farther layer, but the layer structure is optional. For example, when said color sensitive emulsion layers are composed of 2 layers, the layer nearer to the support is higher in sensitivity. Said layers are composed of the 2 or more layers different in the silver iodide content, and the layer highest in the silver iodide content is the layer except the outermost surface layer. The highest silver iodide content of the core of each silver halide grain is, preferably, 6-40mol%, far preferably, 8-30mol%, especially, 10-20mol%. The silver iodide content of the outermost surface layer is, preferably, 0.5-6.0mol%, especially, 0.5-4.0mol%.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a silver halide color photographic material. In particular, regarding high-quality color photographic materials,
More specifically, the present invention relates to a silver halide color photographic material with excellent sharpness and improved graininess.

[Conventional technology]

Photosensitive materials have traditionally been required to have excellent image quality, and in particular recent color photographic materials are required to have high image quality. Furthermore, with the recent trend toward smaller formats of photosensitive materials, the issue of high image quality has become increasingly important. Particularly in the case of photographic materials for color negatives, for example, small formats are being promoted for portability and ease of photographing, but as a result, the photographing screen area becomes smaller and the deterioration of image quality becomes noticeable. Therefore, it has been desired to improve the image quality, especially the graininess and sharpness. In particular, deterioration in sharpness gives a blurred image and has a great impact on the quality of photographs, so improvements are required.

Various attempts have been made to prevent such deterioration of sharpness.

For example, there is a technology that uses dyes that are used in 8 m/m film for photography. This is done by placing a light-absorbing material, for example, immediately below the photosensitive layer, so that when the image that is focused on the film surface is exposed to the photosensitive material, the light will not be scattered and produce a blurred image. This is intended to prevent sharpness deterioration due to halation. However, this technique has the disadvantage that if a large amount of dye is used for the purpose of preventing light scattering, the sensitivity will be significantly lowered. In addition, this technology allows light that has passed through the photosensitive layer to
Alternatively, it only has the effect of reducing the blurring of light reflected and returned by silver halide grains on the side of the support from the photosensitive layer, but cannot prevent light scattering on the side of the light source from the photosensitive layer.

As a technique for preventing light scattering that occurs before reaching the photosensitive layer, Japanese Patent Laid-Open No. 53-37018 discloses a technique in which a green sensitive layer is positioned closest to the light source as a photosensitive layer, thereby improving sharpness. Are listed. However, with this technology, the green-sensitive layer naturally has a high sensitivity, that is, it has the same sensitivity to blue light as green light, so the blue light, which is originally absorbed by the yellow filter and should not be exposed to light, is The green-sensitive layer is also sensitive to light, and although sharpness is improved, color reproducibility is sacrificed.

As a technique to eliminate such drawbacks, Japanese Patent Application Laid-open No. 1983-
As described in No. 126531, there is a technique for controlling the particle size of silver halide grains that cause light scattering to minimize light scattering and reduce side effects such as desensitization.

However, although such technology has few drawbacks, the improvement effect is also not large. Conventional techniques have generally attempted to reduce light scattering by moving the green-sensitive layer, which has the greatest effect on vision, closer to the light source, based on the fact that visibility is greatest for green light. On the other hand, recent coating technology,
In particular, with the technology of coating thinly and uniformly at high speeds, it has become possible to produce thinner films than ever before, and together with the fact that they are free from serious defects such as desensitization, the recent development of This provides a large driving force to produce high-quality photosensitive materials.

With the advancement of manufacturing technology, the performance of high-quality photosensitive materials, especially the sharpness, has improved significantly, but due to the thinning of the film, the color developing agent generated in the photosensitive layer has become closer than before. This has become a problem as it diffuses into other layers and reacts with coloring couplers contained in other layers, deteriorating graininess or causing color turbidity. It is known that in the high-speed layer, since silver halide is present in -a in a large excess relative to the coupler, it diffuses into the low-speed layer located closer to the support, deteriorating the graininess.

On the other hand, although high image quality has been achieved by the conventional improvement means as described above, problems have arisen in terms of the physical strength of the photosensitive material.

In particular, as mentioned above, with the recent downsizing of photographic screen sizes (small format), even small defects become very noticeable when printed, and this has become a problem. .

In particular, pressure resistance is one of the properties strongly required for photosensitive materials for photography, in conjunction with the automation of photography cameras in recent years (for example, automatic winding), and its improvement is desired.

[Purpose of the invention]

The present invention solves the problems of the prior art described above, and provides a color photographic material that improves image quality by significantly improving sharpness and graininess, has high physical strength, and is less likely to cause pressure blur. The purpose is to

[Structure and operation of the invention]

The above object of the present invention is to have two or more silver halide emulsion layers having different color sensitivities on a support, and at least one of the emulsion layers is composed of two or more silver halide emulsion layers having different sensitivities. In the silver halide color photographic light-sensitive material, at least one emulsion layer having color sensitivity consisting of two or more silver halide emulsion layers having different sensitivities is such that at least one layer closer to the support is farthest from the support. and at least one of the color-sensitive layers contains silver halide grains having a layer or phase with a high silver iodide content. This can be achieved by using a silver halide color photographic light-sensitive material.

In the present invention, at least one of the color-sensitive emulsion layers is composed of two or more silver halide emulsion layers having different sensitivities, but such color-sensitive emulsion layers can be arbitrarily selected.

Only one of the two or more color-sensitive layers may be two layers as described above, or a plurality of them may be two layers, and the structure is arbitrary.

In the present invention, at least one of the color-sensitive emulsion layers consisting of two or more silver halide emulsion layers having different sensitivities is at least one of the silver halide emulsion layers closer to the support.
The layers are more sensitive than the more distant layers, but the layer configuration is arbitrary.

For example, when the color-sensitive emulsion layer consists of two layers, the layer closer to the support is the highly sensitive layer. Alternatively, a medium-sensitivity layer may be further provided, and a high-sensitivity layer, a medium-sensitivity layer, and a low-sensitivity layer may be arranged in this order from the support side. Two or more layers with different sensitivities,
It is sufficient that the layer farther from the support has a higher sensitivity than the layer farther from the support.

For example, in a typical color photographic light-sensitive material, a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are preferably formed sequentially from the support. The color photographic photosensitive layer of the present invention is composed of two or more different layers, and at least one of the two color-sensitive layers is configured such that the support is the more sensitive layer. For example, the red-sensitive layer may be a high-sensitivity layer and a 2N low-sensitivity layer, and the layer closer to the support may be the high-sensitivity layer. This is one of the preferred embodiments of the invention. In this case, a green-sensitive layer is provided on the side farther from the support than the red-sensitive layer, and this green-sensitive layer is also two layers, and the low-sensitivity layer of the green-sensitive layer is located closer to the support, and the red-sensitive layer is placed on the side farther from the support. The low-sensitivity layers of the green-sensitive layer and the green-sensitive layer can be arranged adjacent to each other (possibly with an intermediate layer interposed therebetween). Alternatively, as for the green-sensitive layer, the one closer to the support can be made into a high-sensitivity layer. Further, focusing on the green-sensitive layer, the one closer to the support can be made into a high-sensitivity layer, which is also a preferred embodiment of the present invention. The same can be done for the blue-sensitive layer.

In carrying out the present invention, the same color-sensitive layer may be a single layer, but two to three layers are preferable. Too many layers may affect sharpness in terms of film thickness.

High-sensitivity layer (H), medium-sensitivity layer (M), and low-sensitivity layer (L)
If N is provided, M from the support body.

The order can be H, L, H, M, L, or H, L, M.

As a specific example of a preferred layer structure, the support is BS, the high-sensitivity and low-sensitivity red-sensitive layers are RH and RL, and the high-sensitivity and low-sensitivity green-sensitive layers are GH and GL, high sensitivity.

Each low-sensitivity blue-sensitive layer is BH, BL, IL is the intermediate layer, and YC.
Assuming that 1 is a yellow filter layer and Pro is a protective layer, BS, IL, RH, and PL are sequentially formed from the support.

The layer structure can be IL, GL, GH, YC, BL, BH, and Pro. This layer consists of a red-sensitive layer and a green-sensitive layer, with the one closer to the support being the more sensitive layer. Similarly, BS, IL, RH.

RL, IL, GH, GL, YC, BL, Bl (, Pro
It can be made into a layered structure. This layer consists of a red-sensitive layer and a green-sensitive layer, with the one closer to the support being the more sensitive layer. Additionally, BS, IL, and RH.

The layer structure can be RL, IL, GH, GL, YC, BL, BH, and Pro. This is about the green sensitive layer.
The layer closer to the support is the highly sensitive layer. As a modification of this, a configuration may be provided in which [L is further provided between RL and RH. Also, BS, RH, IL, RL, IL
, G.H., Y.C., and B.

It can have a layer structure of YC, where B is one blue-sensitive layer, that is, in this layer structure example, there is one blue-sensitive layer. Also, BS, IC, RM, and RH.

RL, IL, G) I, GL, YC, BL, BH, Pro
Here, RM is a red-sensitive medium-sensitivity layer, that is, in this layer structure example, there are three red-sensitive layers, and the structure is arranged in the order of RM, RH, and RL from the support. It is something. Furthermore BS, IL, RH.

RL, IL, GM, GH, GL,
It can have a layer structure of VC, BL, BH, and Pro, where GM is a green-sensitive medium-sensitivity layer, that is, in this example, the green-sensitive layer has a three-layer structure.

In addition, the present invention can be embodied as a number of layer configurations by appropriately rearranging each of the above layer configurations.

In the light-sensitive material of the present invention, the sensitivity difference between the high-speed emulsion layer and the low-speed emulsion layer is 0.3 to 2. It is preferable to have a difference in OlogE. In addition, when providing a medium-sensitivity emulsion layer, the difference in sensitivity between the high-speed emulsion layer and the medium-speed emulsion layer and the difference between the medium-speed emulsion layer and the low-speed layer can be determined by a well-known method that takes into consideration gradation, etc. It can be calculated as 0.2 to 1.01, but generally
It is preferable to have a difference of 2 o g E (E: exposure charge).

In the light-sensitive material of the present invention, the color-sensitive layer containing the dye image-forming coupler has substantially the same color sensitivity, and at least one of the color-sensitive layers contains a plurality of halogens having different sensitivities. It suffices if the structure has a silver oxide emulsion layer. Here, "the color sensitivities are substantially the same" means, for example, any one of the blue region, green region, and red region among the spectral wavelength regions to which general color multilayer photosensitive materials can be sensitive. The above-mentioned photosensitivity also applies if the photosensitive regions are slightly different from each other in a certain wavelength range.

It is intended that the layers be considered to have substantially the same color sensitivity.

Note that it is preferable that photosensitive layers having the same color sensitivity are adjacent to each other without intervening photosensitive layers having different color sensitivity.

Further, it is preferable that such a non-photosensitive intermediate layer contains a scavenger substance or the like that reacts with the oxidized form of the developing agent to deactivate it.

The silver halide grains having a layer or phase with a high silver iodide content (hereinafter simply referred to as core/shell type silver halide grains) according to the present invention are two layers with different silver iodide contents. It has a grain structure composed of the above layers, and the layer with the highest silver iodide content (hereinafter referred to as the core) is other than the outermost layer (hereinafter referred to as the shell), It refers to silver halide grains consisting essentially of silver iodobromide in which the content of silver iodobromide in the outermost layer is less than 6 mol %.

The inner layer (core) having the highest silver iodide content preferably has a silver iodide content of 6 to 40 mol%, more preferably 8 to 30 mol%, more preferably 10 to 2 mol%.
It is 0%. The silver iodide content of the outermost layer is preferably 0.5 to 6 mol%, more preferably 0.5 to 4.0 mol%.

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

The core portion accounts for 10 to 80% of the entire particle.
%, more preferably 20 to 50%.

In the present invention, the content difference between the core portion with a high silver iodide content and the shell portion with a low silver iodide content of the silver halide grains may have a sharp boundary, or may have a continuous boundary that is not necessarily clear. It may be something that changes. Furthermore, those having an intermediate layer between the core and shell having a silver iodide content between those of the core and the shell are also preferably used, for example, from the viewpoint of improving graininess. When consisting of core/shell type silver halide grains having such an intermediate layer, the volume of the intermediate layer is preferably 5 to 60% of the total grain, and more preferably 2 to 60% of the total volume of the grain.
0 to 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 halide 8 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.

Such a core/shell type emulsion is disclosed in Japanese Patent Application Laid-Open No. 59-177.
535. 60-138538. 59-52238.
60-143331. 60-35726 and 60
It can be manufactured by a known method disclosed in JP-A-258536 and the like.

When a core/shell type silver halide emulsion is grown starting from seed grains as in the method described in the Examples of JP-A-60-138538, it is possible that the center of the grains has a halogen composition region different from that of the core. It's possible. In such a case,
The halogen composition of the seed grains is silver bromide, silver iodobromide, silver chloroiodobromide, and silver chlorobromide.

Silver iodobromide or silver bromide having a silver iodide content of 10 mol % or less is preferred, although silver chloride and other materials having any composition can be used.

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

The distribution state of silver iodide in the above-mentioned core/shell type silver halide grains can be detected by various physical measurement methods. This can be investigated by measuring luminescence at low temperatures, such as, or by X-ray diffraction.

In the present invention, the core/shell type halogen (? It is preferable that there be.

In the present invention, the silver halide emulsion used may be polydisperse or monodisperse. However, as mentioned above, it is preferable to use a monodispersed emulsion. Using monodisperse emulsions allows control of light scattering properties.

That is, the silver halide emulsion used in the present invention is preferably a monodisperse emulsion having a coefficient of variation in grain size distribution of 20% or less, and more preferably a coefficient of variation of 15% or less. This coefficient of variation is: Standard deviation coefficient of variation of particle size (%) = xio.

Average particle size It is defined as a measure of monodispersity.

The film thickness of the photosensitive material of the present invention is preferably 18 μm or less in terms of dry film thickness.

In addition, the thickness of each layer can be determined by enlarging the cross section of the dry sample with a scanning electron microscope and measuring the thickness of each layer.
You can know.

The upper and lower limits of the total dry film thickness of all hydrophilic colloid layers on the side having the emulsion layer (hereinafter referred to as the film thickness on the emulsion side) are determined by the silver halide emulsion, oil agents such as couplers, additives, and gelatin contained in the emulsion. There is a preferable range depending on the volume occupied by the binder. That is, the preferred film thickness on the emulsion side is 5 μm-18 μm.
m, more preferably 10 μm to 16 μm. Further, the distance from the outermost surface of the emulsion surface to the lower end of the emulsion layer closest to the support is preferably 14 μm or less, and the distance from the emulsion layer to the lower end of the emulsion layer next closest to the support is 10 μm, which has a different color sensitivity from the emulsion layer.
m or less is preferable.

Regarding the grain size of the silver halide grains in the emulsion layer, the average grain size of the silver halide grains in each high-sensitivity layer is 0.4 to 3.
．． 0μ, especially 0.7 to 2.5μ is good. When a medium-sensitivity layer is configured with three layers of the same color-sensitivity layer, the particle size is 0.5.
~1.5 μm is preferable, more preferably 0.5~1.5 μm.
2 μm is good.

On the other hand, the average grain size of the silver halide grains in each low luminous intensity layer is preferably 0.2 to 1.5 microns, particularly 0.2 to 1.0 microns.

Even if such silver halide grains are monodisperse,
Although it may be polydisperse, monodisperse is preferable from the viewpoint of improving graininess and sharpness.

Regarding the manufacturing method of emulsion layers having each of these color sensitivities.

There is no limit to this, and various arbitrary methods can be applied, for example, known methods can be adopted. Further, any protective colloid such as gelatin may be used as the protective colloid.

The amount of silver coated in each emulsion layer is preferably about 4 to 40 mg/dnf.

When a blue-sensitive layer is provided, it is preferable that the blue-sensitive layer contains fewer particles with a particle size of 0.3 to 0.5 μm in order to control light scattering.

The grain size of the silver halide grains mentioned above is defined as the length of one side of a cube having the same volume as the silver halide grains.

Next, in the practice of the present invention, benzoyl-type couplers can be preferably used, which can be used as yellow dye image-forming couplers when a blue-sensitive layer is provided to embody the present invention. As the benzoyl type coupler, a coupler represented by the following general formula (Y) can be preferably used.

Below is the general formula ('/) in which Rt, R'' and R3 may be the same or different,
Hydrogen atoms, halogen atoms (e.g. fluorine, chlorine, bromine, etc.), alkyl groups (e.g. methyl, ethyl,
(Allyl, dodecyl, etc.)

Aryl groups (e.g. phenyl, naphthyl, etc.).

Alkoxy groups (e.g., methoxy, ethoxy, dodecyloxy, etc.), acylamino groups (e.g., acetamide, α(p-dodecyloxyphenoxy)butanamide, etc.), carbamoyl groups (e.g., carbamoyl, N,
N-dimethylcarbamoyl, N-δ-(2,4-dit
ert-amylphenoxy), butylcarbamoyl, etc.), alkoxycarbonyl groups (e.g., ethoxycarbonyl, dodecyloxycarbonyl, α(dodecyloxycarbonyl)ethoxycarbonyl, etc.), sulfonamide groups (e.g., methanesulfonamide, p -dodecyloxybenzenesulfonamide, N-benzyldodecanesulfonamide, etc.), or sulfamoyl groups (e.g. sulfamoyl, N-methylsulfamoyl,
N-δ-(2,4-di-tert-amylphenoki,
c) Butylsulfamoyl lNlN-diethylsulfur 1
Each group such as Moyle etc.) is displayed.

R', R', R' and Rt may be the same or different, and each represents a hydrogen atom, an alkyl group (e.g. methyl, ethyl*jerj-butyl, etc.), an alkoxy group (e.g. methoxy, ethoxy, propoxy, etc.). .

octoxy, etc.), aryloxy groups (e.g., phenoxymethylphenoxy, etc.), acylamino groups (
For example, acetamide, α-,(2,,4-tar)
t-amylphenoxy)butanamide, etc.), or sulfonamide groups (for example, methanesulfonamide, do, p
-Dodecylbenzenesulfonamide.

N-benzuldodecanesulfonamide, etc.).

W is a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group (e.g., methyl, ethyl, tert-butyl, etc.), an alkoxy group (e.g., methoxy, ethoxy, propoxy, octoxy, etc.). ), aryloxy groups (e.g., phenoxy, methylphenoxy, etc. groups), or dialkylamino groups (
For example, dimethylamino, N-butyl-N-octylamino, etc.).

X represents a hydrogen atom or a releasable group. A preferable releasable group is represented by the general formula [Y'].

General formula [Y'] Y represents a group of nonmetallic atoms necessary to form a 5- to 6-membered ring (the cyclic compounds formed include, for example, 2.5-dioxo-imidacyline, 2.5-pyrrolidinedione , 1.3
-isoindoledione, 2.3.5-trioxo-imidazolidine, 2゜5-dioxo-triacylidine, 2
．． 4-oxazolidinedione, 2.4-thiazolidinedione, 2(IH)-pyridone, 2(LH)-pyrimidone, 2(IH)-pyrazone, 5(IH)-imidacylon, 5(4H)-)riazolone, 2( IH) -pyrimidone, 2-pyrazolone (5), 2-isothiazolone (5)
), 2(1)1)-quinaoxacylone, 4(3H)-pyrimidone, 2-benzoxacilone, 4-isoxacilone (5), 3-fluorone (21,4-imidacylone (
2), 3-pyrazolone, 2-tetra, zolone (5), 3
-representing each dielectric material such as tetrazolone (5), etc.) Below,
-J'lQ A specific example of a yellow coupler represented by the formula [Y] will be given below.

(Left below) (Y-3) (y-4) OH, i・ [Y-5] (Y-6) (Y-7) (Y-8) (Y-9) l [Y-1O] ( Y-12) 01N, 0 (Y-13) (Y-14) (Y-15) I Below margin In the present invention, silver halide grains in which a core-shell type monodisperse emulsion is doped with iridium have a pressure resistance It is highly effective in improving characteristics, and is also preferable in terms of improving failure characteristics under high illuminance.

The iridium salt or compound for this purpose preferably used in the present invention is not particularly limited, but the stability of the compound,
Industrially possible and preferable compounds in terms of safety and economy include halogenated iridium (I[I) compounds,
Halogenated iridium (IV) compounds, iridium complex salts having halogens, amines, oxalates, etc. as ligands, such as hexachloroiridium (III) or (IV) complex salts, hexaammineiridium (III)
) or (TV) complex salt, trioxalatoiridium (
III) or (IV) complex salts. Preferably, trivalent and tetravalent compounds can be used in any combination of these compounds. These iridium compounds are used after being dissolved in water or an appropriate solvent, but methods commonly used to stabilize solutions of iridium compounds include aqueous hydrogen halide solutions (e.g., hydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.). Or alkali halide
(For example, KCl.

A method of adding NaCl, KBr, NaBr, etc.) can be used.

In the present invention, the amount of the water-soluble iridium compound preferably used in preparing the silver halide emulsion is IX 10-'-I per mole of total silver halide finally formed.
X 10-' moles are suitable, preferably 1 x 1
0-' to 1 x 10-'r-le. halogenated t
l The amount of water-soluble iridium salt added per mol is lXl
When the amount is less than 0-'' mol, the effect may be insufficient, and when it is more than 1X10-' mol, the sensitivity may be extremely low and may be practically inferior.

The iridium salt or compound preferably used in the silver halide emulsion of the present invention may be added before the growth of the shell portion as long as 80% of the grain formation has been completed, but the iridium salt or compound preferably used in the silver halide emulsion of the present invention may be added before the growth of the shell portion. Preference is given to growing in the presence of salt. At this time, the iridium salt may be added at any point during shell growth, may be added in the entire area, may be added in parts, or may be added continuously. , e.g. added to the halide salt solution to grow the shell.

can be done.

The iridium salt or compound preferably used in the silver halide emulsion of the present invention is preferably not substantially present before 80% of the average grain size is formed. Substantially absent means that the coexisting iridium salt is less than 1X10-' mol per mol of the total silver halide emulsion formed. If this range is exceeded, not only the effect of improving pressure resistance characteristics and high-intensity reciprocity law failure characteristics by the iridium salt is small, but also desensitization may occur.

When doping iridium, the layer to which the iridium salt or compound is added is optional, but it is preferably added to the color-sensitive layer, and in the case of two or more color-sensitive layers with different sensitivities, it is preferable to add it to the high-sensitivity layer. , Among the high-sensitivity layers, there are green-sensitive layers and red-sensitive layers.

The effect of doping becomes greater in the order of blue-sensitive layers, and it is preferable to add them to silver halide grains contained in green-sensitive layers.

In the present invention, the method for producing the core/shell emulsion when iridium is added as described above or in other cases will be described below.

A silver halide emulsion having silver halide grains having a core/shell structure can be produced by covering a core of silver halide grains contained in a monodisperse emulsion with a shell. To form monodisperse silver halide grains as cores, grains of a desired size can be obtained by a double jet method while controlling pAg and pH. Further, for highly monodisperse silver halide emulsions, the method described in JP-A-54-48521 can be applied. In a preferred embodiment of the method, a potassium iodobromide-gelatin aqueous solution and an ammoniacal silver nitrate aqueous solution are added to a gelatin aqueous solution containing silver halide particles while changing the addition rate as a function of time. Manufacture. At this time, a highly monodisperse silver halide emulsion can be obtained by appropriately selecting the time function of addition rate, pH, pAg, temperature, etc. Gelatin is preferred as the binder used here, but gelatin derivatives and other polymeric hydrophilic colloids may also be used in combination.

(Silver halide solvent treatment) The silver halide emulsion used in the present invention can be grown in the presence of a known silver halide solvent (hereinafter referred to as solvent treatment).

Silver halide solvents that may be used in the present invention include (a
) U.S. Patent No. 3.271.157, U.S. Patent No. 3.531,
Organic thioethers described in JP-A-54-1019 and JP-A-54-158917, etc., (b) JP-A-54-158917, etc.;
No. 82408, No. 55-77737 and No. 55-29
Thiourea derivatives described in 829 publication etc., (c)
AgX solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319, (d) JP-A-54-100717
imidazoles, (e) sulfites, and
(f) Thiocyanate, (g) Ammonia, (h) Hydroxyalkyl-substituted ethylenediamines described in JP-A-57-196228, (i) JP-A-57-196228
Examples include substituted mercaptotetrazoles described in Japanese Patent No. 202531.

The following margin silver halide emulsions include silver halide used in ordinary silver halide emulsions such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide and silver chloride. Silver bromide, silver iodobromide, and silver chloroiodobromide are particularly preferred.

The silver halide grains used in the silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The grains may be grown all at once or after forming seed grains. You can let it grow. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Alternatively, while taking into account the critical growth rate of silver halide crystals, halide ions and silver ions may be added simultaneously and sequentially while controlling IIH and 9Ag in the mixing pot. This method allows crystals to be generated. Silver halide grains with a regular shape and nearly uniform grain size are obtained. Conversion methods may be used at any step in the formation of AgX to change the halogen composition of the particles.

Known silver halide solvents such as ammonia, thioether, thiourea, etc. can be present during the growth of silver halide grains.

In the process of forming and/or growing silver halide grains, cadmium salts such as those mentioned above, zinc salts, lead salts, thallium salts, iridium salts (including complex salts),
Metal ions can be added using at least one selected from rhodium salts (including complex salts) and iron salts (including IF salts) to contain these metal elements inside the particles and/or on the particle surfaces. Further, by placing the particles in an appropriate reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

The silver halide emulsion may be freed from unnecessary soluble salts after the growth of silver halide grains has finished, or may be left in the silver halide emulsion. D 1s
closure (hereinafter abbreviated as RD)) It can be carried out based on the method described in No. 17643, Section 3.

The silver halide grains used in combination may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside of the grain and the surface layer.

The silver halide grains may be such that the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain.

The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of the 1007 plane to the +1111 plane can be used.

Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The size of silver halide grains is 0.05 to 30, μ
, preferably 0.1 to 20μ.

Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). 1Ia, which has a value of 0.20 or less when divided by the average particle size, where the particle size follows the above definition, may be used alone or in a mixture of several types.

Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

Silver halide emulsions can be chemically sensitized by conventional methods. HrJ, a sulfur sensitization method, a selenium sensitization method, a reduction exacerbation method, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination.

Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. Aggravating pigments may be used alone, but 211 or more may be used in combination. Even if the emulsion contains a supersensitizer, which is a dye that itself does not have a spectral sensitizing effect along with the sensitizing dye, or a compound that does not substantially absorb visible light, but which strengthens the sensitizing effect of the sensitizing dye. good.

Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes and hemioxanol dyes are used.

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, photographs may be taken during chemical ripening, at the end of chemical ripening, and/or after chemical ripening and before coating a silver halide emulsion. Compounds known in the art as antifoggants or stabilizers can be added.

Binder (or protective colloid) for silver halide emulsions
Although it is advantageous to use gelatin, gelatin derivatives, graft polymers of gelatin and other polymers,
Hydrophilic colloids such as other proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

The photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention contains one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. It can be used to harden the membrane. Hardeners can harden photosensitive materials to the extent that there is no need to add hardeners to the processing solution! It is also possible to add a hardening agent to the processing solution.

For example, aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (1,3,5- triacryloyl-hexahydro-3-triazine, 1.
3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-
S-triazine, etc.), mucohalogens [1 (mucochloric acid, mucophenoxychloric acid, etc.), etc.] can be used alone or in combination.

A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility. Preferred plasticizers are A of Section X1 of RD17643.
It is a compound described in .

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 (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or these and acrylic acid, A polymer containing a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used.

The emulsion layer of the photosensitive material contains a dye-forming agent that forms a dye through a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, p-phenylenediamine derivatives, aminophenol derivatives, etc.) during color development processing. A coupler is used. The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler in the blue emulsion layer; A magenta dye-forming coupler is used in the green-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

It is desirable that these dye-forming couplers have a group called a ballast in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Zero dye formation can be either 4-equivalent, in which 100 silver ions need to be reduced, or 2-equivalent, in which only 2 molecules of silver ions need to be reduced.

Couplers include colored couplers that have a color correction effect, and by coupling with oxidized developing agents, development inhibitors, development accelerators, bleach accelerators, developers, halogenated solvents, toning agents, Included are compounds that release photographically useful fragments such as hardeners, fogging agents, anti-capri agents, chemical sensitizers, spectral sensitizers, and desensitizers.

Among these, couplers that release a development inhibitor during development and improve image sharpness and image graininess are called DIR couplers. In place of the DIR coupler, a DIR compound which undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used.

The DIR couplers and DIR compounds used include those with an inhibitor directly attached to the coupling position and those with an inhibitor attached to the coupling position.
An intramolecular nucleophilic reaction within the group that is bonded to the coupling position via a valent group and fied by the coupling reaction,
Included are those in which the inhibitor is bonded so as to be released by an intramolecular electron transfer reaction or the like (referred to as timing DIR couplers and timing DIR compounds). Furthermore, inhibitors that can be dispersed after release and those that are not so dispersible can be used alone or in combination depending on the purpose. A colorless coupler (also called a competitive coupler) which undergoes a coupling reaction with an oxidized aromatic primary amine developer but does not form a dye can also be used in combination with a dye-forming coupler.

As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used.

Among these, benzoylacetanilide-based and pivaloylacetanilide-based compounds are useful. Specific examples of yellow coloring couplers that can be used include, for example, U.S. Patent No. 2,87
No. 5,057, No. 3゜265.506, No. 3,4
No. 08.194, No. 3.551.155, No. 3,
No. 582.322, No. 3,725.072, No. 3
．． No. 891,445, West German Patent No. 1.547.8611
No. 1, West German Application No. 2.219.917, No. 2,2
61,361, British Patent No. 2414.006, British Patent No. 1,425.020, Japanese Patent Publication No. 1983-10783, Japanese Patent Publication No. 47-26133, Japanese Patent Publication No. 48-73147, British Patent No. 5
No. 0-6341, No. 50-87650, No. 50-12
No. 3342, No. 50-130442, No. 51-218
No. 27, No. 51-102636, No. 52-82424
No. 52-115219, No. 58-95346, etc.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indacylon couplers, and the like can be used.

Specific examples of magenta color-forming couplers that can be used include, for example, U.S. Pat.
No. 3,311゜476, No. 3.419,39
No. 1, No. 3,519.429, No. 3.558.3
No. 19, No. 3.582.322, No. 3.615.
No. 506, No. 3,834,908, No. 3,891
．． No. 445 - West German Patent No. 1,810.464, West German Patent Application (OLS) No. 2.408,665, OLS No. 2.4
No. 17,945, No. 2,418.959, No. 2.
No. 424,467, Special Publication No. 40-6031, Japanese Patent Publication No. 4
No. 9-74027, No. 49-74028, No. 49-1
No. 29538, No. 50-60233, No. 50-159
No. 336, No. 51-20826, No. 51-26541
Examples include those described in Japanese Patent Application No. 52-42121, No. 52-58922, No. 53-55122, and Japanese Patent Application No. 55-110943.

Phenol or naphthol couplers are commonly used as cyan dye-forming couplers. Specific examples of cyan color-forming couplers that can be used include, for example, U.S. Patent No. 2.42.
3.730, 2.474.293, 2.8
No. 01,171, No. 2.895,826, No. 3,
No. 476.563, No. 3,737,326, No. 3
．． No. 758.308, specification No. 3.893.044, JP-A-47-37425, JP-A No. 50-10135,
No. 50-25228, No. 50-112038, No. 5
Couplers described in Japanese Patent Application Publication No. 0-117422 and Japanese Patent Application Publication No. 5G-130441, and Japanese Patent Application Laid-open No. 58-98731 are preferred.

Dye-forming couplers, colored couplers, DIR couplers, DIR that do not need to be adsorbed on the silver halide crystal surface
compounds, image stabilizers, color antifoggants, ultraviolet absorbers,
Among fluorescent brighteners, hydrophobic compounds can be prepared using various methods such as solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. It can be selected as appropriate depending on the situation. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, and the boiling point is usually about 150°C.
Dissolve in the above high boiling point organic solvents in combination with low boiling point and/or water-soluble organic solvents as necessary, mix with a surfactant in a wood-friendly binder such as gelatin aqueous solution, and use a stirrer or homogenizer. , after emulsification and dispersion using a dispersion means such as a colloid mill, flow lift mixer, or ultrasonic device.

It may be added to the desired hydrophilic colloid liquid.

A step of removing the low-boiling organic solvent may be included simultaneously with the dispersion or dispersion.

Examples of high-boiling point solvents include phenol derivatives, phthalate alkyl esters, phosphate esters, citrate esters, benzoate esters, alkylamides, fatty acid esters, trimesate esters, etc., which do not react with the oxidized form of the developing agent, and have a boiling point of 150°C or higher. A solvent is used.

Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Organic solvents with low boiling points that are substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform,
Examples include carbon tetrachloride, nitromethane, nitroethane, and benzene.

When dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, fluorescent whitening agents, etc. have acid groups such as carboxylic acid or sulfonic acid, an alkaline aqueous solution is used. It can also be introduced into hydrophilic colloids as a hydrophilic colloid.

Anionic surfactants, nonionic surfactants, Cationic surfactants and amphoteric surfactants can be used.

The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsion layers of the light-sensitive material (between the same color-sensitive layers and/or between different color-sensitive layers), causing color turbidity or deterioration of sharpness.
A color anticapri agent can be used to prevent graininess from becoming noticeable.

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

An image stabilizer can be used in the photosensitive material to prevent deterioration of the dye image. Compounds that can be preferably used are those described in RD No. 17643, Section 2 J.

Hydrophilic colloid layers such as protective layers and intermediate layers of photosensitive materials may contain ultraviolet absorbers to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to ultraviolet rays. good.

In order to prevent deterioration of maze/dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in the light-sensitive material.

When dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer of a photosensitive material, they may be mordanted with a mordant such as a cationic polymer.

Compounds that change the developability, such as development accelerators and development retarders, and bleaching accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layers of the light-sensitive material. A compound that can be preferably used as a development accelerator is RD 1
The compound is a compound described in Section XXI B to D of No. 7643, and the development retardant is a compound described in Section XXI E of No. 17643. A black and white developing agent and/or its precursor may be used to accelerate development or for other purposes.

The emulsion layer of a photographic light-sensitive material is made of polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium compounds, urethane derivatives, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also contain urea derivatives, imidazole derivatives, and the like.

A fluorescent whitening agent can be used in the photosensitive material for the purpose of emphasizing the whiteness of the white background and making the coloration of the white background less noticeable. Compounds that can be preferably used as fluorescent brighteners are described in section V of RD 17643.

The photosensitive material can be provided with auxiliary layers such as a filter layer, a haley silane prevention layer, an irradiation prevention layer, and the like. These layers and/or the emulsion layer may contain dyes that are washed out of the light-sensitive material or bleached during the development process.

Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like.

A matting agent can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of reducing the gloss of the light-sensitive material, improving the ease of writing, and preventing the light-sensitive materials from sticking together. Any matting agent can be used, but examples include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, polymers of acrylic acid and methacrylic acid and their esters, polyvinyl resin, polycarbonate, and styrene. and copolymers thereof. The particle size of the matting agent is preferably 0.05 .mu.m to 10 .mu.m, and the amount added is preferably 1 to 300 mmg/nl.

A lubricant can be added to the photosensitive material in order to reduce slippage 1ffff.

An antistatic agent can be added to the photosensitive material for the purpose of preventing static electricity. 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 used as a protective colloid in the emulsion layer other than the emulsion layer on the side where the emulsion layer is MI layered with respect to the emulsion layer and/or the support. It may be used in layers. Preferably used antistatic agents are the compounds described in RD 17643 x■.

The photographic layer and/or other hydrophilic colloid layer of the light-sensitive material has properties such as improving coating properties, preventing static electricity, improving slipperiness, emulsification and dispersion, preventing adhesion, and photographic properties (development acceleration, hardening, sensitization, etc.). Various surfactants can be used for the purpose of improvement.

The support used in the photosensitive material of the present invention includes α-olefin polymers (e.g. polyethylene, polypropylene,
Flexible reflective supports such as paper laminated with ethylene/butene copolymer), synthetic paper, etc., semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene phthalate, polycarbonate, polyamide, etc. These include films made of , flexible supports made of these films with reflective layers, glass, metals, ceramics, etc.

After subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, the photosensitive material can be used directly or to improve the adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, etc. of the support surface. It may be applied through one or more subbing layers to improve antihalation properties, frictional properties, and/or other properties.

When coating the photosensitive material, a thickener may be used to improve coating properties. Also, for things like hardeners, which are so reactive that if added to the coating solution in advance, they will gel before coating, it is best to mix them using a static mixer or the like just before coating. preferable.

As a coating method, extrusion coating and curtain coating, which allow two or more types of layers to be applied simultaneously, are particularly useful, but depending on the purpose, basket coating may also be used. Further, the coating speed can be arbitrarily selected.

Examples of surfactants include, but are not limited to, natural surfactants such as saponin, nonionic surfactants such as alkylene oxide, glycerin, and dalicidol, higher alkylamines, quaternary ammonium salts, pyridine, and others. Cationic surfactants such as heterocycles, phosphoniums or sulfoniums, carboxylic acids, sulfonic acids,
Anionic surfactants containing acidic groups such as phosphoric acid, sulfuric acid esters, and phosphoric acid esters; amphoteric surfactants such as amino acids, aminosulfonic acids, and sulfuric acid or phosphoric acid esters of amino alcohols may be added.

Moreover, it is also possible to use a fluorine-based surfactant for the same purpose.

In order to obtain a dye image using the photosensitive material of the present invention, after exposure, color photographic processing is performed. However, instead of the process using a bleach solution and the process using a fixer, a bleach-fixing process can be performed using a one-bath bleach-fix solution, and color development, bleaching, etc. It is also possible to carry out a monobath processing step using a one-bath development, bleach-fixing processing solution in which fixing can be carried out in one bath.

In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed.In these processes, a color developing agent, or An activator treatment step may be performed in which the precursor is contained in the material and the development treatment is performed using an activator solution, or a seven-activator treatment may be applied to the monobath treatment. Typical treatments during these treatments are shown below.
Bleaching process Fixed fixing process/Color development process - Bleach-fixing process/Pre-hardening process - Color developing process - Stop fixing process - Water washing process - Bleaching process Constant fixing process - Washing process - Post-hardening process/Color development process - Water washing process - Supplementary color development process - Stop process - Bleach process Constant fixation process/Activator process - Bleach-fix process/Activator process - Bleaching process Constant fixation process/monobath process The treatment temperature is usually selected in the range of 10°C to 65°C,
The temperature may exceed 65°C. Preferably from 25°C
Processed at 45°C.

The color developing agent is generally an alkaline aqueous solution containing a color developing agent.The color developing agent is an aromatic primary amine color developing agent, and includes aminophenol derivatives and p-phenylezine amine derivatives. These color developing agents can be used as salts of organic acids and inorganic acids; for example, hydrochloric acid, sulfate, p-toluenesulfonate, sulfite, oxalate, benzenesulfonate, etc. can be used. can.

These compounds generally have a concentration of about 0.0% in color developer 1z.
A concentration of 1 to 30 g, more preferably a color developer lIl
It is used at a concentration of about 1 to 15 g. If the amount added is less than 0.1 g, sufficient color density cannot be obtained.

Examples of the aminophenol-based developer include 0-aminophenol, p-aminophenol, 5-aminophenol,
Included are 2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene, and the like.

Particularly useful primary aromatic amine color developers include N, N-
A dialkyl-p-phenylenediamine compound,
The alkyl group and phenyl group may be substituted or unsubstituted, and examples of particularly useful compounds include N.

N-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-amino Aniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N,N-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3 −
Examples include methylaniline-1)-) luenesulfonate.

Further, the above color developing agents may be used alone or in combination of two or more kinds.Furthermore, the above color developing agents may be incorporated into the 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 a color developing solution, and the bleach-fixing process is carried out immediately after the alkaline solution treatment.

The color developing solution used in the present invention may contain alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. It also contains various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, development regulators such as citrazic acid, and preservatives such as hydroxylamine or sulfites. You may.

Furthermore, various antifoaming agents and surfactants, and alkaline solvents such as methanol, dimethylformamide or dimethyl sulfoxide, etc. can be appropriately contained.

p) of the color developing solution used in the present invention is usually 7 or more, preferably about 9 to 13.

In addition, the color developing solution used in the present invention may contain antioxidants such as diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, pentose, or hexose, pyrogallol-1,
3-dimethyl ether etc. may be contained.

In the color developing solution used in the present invention, various chelating agents can be used in combination as metal ion sequestering agents. ,■
-Hydroxyethylidene-1, Organic phosphonic acids such as 1'-diphosphonic acid, aminotri(methylenephosphonic acid)
or aminopolyphosphonic acid such as ethylenediaminetetraphosphoric acid, oxycarboxylic acid such as citric acid or gluconic acid, phosphonocarboxylic acid such as 2-phosphonobutane or 1,2,4-tricarboxylic acid, polyphosphoric acid such as tripolyphosphoric acid or hexametaphosphoric acid. etc., polyhydroxy compounds, etc.

The bleaching process may be performed simultaneously with the fixing process as described above, or may be performed separately.

As a bleaching agent, a metal complex salt of an organic acid is used, such as a polycarboxylic acid, an aminopolycarboxylic acid, or an organic acid such as oxalic acid or citric acid coordinated with a metal ion such as iron, cobalt, or copper. .

Among the above organic acids, the most preferred organic acids include polycarboxylic acids and aminopolycarboxylic acids. Specific examples of these include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, and iminodiacetic acid. ,
Dihydroxyethylglycine citric acid (or tartaric acid),
Examples include ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediaminetetrapropionic acid, and phenylenediaminetetraacetic acid. These polycarboxylic acids are alkali metal salts,
It may be an ammonium salt or a water-soluble amine salt. These bleaching agents are used in amounts of 5 to 450 g/l, more preferably 20 to 250 g/l.

In addition to the above bleaching agent, the bleaching solution may contain a sulfite as a preservative, if necessary. Alternatively, it may be a bleaching solution containing ethylenediaminetetate, iron (Il+) cerate complex salt bleaching agent, and a large amount of a halide such as ammonium bromide. In addition, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, and the like can also be used.

The bleaching solution used in the present invention includes JP-A No. 46-280, JP-B No. 45-8506, JP-B No. 46-556, Belgian Patent No. 770,910, JP-A No. 45-8836,
Various bleach accelerators described in JP-A-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added.

The pH of the bleaching solution used is 2.0 or higher, but generally it is 4.
．． It is used between 0 and 9.5, preferably between 4.5 and 8.0, and most preferably between 5.0 and 7.0.

A fixer having a commonly used composition can be used. As a fixing agent, a compound that reacts with silver halide to form a water-soluble complex salt, such as a thiosulfate such as potassium thiosulfate, sodium thiosulfate, or ammonium thiosulfate, or potassium thiocyanate, which is used in ordinary fixing processing, may be used. Typical examples thereof include thiocyanates such as sodium thiocyanate and ammonium thiocyanate, thiourea, and thioether. These fixatives are 5
It is used in an amount of 70 to 250 g/a or more, but it is generally used in an amount of 70 to 250 g/a.

Incidentally, a part of the fixing agent can be contained in the bleaching tank, or conversely, a part of the bleaching agent can also be contained in the fixing tank.

The bleaching solution and/or fixing solution may contain various pH 1L 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. These agents may be contained alone or in combination of two or more. Furthermore, various fluorescent whitening agents, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and nitrates, and hardening agents such as water-soluble aluminum salts. , methanol, dimethylsulfamide, dimethylsulfoxide, and other organic solvents may be appropriately contained.

The pl of the fixer is used at 3.0 or more, but -a is used at 4.5 to 10, 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 above bleaching process, and preferred compounds and concentrations in the processing solution are also the same as in the above bleaching process.

The bleach-fixing solution contains a silver halide fixing agent in addition to the above bleaching agent, and if necessary, a sulfite salt as a preservative. Also, a bleach-fix solution consisting of an ethylenediaminetetraacetate iron (11) lft salt bleach and a small amount of a halide such as ammonium bromide other than the above-mentioned silver halide fixer, or conversely, a halide such as ammonium bromide. A bleach-fix solution containing a large amount of iron ethylenediaminetetraacetate (iron ethylenediaminetetraacetate)
A special bleach-fix solution having a composition consisting of a combination of an I[t)if salt bleach and a large amount of a halide such as ammonium bromide can also be used. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can.

Examples of the silver halide fixing agent that can be included in the bleach-fixing solution include the fixing agents described in the above fixing process. 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 in the fixing process described above.

The bleach-fix solution is used at a pH of 4.0 or higher, but is generally used at a pH of 5.0 to 9.5, preferably 6.0 to 8.
5, most preferably 6.5 to 8.5.

The following is a margin [Examples] Examples of the present invention are shown below, but the present invention is not limited thereto.

First, the preparation of a silver halide emulsion will be explained, and then samples according to examples of the present invention using the same will be explained together with comparative examples.

(Preparation of silver halide emulsion) Into a reaction vessel, seed particles of silver halide and an aqueous gelatin solution were charged in advance, and while controlling the pAg and pH in the reaction vessel, an ammoniacal silver nitrate aqueous solution and a potassium iodobromide aqueous solution ( 11 and potassium iodobromide aqueous solution (2-1) or potassium bromide aqueous solution (2-2), which has a lower potassium iodide content than solution (1), are added in proportion to the increase in surface area during grain growth. , the addition ratio of solution (2-1) or solution (2-2) to solution (1) was increased at an appropriate particle size, and the addition was continued.
2-1) or the increase in the addition ratio of solution (2-2)
Some were done in stages. Next, a Kao Atlas Demol N aqueous solution and a magnesium sulfate aqueous solution were added to perform precipitation desalting, gelatin was added, and pA g7.
8, I) An emulsion of H6,O was obtained. Furthermore, sodium thiosulfate, chloroauric acid, and ammonium rhodanate were added for chemical ripening, resulting in 4-hydroxy-6-methyl-1,
3,3a,? -Tetrazaindene and 6-nidropenzimidazole were added, and gelatin was further added to obtain a core/shell type silver iodobromide emulsion.

Here, solution (11 and solution (2-1) or solution (2-
By changing the addition ratio of 2), the silver iodide mol% was changed, and by changing the addition amounts of ammoniacal silver nitrate and potassium halide, the grain size was changed. By changing the particle size when changing the addition ratio of solution (2-1) or solution (2-2), the outermost shell thickness and middle shell thickness can be changed, and furthermore, the pAg during the reaction can be changed. By changing the crystal habit by changing the crystal habit, and further adding water-soluble iridium salts shown in Table 1 during the growth of the outermost shell, core/shell type silver iodobromide emulsion samples EM-1-- as shown in Table 1 were prepared. Eight rounds of EM=5-2 were produced.

Each of the emulsion samples shown in Table 1 was found to be an emulsion having the average grain size and coefficient of variation of grain size distribution shown in the table by electron microscopy.

The following margin (sample preparation and evaluation) The preparation of the sample, etc. will be described below. In all the examples below, the amount added to the silver halide photographic light-sensitive material is based on 11 parts unless otherwise specified. In addition, silver halide and colloidal silver are shown in terms of silver.

Multilayer color photographic element sample 1 was prepared by sequentially forming layers having the compositions shown below on a triacetyl cellulose film support from the support side.

Sample-1 (comparison) First layer; antihalation layer (HC-1) Gelatin layer containing black colloidal silver.

Second layer: Intermediate layer (■) Gelatin layer containing an emulsified dispersion of 2.5-di-t-octylhydroquinone.

Third layer; low sensitivity red-sensitive silver halide emulsion JiJ (RL
-1) Average particle size (r) 0.33 μm, 8 gI 5.
A polydisperse emulsion consisting of AgBr1 containing 7 mol % (emulsion 1
-1)...Silver coating amount 1.8g/sensitizing dye ■...6 x 10-' moles per 1 mole of silver Sensitizing dye ■...... per 1 mole of silver 1.0X10-5 molar cyan coupler (C-1)...0.06 mol per 1 mol of silver Colored cyan coupler (CC-1)...i per 1 mol of silver 0.003 mol DIR compound (D-1) 0.003 mol per mol of SN 4th layer: High sensitivity red-sensitive silver halide emulsion [(RH-1)
Average particle size (r) 0.60. A polydisperse emulsion consisting of AgBr1 containing u m, 8 gl s, 7 mol % (emulsion 1-2
)...Amount of silver applied 1.5g/Aggravating pigment! ...... 3X10-' moles of sensitizing dye per mole of silver■...1. OX 10-'Morsian coupler (C-1) 0.01 per mol of i
8 mole colored cyan coupler (CC-1)...Silver 1
0.0015 mol to mol DIR compound (D-1)... 0.001 mol to 111 mol 5th layer; Intermediate layer (■ Le,) Same as the second layer, gelatin layer.

6th layer; low-range glaucoma silver halide emulsion layer (GL-1)
Emulsion-1-1... Coated silver amount 1.8g/nf
Sensitizing dye ■... 2.5 x 10-' mol per 111 mol Sensitizing dye ■... ≦1.2 x 1 O-S-I per 1 mol: J remagenta coupler (M-1)...O per mole of silver
, oso mole colored magenta coupler (CM-1)...1
! 0.009 mol to 1 mol DIR compound (D-1) 0.0040 mol to 1 mol silver 7th layer; High-sensitivity green-sensitive silver halide emulsion layer (Gll-1)
) Emulsion-1-2... Coated silver ft1.4g/
rr? Sensitizing dye ■... 1.5 x 10-' mol sensitizing dye ■ per 1 mole of silver
・・・・・・ 1 mole of 8 carp. OX 10-' mole magenta coupler (M-1)...0.0 per mole of silver
20 molar colored magenta coupler (CM-1)...
8th layer: 0.002 mol per mol of primate; Yellow Filter Ji! (VC-1) A gelatin layer containing yellow colloidal silver and an emulsified dispersion of 2,5-di-t-octylhydroquinone.

9th layer: Low-speed blue-sensitive silver halide emulsion layer (BL-1
) A polydisperse emulsion (emulsion 1-2) consisting of AgBr1 with an average grain size of 0.33 μm and containing 5.7 mol% of AgI...
Silver coating amount: 0.9 g/m Sensitizing dye ■... 1.3 x 10-' Morle Yellow Coupler (EY-1) 1 mole per 1 mole 0.15 mole to mole 10th layer: Highly sensitive blue-sensitive emulsion layer (B11-1) Polydispersed emulsion (emulsion ■) consisting of AgBrI with an average grain size of 0.60 μm and containing 9 mol% of Agl (emulsion ■)...Silver Coating amount 0.5g/
n (sensitizing dye ■... 1.0 x 10-' mol per 1 mol of silver Yellow cuff puller (Y-1)... 0 per 1 mol of silver
．． 08 mol DIR compound (D-1) 0.0020 mol per 811 mol 11N; First protective layer (Pro-1) Silver iodobromide (Ag
r 1 mol% average particle size 0.07 μm) Silver coatingff10.
2g/n (gelatin layer containing ultraviolet absorbers UV-1 and UV-2.

12th layer; second protective layer (Pro-2) Gelatin layer containing polymethyl methacrylate particles (1.5 μm in diameter) and formalin scavenger (H5-1).

In addition to the above composition, each layer contains a gelatin hardener (H-1
) and surfactants 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 ■; anhydro 9-ethyl-3,3f-di(
3-sulfopropyl)-4,5,4'.

51-dibenzothiacarbocyanine hydroxide tw color sensitive im; anhydro 5,5°-diphenyl-9
-ethyl-3,3'-di(3-sulfopropyl)oxacarbocyanine hydroxide sensitizing dye■; anhydro9-ethyl-3,3'-di(
3-sulfopropyl)-5,6,5'.

61-dibenzoxacarbocyanine hydroxide sensitizing dye ■; Anhydro 3.39-di(3-sulfopropyl)-4,5-benzo-51-methoxythiacyanine Below margin = ;>
Σ(5)
Country Q Explosive country t-C5H+ l UV-1 I UV-2 S-1 Na Next, as shown in Table 2, samples 2 to 10 were created by changing the layer structure, emulsion, coupler, etc. . Table 2 also describes Sample 1.

In Table-2, B■-1 to 5. BL-1~5. G11l~5
゜GLI~5. RH-1 to 3. RL-1 to RL-3 specify the material of each layer by changing the emulsion and the coupler used, and the contents are shown in Table 3. Further, the emulsion numbers in Table 3 indicate the contents of the emulsions as described above. In Table 1, layers using core/shell emulsions are marked with Δ, layers using monodisperse emulsions are marked with *, and layers doped with iridium are marked with *. Ta.

Samples 4 to 13 have layer structures and emulsions used that meet the requirements of the present invention, and are samples for implementing the present invention. Samples 4 and 13 have a structure in which the high-sensitivity layer of the green-sensitive layer is located closer to the support, and samples 8 to 13 have a structure in which the high-sensitivity layer of the green-sensitive layer is also located closer to the support. There is. In Sample 7, the green-sensitive layer was made of a monodispersed emulsion, in Sample 8, the red-sensitive layer was also made of a Ton dispersed emulsion, and in Samples 9 to 13, all the color-sensitive layers were made of a monodispersed emulsion.

The green-sensitive layer of sample 10 is doped with iridium, and in samples 11 to 13, all the color-sensitive layers are doped with iridium. Among these, Samples 12 and 13 use a benzoyl-based yellow coupler as the yellow coupler. (See above for the emulsions of each sample, and see Table 3 for the couplers).

Margin below ・°:″.

:'-1 Table 3 Material composition of each layer Samples 1 to 13 thus obtained were processed using a testing machine that bent them at an angle of 165 degrees with the emulsion side facing outward.

Separately, Samples 1 to 13 were exposed to white light and subjected to the following development treatment.

Processing process (38℃) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Fixing
Wash with water for 6 minutes and 30 seconds
Stabilization for 3 minutes and 15 seconds Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

Color developer> 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate
4.75 g anhydrous sodium sulfite
4.25g Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37
．． 5 g Sodium Bromide 1.3
g Nitrilotriacetic acid trisodium salt (l hydrate) 2.5 g
Potassium hydroxide 1.0g Add water to make 11.

(Bleach solution) Ethylenediaminetetraacetic acid iron ammonium salt 100. g Ethylenediaminetetraacetic acid 2 ammonium salt 10. OJ ammonium bromide 150.0 g glacial acetic acid 10.0 IIIl Add water to make up to 1 liter, and adjust the pH to 6.0 using aqueous ammonia.

<Fixer> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water and 1!
! Close and adjust pH to 6.0 using acetic acid.

Stabilizer> Formalin (37% aqueous solution) 1.5m
J Conidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5mj
! Add water to make 11.

Blue light (B) for each sample obtained, respectively.

Using green light (G) and red light (R), sharpness (MTF)
) and RMS were measured.

The sharpness improvement effect is due to the M T F (Modu) of the dye image.
la-tion Transfer Function
), and the relative value of MTF at 50 bottles/drinking (sample IVk
(Ll is 100).

Graininess was also evaluated using the RMS value, which was expressed as 1000 times the standard deviation of the density value produced when scanning the minimum density + 1.2 with a microdecitometer having an aperture scanning area of 250 μd.

The above measurement results are shown in Table-4.

Further, each sample was processed using a testing machine that bends it at 165 degrees and then developed.The yellow pressure fog that occurred at the folded portion of each sample was filtered using a blue filter, the magenta pressure fog was filtered using a green filter, and the cyan pressure fog was filtered using a blue filter. It was measured using a densitometer through a red filter. Table the results.
4.

Here, ΔDl+ΔDGI ΔDR represents the value obtained by subtracting the fog of the unfolded portion from the maximum density of the folded portion.

The smaller this value is, the smaller the pressure build-up is, which is preferable.

As is clear from Table 4 below, the samples according to the present invention each have excellent properties.

Samples 1 to 3, which are comparative samples, have a high-sensitivity layer closer to the support for the green-sensitive layer (Samples 1 and 3), or use a core/shell emulsion in the high-sensitivity layer (Sample 2.
3) However, although the MTF and RMS of the layer are slightly improved by the combination of each individual technique, the effect is not large and the pressure fog is not improved. However, the green-sensitive layer is the layer structure of the present invention, and the high-sensitivity layer is the core layer of the present invention.
Regarding Sample 4 (sample of the present invention), which is a shell emulsion, MTF and RMS are also improved, and the effect of improving pressure blur is significant. Moreover, if a core/shell emulsion is used in both the high-sensitivity and low-sensitivity layers of the green-sensitive layer as in Sample 5, the effect will be even greater. In sample 6, good results were obtained using emulsion 3 (a triple core/shell emulsion with an AgI content within a preferable range). Furthermore, when a monodisperse emulsion is used as in sample 7, the effect is great. As described above, using a monodisperse emulsion in the green-sensitive layer has a great effect, but the effect can be even greater by using a monodisperse core/shell emulsion in the red-sensitive high- and low-sensitivity layers as in sample 8. If the entire layer is made of such an emulsion as in Sample 9, the effect will be even greater. Sample 10
The effect was further enhanced by doping iridium into the emulsion of the green-sensitive layer. In Sample 11, the emulsions of the red-sensitive layer and the blue-sensitive layer were also doped with iridium to obtain an even greater effect. Furthermore, samples 12.13 used a benzoyl-based yellow coupler in the blue-sensitive layer and obtained even better results.

〔Effect of the invention〕

As described above, according to the present invention, it is possible to provide a silver halide color photographic light-sensitive material which has great physical strength, such as greatly improved sharpness and graininess, and can suppress pressure blurring.

Claims (1)

[Claims] 1. Two or more silver halide emulsion layers having different color sensitivities on a support, and at least one of the emulsion layers has two or more silver halide emulsion layers having different sensitivities. In the silver halide color photographic light-sensitive material consisting of at least one color-sensitive emulsion layer consisting of two or more silver halide emulsion layers having different sensitivities, at least one layer closer to the support is farthest from the support. and at least one of the color-sensitive layers contains silver halide grains having a layer or phase with a high silver iodide content. A silver halide photographic material with a novel layer structure.