JPS62206543A - Silver halide color photographic sensitive material with novel layer structure - Google Patents

Abstract

PURPOSE:To improve both of sharpness and graininess by forming >=2 color sensitive silver halide emulsion layers different in sensitivity, with higher sensitivity for a layer nearer to a support than for a farther layer, and incorporating in a photosensitive material a compound capable of releasing a diffusive development inhibitor at the time of development. CONSTITUTION:The 2 or more color sensitive silver halide emulsion layers different in sensitivity are formed, and at least one of these layers nearer to the support is higher in sensitivity than the farther layer, and the photosensitive material contains the compound capable of releasing the diffusive development inhibitor (DDI) at the time of development. Said diffusive DIR (development inhibitor releasing) compd. is shown by the formula. A DIR compd. capable of releasing a nondiffusive development inhibitor by intermolecular reaction may be used in combination with the diffusive DIR compd. Said >=2 color sensitive silver halide emulsion layers different in sensitivity are optional in their layer structure. When they are composed of 2, the layer nearer the support is made higher in sensitivity than the farther layer.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, a silver halide color having excellent sharpness and graininess, and further excellent color reproducibility. It relates to photographic materials.

[Conventional technology]

In general, silver halide color photographic light-sensitive materials (hereinafter abbreviated as light-sensitive materials) require that the shading between the pixel groups forming the image is smooth and not rough, that is, the graininess is good, or that the outline of the image is smooth. Photographic properties are required, such as being able to clearly depict minute images without blurring, that is, having good sharpness. In recent years, with the miniaturization of cameras, such demands have become stronger and stronger.

As a technique for improving graininess, it is known to provide an intermediate layer between a high-speed emulsion layer and a low-speed emulsion layer. In Japanese Patent Publication No. 49-15495, a gelatin layer or a medium-sensitivity silver halide emulsion layer with low coloring density is used as an intermediate layer;
JP-A No. 53-7230 discloses, as an intermediate layer, a medium-sensitivity halogenated m-layer containing a DIR compound that reacts with an oxidized color developing agent to release a phenomenon suppressing substance; No. 1, No. 2003-11-113 describes techniques such as providing a non-photosensitive intermediate layer containing a color that develops the same hue as the high-sensitivity emulsion layer as an intermediate layer. However, these techniques for providing an intermediate layer not only do not improve graininess sufficiently, but also have many problems, such as the provision of an intermediate layer increases the film thickness and deteriorates sharpness. ing.

Furthermore, various techniques for improving sharpness are known, one of which is a light scattering prevention technique and one of which is an edge effect enhancement technique.

Examples of the latter technique include a technique using a so-called DIR coupler and a method using an unsharp mask. Among these methods, the method using an unsharp mask has practical limitations as it may result in decreased sensitivity and deterioration of graininess. DI
Many techniques using R couplers are known, and useful IR couplers include Japanese Patent Publication No. 55-34933, Japanese Patent Publication No. 57-93344, U.S. Pat. No. 3.227.554, U.S. Pat. No. 3,617.291,
There are compounds described in No. 3,701,783 and the like. However, when using a DfR coupler to emphasize the edge effect, the MTF (modu
laLion transfer function=
Although the modulation transfer function (modulation transfer function) is improved, it is not possible to expect an improvement in MTF in the high frequency region necessary for high magnification, and there are also undesirable side effects such as a decrease in sensitivity and a decrease in density. Diffusivity D
If you use DIR couplers such as IR and timing DIR, which have long-distance effects, you can reduce the decrease in sensitivity and density, but the area where MTF can be improved is further shifted to the lower frequency side, and the sharpness at high magnification is improved. I don't expect much improvement.

On the other hand, known techniques for preventing light scattering include adding a coloring substance, reducing the amount of silver halide, and making the film thinner. Among these, a large reduction in the amount of coated silver reduces the number of coloring points, leading to deterioration of graininess.

There is also a reduction in the amount of gelatin, coupler, coupler solvent, etc. in the coating solution, but all of these methods lead to deterioration in coating properties and a decrease in coloring density, so they have their limits.

In the former case, attempts have been made for a long time to add colored substances to suppress light scattering and improve sharpness. For example, methods of dyeing with water-soluble dyes to prevent irradiation are known, but However, it has not been possible to sufficiently improve the MTF in the high frequency region due to undesirable side effects such as a decrease in the MTF.

As described above, a technique for simultaneously improving sharpness and graininess has not yet been established, and furthermore, the level of image quality required is becoming increasingly higher, and improvements are strongly desired.

[Purpose of the invention]

A first object of the present invention is to provide a silver halide color photographic material that is excellent in both sharpness and graininess.

A second object of the present invention is to provide a silver halide color photographic material with excellent color reproducibility.

[Means for solving problems]

The above objects of the present invention are achieved by the following silver halide color photographic light-sensitive material. That is, it has two or more silver halide emulsion layers having different color sensitivities on a support, and the emulsion layers have a small opacity (one of which is composed of two or more silver halide emulsion layers having different sensitivities). In the silver color photographic light-sensitive material, at least one of the above-mentioned 2N having different sensitivities is used.
The color-sensitive emulsion layer consisting of the above silver halide emulsion layer has higher sensitivity than the layer closer to the support at least than the layer farther away from the support, and the light-sensitive material has a diffusive property during development. The above object is achieved by a silver halide color photographic light-sensitive material characterized in that it contains a compound that releases a development inhibitor.

The present invention will be explained in more detail below.

In the present invention, the diffusibility of the diffusible development inhibitor released during development can be evaluated by the following method.

Light-sensitive material samples (1) and (2) were prepared, each consisting of a layer having the following composition on a (transparent) support.

Sample ■: Sample having a green-sensitive silver halide emulsion layer Iodobromide spectrally sensitized to green sensitivity if! (Silver iodide 6 mol%
, average particle size 0.48 μm) and exemplary coupler (M-2)
A gelatin coating solution containing 0.07 mol per mol of 2 rods was coated with a silver amount of 1.1 g/rrr and a gelatin coating amount of 3.
0 g/rrl, and on top of that is a protective layer; gelatin containing KM iodobromide (silver iodide 2 mol%, average particle size 0.08 μm) which has not been chemically or spectral sensitized. The coating liquid was applied so that the coating ff1ffi was 0.1 g/rd and the amount of gelatin applied was 0.8 g/rd.

Sample ■: The protective layer of Sample ■ above except that silver iodobromide was removed.

In addition to the above, each layer contains a gelatin hardening agent and a surfactant.

The sample (1) was exposed to white light using a wedge and then processed in accordance with the processing method described in Example 1 below, except that the development time was 2 minutes and 40 seconds. One developer was added with various development inhibitors in an amount that suppressed the sensitivity of sample (1) to 60% (logarithmically expressed, -Δlog E = 0.22), and the other was one without any development inhibitor added. Using.

Assuming that the sensitivity of sample ■ when no development inhibitor is added is 80, the sensitivity of sample ■ is S0/, the sensitivity of sample ■ when development inhibitor is added is 82, and the devil S1 of sample ■, then sample ■ Desensitization degree ΔSo = So'-3z, Desensitization sensitivity Δ5 of sample ① = 56 = SI Diffusivity = ΔS/ΔS0.

However, all sensitivities were set as the logarithm (-1ogE) of the reciprocal of the exposure amount at the density point of fog density +0.3.

The value obtained by this method was used as a measure of diffusivity.

Table 1 illustrates the diffusibility of different types of development inhibitors.

Hereinafter, in the present invention, compounds having a diffusivity of 0.34 or more are referred to as diffusible DIR compounds. As is clear from Example 1, which will be described later, materials with relatively low diffusivity, such as the example D
Sample 2, 7.12 using IR compound '&[)-3 is 1.
1. Since E is also small, among those with a diffusivity of 0.34 or more, one with a large diffusivity is preferable.

In the present invention, those having a diffusivity of 0.4 or more are more preferable.

In the silver halide color photographic light-sensitive material of the present invention, each emulsion layer (or at least one layer) having the same light sensitivity can be divided into three or more layers, but the DIR of the present invention
Due to the diffusivity of the inhibitor or inhibitor precursor produced from the compound in the layers, it is preferred that there be no more than three layers.

Below, the diffusible DIR compound used in the present invention will be described.

A diffusible DIR compound can generally be represented by the following formula (1).

Diffusible DIR Compound General Formula (1) %Formula%) In the formula, A represents a coupler component, m represents 1 or 2, and Y is bonded to the coupling position of the coupler component A to form a bond with the oxidized product of the color developing agent. It is a group that leaves by reaction and represents a highly diffusible development inhibitor or a group capable of releasing a development inhibitor.

A only needs to have the properties of a coupler, and it is not necessarily necessary to create a dye by coupling.

In the present invention, the group Y in the above general formula (1) is D represented by the following formulas (2A) to (2E), (3) to (5).
IR compounds can be preferably used. More preferably, the leaving group Y has the formula (2A) (2B) (2B) (4
), particularly preferably a compound represented by the formula (2B
) (2E) (4).

General formula of Y (2A) General formula of Y (2B) General formula of Y (2C) General formula of Y (2D) General formula of Y (2E) X is o, S or Se General formula of Y (3) Y General formula (4) t General formula (5) of Y In the above general formulas (2A) to (2D) and (3), R
1 is an alkyl group, an alkoxy group, an acylamino group, a halogen atom, an alkoxycarbonyl group, a thiazolilideneamino group, an oxycarponyl group, an acyloxy group, a carbamoyl group, an N-alkylcarbamoyl group, N,
N-dialkylcarbamoyl group, nitro group, amino group,
N-arylcarbamoyloxy group, sulfamoyl group, N-alkylcarbamoyloxy group, hydroxy group,
It represents an alkoxycarbonylamino group, an alkylthio group, an arylthio group, an aryl group, a heterocyclic group, a cyano group, an alkylsulfonyl group, or an aryloxycarbonylamino group. n represents 1 or 2, and when n is 2, R may be the same or different (, the total number of carbon atoms contained in one Rt is preferably θ to 10).

R2 in the above general formula (2E) is R3 in (2A) to (2D)
X represents an oxygen atom or a sulfur atom, and in general formula (4), R2 represents an alkyl group, an aryl group, or a heterocyclic group.

In the general formula (5), R3 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R4 represents a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an acylamino group, an alkoxycarbonylamino group, or an aryloxy group. It represents a carbonylamino group, an alkanesulfonamide group, a cyano group, a heterocyclic group, an alkylthio group, or an amino group.

When R,, R,, R, or R4 represents an alkyl group, it may be substituted or unsubstituted, linear or branched, or cyclic alkyl. Substituents include halogen atoms, nitro groups, cyano groups, aryl groups,
Examples include an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a carbamoyl group, a hydroxy group, an alkanesulfonyl group, an arylsulfonyl group, an alkylthio group, and an arylthio group.

When R,, R,, R, or R4 represents an aryl group, the aryl group may be substituted.

Substituents include alkyl groups, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, halogen atoms, nitro groups, amino groups, sulfamoyl groups, hydroxy groups, carbamoyl groups, aryloxycarbonylamino groups, alkoxycarbonylamino groups, acylamino groups, cyano group or ureido group.

When Rt, Rz, R3 or R4 represents a heterocyclic group, it represents a 5R or 6-membered monocyclic or fused ring containing a nitrogen atom, oxygen atom, or sulfur atom as a heteroatom,
Pyridyl group, quinolyl group, furyl group, benzothiazolyl group, oxacylyl group, imidazolyl group, thiazolyl group,
It is selected from a triazolyl group, a benzotriazolyl group, an imide group, an oxazine group, etc., and these may be further substituted with the substituents listed for the aryl group.

In general formulas (2E) and (4), the number of carbon atoms contained in R is preferably 1 to 15.

In the above general formula (5), the total number of carbon atoms contained in R3 and R4 is preferably 1 to 15.

In the above general formula (1), Y can take the structure of the following general formula (6).

General formula (6) of Y % formula % In the formula, the TIME group is bonded to the coupling position of the coupler,
It is a group that can be cleaved by reaction with a color developing agent, and is a group that can release an INHIBIT group in an appropriately controlled manner after being cleaved from a coupler.

The INHIBIT group is a group that provides a development inhibitor or a compound capable of releasing a development inhibitor.

In general formula (6), the -TIME-INHIBIT group can be represented by the following general formulas (7) to (13).

゛ General formula of Y (7) General formula of Y (8) CHz INHIBIT General formula of Y (9) (Rs)z General formula of Y (10) % formula % General formula of Y (11) General formula of Y ( 12) General formula (13) of Y In general formulas (7) to (13), R3 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkoxycarbonyl group, an anilino group, an acylamino group, ureido group, cyano group, nitro group,
Represents a sulfonamide group, sulfamoyl group, carbamoyl group, aryl group, carboxy group, sulfo group, hydroxy group, alkanesulfonyl group, and has general formulas (7), (8), (9), (11) and (13)
, β represents 1 or 2, and in general formulas (7), (11), (12) and (13), k represents an integer from 0 to 2, and general formulas (7), (10) and ( In 11), R4 represents an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, or an aryl group, and is represented by the general formula (12) and (
In 13), B represents an oxygen atom. ), and the INHIBIT group has the general formula (2A), (2B), (3)
, has the same meaning as the general formula defined in (4) and (5), but differs in the number of carbon atoms.

However, in general formulas (2A), (2B) and (3),
-The total number of carbon atoms contained in each R in the molecule is 1 to 32
In the general formula (4), the number of carbon atoms contained in R2 is 1 to 32, and in the general formula (5), R1 and R
The total number of carbon atoms contained in 4 is 0 to 32.

When R2 and R represent an alkyl group, they may be substituted or unsubstituted, chain or cyclic. Examples of the substituent include the substituents listed when R3-R4 are an alkyl group.

When Rs and R& represent an aryl group, the aryl group may be substituted. R as a substituent.

- The substituents listed when R4 is an aryl group can be mentioned.

Among the above diffusible DIR compounds, -11 formula (2A),
Particularly preferred are those having a leaving group represented by (2B), (2E) or 5).

The yellow image-forming coupler residue represented by A in general formula (1) includes pivaloylacetanilide type, benzoylacetanilide type, malondiester type,
malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type, malon ester monoamide type,
Coupler residues of benzothiazolylacetate type, benzoxacylylacetamide type, benzoxacylylacetate type, aron diester type, benzimidazolylacetamide type or benzimidazolylacetate type, heterozygous compounds included in U.S. Pat. No. 3,841,880 Coupler residues derived from ring-substituted acetamides or heterocycle-substituted acetates or U.S. Pat. No. 3.770.44
No. 6, British Patent No. 1,459.171, West German Patent (O
LS) No. 2.503,099, Japanese Unexamined Patent Publication No. 50-1397
No. 38 or Research Disclosure 15737
Examples thereof include coupler residues derived from acylacetamides described in No. 1, No. 4,046, and heteroprototypical coupler residues described in US Pat. No. 4,046.574.

The magenta image-forming coupler residue represented by A includes a 5-oxo-2-pyrazoline nucleus, Bira'/'tff-
(1,5-a) Coupler residues having a benzimidazole core or a cyanoacetophenone type coupler residue are preferred.

The cyan image-forming coupler residue represented by A is preferably a coupler residue having a phenol nucleus or an α-naphthol nucleus, or an indacylon or pyrazolotriazole coupler residue.

Furthermore, the effect as a DIR coupler is the same even if the coupler does not substantially form a dye after coupling with the oxidized form of the developing agent and releasing the development inhibitor. Coupler residues of this type represented by A include U.S. Pat.
No. 2,213, No. 4.088.491, No. 3.6
32.345, 3.958.993 or 3
．． Examples include the coupler residues described in No. 961,959.

Next, preferred specific examples of DIR compounds that can be used in the present invention are listed. However, as a matter of course, the DIR of the present invention
The compounds are not limited to those shown below.

0 b
10
D-5 N -N C+dbs00CCHCOOC+zHzsl D-12 0H H NH! CHs CH2 N=N C+*U□0CQCHCOOC,□h.

N(h to lJz to Htl; Hz
L; ND-26 0H uz 0■ (0?+ ω C1')
C10
RoOwl
Ro's
0 of
b0
L D-450H D-46 CHs CHs 0■ NU.

r I Ox O3H +1LI.

D-55 D-56 CzHs C5) l++Ltλ H 0!1 to tHs +111 C++Hz These compounds are described in U.S. Pat. 3
．． No. 958.993, No. 2.070.266, Research Disclosure No. 21228, December 1981, etc. can be used to synthesize the compound.

The amounts of these compounds to be used may be the same as those for ordinary DIR couplers. Preferably 0 per mole of silver halide
．． 0001 to 0.10 mol, more preferably 0.00 mol
It is 10 to 0.020 mol.

Further, in combination with the diffusible DIR compound of the present invention, a DIR compound that releases a non-diffusible development-inhibiting group through an intramolecular reaction can be used. Alternatively, different or similar leaving groups, each separated from a separate molecule, may be used in combination with a DIR compound in which an intermolecular reaction produces a compound whose photographic behavior can be altered. In each case, the ratio of their combination may be arbitrary, but the DI of the present invention
The higher the ratio of R, the better.

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. Of two or more layers having different sensitivities, at least one layer farther from the support may be more sensitive than the other layer.

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. It can be used as a material. For example, the red-sensitive layer can be composed of two layers, a high-sensitivity layer and a low-sensitivity layer, with the one closer to the support being the higher-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)
When providing layers, M from the support.

The order may 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 one yellow filter layer is used 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.

The layer structure can be RL, IL, GH, GL, 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. Additionally, BS, IL, and RH.

R.L., 1. L, GH, GL, YC, BL, BH, Pro
It can be made into a layered structure. This is a green-sensitive layer in which the one closer to the support is the higher-sensitivity layer. In addition to this modification, a configuration can be provided in which an IL is further provided between RL and RH. Also, BS, RH, IL, 'RL,
IL,G)(,YC,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, rc, RM, RH.

RL, IL, GH, 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, YC, BL, BH, P
ro layer structure, 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 OIlogE. 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 by 0.2 to 1. O
It is preferable to have a difference in It o g E (E: exposure charge).

In the light-sensitive material of the present invention, the color-sensitive layers containing dye image-forming couplers have substantially the same color sensitivity, and at least one color-sensitive layer contains a plurality of halogens of different types. It suffices if the structure has a silver oxide emulsion layer. Here, "the color sensitivity is substantially the same" means, for example, any one of the blue, green, and red wavelength ranges within the spectral wavelength range to which the color multilayer photosensitive material of -a can be sensitive. This means that the photosensitive layer is considered to have substantially the same color sensitivity even if the photosensitive regions are slightly different from each other in a certain wavelength range.

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.

Furthermore, it is highly desirable that such a non-photosensitive intermediate layer contain a scavenger substance or the like that reacts with the oxidized form of the developing agent to deactivate it.

As for the composition of silver halide in each emulsion layer, any silver halide composition can be used as described below. Silver iodobromide or silver bromide is preferred, but silver chlorobromide, silver chloroiodobromide, etc. may also be used.

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 luminance 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-sensitivity layer is preferably from 0.2 to 1.5 microns, particularly from 0.2 to 1.0 microns.

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

There are no restrictions on the method of manufacturing the emulsion layer having each of these color sensitivities, and various arbitrary methods can be applied, for example, known methods can be employed. Further, any protective colloid such as gelatin may be used as the protective colloid.

The amount of silver coated in each emulsion layer is 4 to 40 mg/dn? degree is preferred.

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.

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 defined as 'Standard deviation coefficient of variation (%) of particle size = xlOO average value of particle size, and is 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 taking an enlarged photograph of the cross section of the dried sample using 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 to 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.

In the present invention, silver halide grains having any grain structure can be used. For example, core/shell type silver halide grains can be preferably used. An example of this is a grain structure consisting of 2N or more layers having different silver iodide contents. When using grains with such a structure, the layer with the highest silver iodide content (referred to as the core) is the outermost layer (referred to as the shell).
Silver iodobromide other than the above is preferred. The inner layer (core), which has the highest silver iodide content, has a silver iodide content of 6 to 40 mol%.
8 to 30, more preferably 8 to 30
It is mol%, more preferably 10-20%. 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%.
~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, when using grains having the above-mentioned structure, the difference in content between the core portion with a high silver iodide content and the shell portion with a low silver iodide content has a sharp boundary. Alternatively, the boundary may change continuously and the boundary may not necessarily be clear. Also preferably used is one having an intermediate layer between the core and the shell having a silver iodide content between the core and the shell. In the case of core/shell type silver halide grains having such an intermediate layer, the volume of the intermediate layer is preferably 5 to 60%, more preferably 20 to 55%, of the entire grain.

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.

When core/shell type silver halide grains are used in the present invention, the average silver iodide content 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.

When core/shell type silver halide grains are used in the present invention, they may be normal crystals such as cubes, tetradecahedrons, and octahedrons, may be composed of twin crystals, or may be a mixture thereof. It is preferable that it is a normal crystal.

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.

General formula (Y) In the formula, R+, nt and R3 may be the same or different,
Hydrogen atoms, halogen atoms (e.g. fluorine, chlorine, bromine, etc.), alkyl groups (e.g. methyl, ethyl,
groups such as allyl and dodecyl).

A, aryl group (for example, phenyl, naphthyl, etc. groups).

Alkoxy groups (e.g., methoxy, ethoxy, dodecyloxy, etc.), acylamino groups (e.g., acetamide, α(p-dodecoxyphenoxy)butanamide, etc.), carbamoyl groups (e.g., carbamoyl,
N,N-dimethylcarbamoyl, N-δ-(2,4-di-tart-amylphenoxy), butylcarbamoyl, etc.), alkoxycarbonyl groups (e.g. ethoxycarbonyl, dodecyloxycarbonyl, α(dodecyloxycarbonyl)ethoxy) groups such as carbonyl), sulfonamide groups (e.g. methanesulfonamide, p-
dodecyloxybenzenesulfonamide, N-benzyldodecanesulfonamide, etc.), or sulfamoyl groups (e.g. sulfamoyl, N-methylsulfamoyl, N-δ-(2,4-di-tart-amylphenoxy, cy)butyl) represents each group such as sulfamoyl lNlN-diethylsulfamoyl.

R4, R5, R& and R7 may be the same or different,
hydrogen atom, alkyl group (e.g. methyl, ethyl,
tert-butyl), alkoxy groups (eg methoxy, ethoxy, propoxy).

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

N-bensyldodecanesulfonamide, etc.).

W represents 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.), an aryloxy group (e.g., phenoxy, methylphenoxy, etc., 8 groups), or a dialkylamino group (e.g., dimethylamino, N-butyl-N-octylamino, etc.).

Alternatively, a group representing a hydrogen atom or a removable group, which is preferable as a removable group, is represented by the general formula [Y'].

General formula (Y/) Y represents a nonmetallic atomic group necessary to form a 5- to 6-membered ring (the cyclic compounds formed are, for example, 2.5-dioxo-imidacyline, 2.5-pyrrolidinedione , 1.3
-isoindoledione, 2.3.5-)rioxoimidazolidine, 2゜5-dioxo-triacylidine, 2
．． 4-oxazolidinedione, 2,4-thiazolidinedione, 2(IH)-pyridone, 2(IH)-pyrimidone, 2(IH)-pyrazone, 5(IH)-imidacylon, 5. (・I H) −) Riazolone, 2(LH
)-pyrimidone, 2-pyrazolone (51,2-isoteazolone (5), 2(IH)-quinaoxacylone, 4(3
H)-Pyrimidone, 2-Benzoxacilone, 4-Isoxacilone (5), 3-Furonic), 4-Imida.

Zolone (2), 3-pyrazolone, 2-tetra, zolone (
5) represents each diluent such as 3-tetrazolone (5), )
Specific examples of the yellow coupler represented by the general formula [Y] are listed below.

・-oz; [“−]　　　　..

(Y-3) l uH, Ll h 3 (Y-4) (Y-s] (Y-63 (Y-7) (y-10) (Y-11) t (y-12) CI, 0 ( Y-13) (Y-14) (Y-1s) I The silver halide emulsion contains silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide and silver halide. Any material commonly used in silver halide emulsions such as silver chloride can be used, but 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. The method of creating and growing the zero-species particles that may be grown 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 consideration the critical growth rate of silver halide crystals, halide ions and silver ions may be added simultaneously and sequentially while controlling the PH and PAg in the mixing pot. 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.

, silver halide grains contain cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including IF salts), rhodium salts (including complex salts), and iron salts during the grain formation and/or growth process. Metal ions can be added using at least one selected from salts (including complex salts) to contain these metal elements inside the particles and/or on the particle surfaces, and the particles can be placed in an appropriate reducing atmosphere. By this, a reduction sensitizing liquid can be applied to the inside of the particles and/or to the surface of the particles.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, Research Disc
loss (hereinafter abbreviated as RD) can be carried out based on the method described in No. 17643, Section 3.

The silver halide grains 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.

Silver halide grains may have regular crystal shapes such as cubes, octahedrons, and dodecahedrons, or may have irregular crystal shapes such as spherical or plate shapes. In the particles, any ratio of (1001 planes to (111) planes) 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 30μ,
Preferably, those having a diameter of 0.1 to 20μ can be used.

Silver halide emulsions may have any grain size distribution.6 Emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution (monodisperse emulsions) may be used. The term "monodisperse emulsion" as used herein refers to one in which the standard deviation of the grain size distribution divided by the average grain size is 0.20 or less. Here, the grain size is according to the above definition. ) may be used alone or in combination.

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. Namely, sulfur enhancement method, selenium sensitization method, reduction sensitization method,
Noble metal enhancement methods using gold or other noble metal compounds 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. The sensitizing dyes may be used alone or in combination of two or more. Even if a superchromic enhancer, which is a dye that does not itself have a spectral sensitizing effect along with the sensitizing dye, or a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye, is included in the emulsion. 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 polymeric 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. The hardening agent can be added in an amount capable of hardening the photosensitive material to such an extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the 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- ) lyacryloyl-hexahydro-5-) riazine, 1.
3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-
5-) riazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic 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 in section x■ 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.

In the emulsion layer of a photosensitive material, a dye is formed by a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, p-phenylenediamine derivative, aminophenol?, R-form, etc.) during color development processing. A dye-forming 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 for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the angry 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 window optical materials may be produced using different combinations from the above.

It is desirable that these dye-forming couplers have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. The effect of color correction on the 0 pigment-forming power puller, whether it is a 4-equivalent type in which 100 silver ions need to be reduced or a 2-equivalent type in which only 2 molecules of silver ions need to be reduced. By compounding with an oxidized form of a colored coupler and a developing agent having the following properties, a development accelerator, a purity accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, a fogging agent, an antifogging agent, Compounds that release photographically useful fragments such as chemical sensitizers, spectral sensitizers, and desensitizers are included. 0. Coupling reactions with oxidized aromatic primary amine developers However, colorless couplers that do not form dyes (also referred to as competitive couplers) can also be used in conjunction with dye-forming couplers.

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

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. 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
．． 891,445, West German Patent No. 1.547.868, West German Application No. 2.219.917, West German Patent No. 2,261
．． No. 361, No. 2゜414.006, British Patent No. 1
．． 425.020, JP 51-10783, JP 47-26133, JP 48-73147, JP 50-
No. 6341, No. 50-87650, No. 50-1233
No. 42, No. 50-130442, No. 51-21827
No. 51-102636, No. 52-82424,
It is described in No. 52-115219, No. 58-95346, etc.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, virazolohenreimidazole 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. 2,600.788, 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
．． 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, Japanese Patent 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 generally used as cyan dye-forming couplers, and 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. 476.5!3, 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, Japanese Patent Application Publication No. 50-130441, etc., and couplers described in Japanese Patent Application Laid-open No. 58-98731 are preferred.

Toga, white.

Among the DIR compounds of the present invention that do not need to be adsorbed onto the surface of silver halide crystals, and other similar DIR couplers and DIR compounds, hydrophobic compounds can be used by solid dispersion method, latex dispersion method, oil droplet in water method, etc. Various methods can be used, such as a type emulsion dispersion method, which can be appropriately selected depending on the chemical structure of the compound, etc. The oil-in-water type emulsification dispersion method can be applied using conventionally known methods for dispersing hydrophobic additives, and usually a high boiling point a solvent with a boiling point of about 150°C or higher is mixed with a low boiling point and/or water-soluble organic solvent as necessary. Dissolve using a solvent and emulsify and disperse using a surfactant in a hydrophilic binder such as an aqueous gelatin solution using a dispersion means such as a stirrer, homogenizer, colloid mill, floatant mixer, or ultrasonic device. After that, it may be added to the desired hydrophilic colloid liquid. Low boiling point at the same time as dispersion or dispersion 8! A step of removing the solvent may be included.

Examples of high-boiling point solvents include organic compounds with a boiling point of 150°C or higher, such as phenol derivatives, phthalate alkyl esters, phosphate esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, and trimesic acid esters, which do not react with the oxidized form of the developing agent. )8 medium is used.

Low boiling or water-soluble 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, pukunol, chloroform,
Examples include carbon tetrachloride, nitromethane, nitroethane, and benzene.

The same applies to dye-forming couplers, colored couplers, image stabilizers, color antifoggants, ultraviolet absorbers, and fluorescent whitening agents.

Note that the DIR compound of the present invention and other DIR compounds may be used by being dispersed separately with couplers, etc., or they may be mixed and dispersed simultaneously with couplers, colored couplers, etc.

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 magenta 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 retardants, and bleaching accelerators can be added to the silver halide emulsion layer and/or other wood-philic 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 micontrast, or accelerating 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 which can preferably be 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, an antihalation layer, and an antiirradiation layer. These dyes and/or emulsion layers may contain dyes that are washed out or bleached from the light-sensitive material during development.

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 cloak agent is preferably 0.05μ to 10μ. The amount added is preferably 1 to 300 mg/tolerance.

A lubricant can be added to the photosensitive material to reduce sliding friction.

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 the protective colloid layer other than the emulsion layer on the side on which the emulsion layer is laminated with respect to the emulsion layer and/or the support. Preferably used antistatic agents which may be used are the compounds described in RD 17643 x■.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material may be used to improve coating properties, prevent static electricity, improve slipperiness, emulsification and dispersion, prevent adhesion, and improve photographic properties (development acceleration, hardening, aggravation, etc.). Various surfactants can be used for this purpose. .

The support used in the photosensitive material of the present invention includes α-olefin polymers (e.g. polyethylene, polypropylene,
flexible reflective supports such as synthetic paper, 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 photosensitive materials, thickeners may be used to improve coating properties.For example, thickeners, such as hardeners, have quick reactivity and can be added to the coating solution in advance to cause gelation before coating. For materials that may cause such problems, it is preferable to mix them using a static mixer or the like immediately before application.

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. .

To obtain a dye image using the photosensitive material of the present invention, after exposure,
Color photographic processing is performed, and color processing includes a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process. Instead of the process used above, a bleach-fixing process can be carried out using a one-bath bleach-fixing solution, or a one-bath developing, bleach-fixing solution that allows color development, bleaching, and fixing to be performed in one bath. It is also possible to perform a monobath treatment process using

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 treatments, instead of the color development process, an activation bake process may be performed in which a color developing agent or its precursor is contained in the material and the development process is performed using an activator solution. Can be applied. 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 25°C to
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, sherate, benzenesulfonate, etc. can be used. can.

These compounds are generally about 0.0% in color developer 11.
A concentration of 1 to 30 g, more preferably about 1 to 15 g per color developer 11 is used. If the amount added is less than o or tg, sufficient color density cannot be obtained.

Examples of the aminophenol-based developing side include O-aminophenol, p-aminophenol, and 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,
Alkyl groups and phenyl groups may be substituted or unsubstituted. Among them, an example of a particularly useful compound is N.

N-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N.

N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamine)-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-p-+-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 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, as well as organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide, etc. can be appropriately contained.

The pH of the color developing solution used in the present invention is usually 7 or more,
Preferably it is about 9-13.

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.
-organic phosphonic acids such as hydroxyethylidene-1,1'-diphosphonic acid, aminopolyphosphonic acids such as aminotri(methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acids such as citric acid or gluconic acid, 2-phosphonobutane, 1 , phosphonocarboxylic acids such as 2,4-tricarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compounds.

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'-)acetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, and iminodiaminetetraacetic acid. acetic 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,
These bleaching agents, which may be ammonium salts or water-soluble amine salts, 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. Also, iron(1) ethylenediaminetetraacetate i! The bleaching solution may be a bleaching solution containing a salt bleach and a large amount of a halide such as ammonium bromide. In addition to ammonium bromide, the halide may include 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 include thiocyanates such as sodium thiocyanate and ammonium thiocyanate, thiourea, and 1,000-onythyl. These fixatives are 5
g / 1 or more, used in an amount that can be dissolved,
Generally used at 70-250 g/l.

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 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. Also,
Preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids or nitroalcohols, stabilizers for nitrate caps, hardening agents such as water-soluble aluminum salts, methanol, Organic solvents such as dimethylsulfamide and dimethylsulfoxide can be appropriately contained.

The pH of the fixer is used at 3.0 or higher, but generally it is 4.
．． 5-1O, preferably 5-9.5, most preferably 6-9.

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, iron ethylenediaminetetraacetate (I[[)! A bleach-fix solution consisting of a monosalt bleach and a small amount of a halide such as ammonium bromide other than the silver halide fixing agent mentioned above, or conversely, a composition containing a large amount of a halide such as ammonium bromide. Bleach-fix solution, and even iron ethylenediaminetetraacetate (m) i! A special bleach-fix solution having a composition consisting of a combination of a salt bleach and a large amount of a halide such as ammonium bromide may also be used. In addition to ammonium bromide, the halides include hydrochloric acid, hydrobromic acid,
Lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, and the like can also be used.

Examples of the silver halide fixing agent that can be included in the bleach-fixing solution include the fixing agents described in the above-mentioned fixing process. The concentration of the fixing agent and the 9H buffer scraper and other additives that can be contained in the bleach-fixing solution are the same as in the above-mentioned fixing process.

The pH of the bleach-fix solution used is 460 or higher, generally 5.0 to 9.5, preferably 6.0 to 8.
5, most preferably 6.5 to 8.5.

〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

In all of the following examples, the amount added to the silver halide photographic material is expressed per unit unless otherwise specified. In addition, halogenated S and colloidal silver are shown in terms of silver.

A multilayer color photographic element sample 1 was prepared by sequentially forming each layer having the composition 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 (1,L) Gelatin layer containing an emulsified dispersion of 2.5-di-t-octylhydroquinone.

3rd layer; low sensitivity red-sensitive silver halide emulsion layer (RL-1)
Monodispersed emulsion (emulsion 1) consisting of AgBr1 containing average grain size (r) 0.38 μm and Ag [6 mol%...Amount of silver coated 1.8 g/ITr Sensitizing dye ■...Grudge 1 6 x 10-S mol per mole Sensitizing dye ■... 1.0 x IO-5 per 1 mole of S mol Cyan coupler (c-1)... per 1 mole of silver 0.06 mol colored cyan coupler (CC-1)...Silver 1
0.003 mol to mol DIR compound (ED-1)...1m 0.0035 mol to 1 mol 4th layer; high-frequency red-sensitive silver halide emulsion layer (R■-1 ) Average particle size ('F) 0.5μ,
Monodispersed emulsion (emulsion ■) consisting of AgBr1 containing 7.0 mol% of Agl... Silver coating amount 1.3 g/m Sensitizing dye I... 3XlO-' mole sensitization per 1 mole of wi Dye ■... 1.0 x 10-' mol cyan coupler (C-1) per 1 mol of silver 0.02 mol colored cyan coupler (CC-1) per 1 mol of silver )・・・・・・Silver 1
0.0015 mol to mol DIR compound (ED-1)...0.001 mol to 1 mol of silver 5th layer; Intermediate layer (1,L) Same as 2nd layer, gelatin layer .

No. 61 is a low-sensitivity green-sensitive silver halide emulsion [(GL-1)
Emulsion - ■... Coating weight 1.5/rrl sensitizing dye ■... 2.5 x 10-' mol sensitizing dye for 1 mole of silver ■...
... 1.2 x 10-' mol per 1 mole of magenta coupler (M-1)...0.
050 molar colored magenta coupler (CM-1)...
0.009 mol to 1 mol of silver DIR compound (D-1) 0.0040 mol to 1 mol of silver 7th layer; High-sensitivity green-sensitive silver halide emulsion [(G11-1)
) Emulsion - ■... Coated silver amount 1.4 g/rrr Sensitizing dye ■... 111 moles! , 5X104 mole sensitizing dye ■...
... 1.0 x 10-' moles per mole of silver Magenta coupler (M-1) ...0.020 per mole of m
Mol colored magenta coupler (CM-1)...0.002 mol per mol of silver DIR compound (ED-1)...0.0o10 mol to 5j11 mol 8N; 4 (O-Fee) Lt
A gelatin layer comprising an emulsified dispersion of yellow colloidal silver and 2,5-di-octylhydroquinone.

9th N: Low sensitivity blue-sensitive silver halide emulsion layer (BL-1)
Sensitizing dye with an average particle size of 0.48 μs and containing 16 mol% of A6... 1.3xlO-' mol per 1 mol of silver Yellow coupler (EY-1)...S 1 0 for molar ζ
．． 29 mol 1st O layer; high-sensitivity blue-light emulsion layer (BH-1) average grain size 0
．． 8 μm, monodispersed emulsion (emulsion) consisting of AgBr1 containing 115 mol% of Ag... Silver coating amount: 0.5 g 1 cd multiplied dye ■... t, ox io-' mole yellow per 1 mole of silver Coupler (EY-1)...0.0% per mole of silver.
08 mol DIR compound (ED-1) 0.0015 mol per 1 mol 11th layer; 1st layer 3iN (Pro-1) Silver iodobromide (A
gl 1 mol% average particle size 0.07 μm)
5g/i Ultraviolet absorber Gelatin N containing UV-1 and tlV-2
.

12th layer; second protective layer (Pro 2) polymethyl methacrylate particles (diameter 1.5 μm) & formalin scavenger (H3-
Gelatin layer containing 1) In addition to the above composition, each layer contains a gelatin hardening agent (H-1
) and surfactants were added.

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

Sensitizing dye 1; Anhydro 5,5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)thiacarbocyanine hydroxide enhancing dye ■; Anhydro 9-ethyl-3,3'-di(
3-sulfopropyl)-4゜5.4',5'-dibenzothiacarbocyanine hydroxide sensitizing dye ■; anhydro5,5'-dipheny) Lt-9
-ethyl-3,3'-di(3-sulfopropyl)oxacarbocyanine hydroxide sensitizing dye■; anhydro9-ethyl-3,3'-di(
3-sulfopropyl)-5, G, 5″56′-dibenzoxacarbocyanine hydroxide sensitizing dye Cyanine 0,i(,,(L) ED-1 0M-1 l Y-1 V-1 H V-2 C2%5C(lNHtztlis H,C-C"' DIR compound added in sample 1 and its amount Samples 2 to 16 are created by changing.

The composition of each sample is shown in Table 2. In the table, the numbers in the DIR column indicate the D numbers of the DIR compounds exemplified above. In the table, the layer structure is in order, starting from the support: red-sensitive, low-sensitivity IRL, red-sensitive, high-sensitivity. [RH, green-sensitive, low-sensitivity layer CLS, green-sensitive, high-sensitivity JliGH, and has a comparative layer structure. Also, what does it say "reverse layer-1" mean 1 from the support side? The order is H, RL, GL, and GW, and the low-sensitivity layers (RL and GL) are adjacent to each other. Reverse J! ! -2 means the same <RH
.

The order is RL, GH, and OL. Furthermore, as sample 17, instead of the monodispersed emulsion in sample Mail,
In step 2, a polydisperse emulsion (coefficient of variation 40) was prepared.

Margins below Each sample mt-17 thus prepared was subjected to wedge fog light using white light, and then subjected to the following development treatment.

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

(Color developer) Below margin 4-amino-3-methyl, N-ethyl-to(β-hydroxyethyl)-anilino 6M61 m 4 ,
75 g anhydrous sodium sulfite 4.2
5 g Hydroxylamine 1/2 sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (l hydrate) 2.5 g Potassium hydroxide 1.0 g Water In addition, let it be B.

(Bleach solution) Ethylenediaminetetraacetic acid iron ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide tso, o g Glacial acetic acid 10.0ml! Add water and enjoy! Bind and use ammonia water to pH = 6.0
Adjust to.

(Fixer) Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to 11
and adjust the pH to 6.0 using acetic acid.

(Stabilizer) Formalin (37% aqueous solution) 1.5n+
4! Konida Sox (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5m
l! Add water to make 11.

Regarding the obtained sample, MTE and RM were determined as follows.
The results of measuring S and IIE are shown in Table 3 for the green-sensitive layer and in Table 4 for the red-sensitive layer.

MTF: The sharpness improvement effect is the MTF (Modu
laLion Transfer Function
), and find each M for 10, 30, and 50 dragons.
It is expressed as a relative value of TF (specimen magnet 1 is set as 100).

RMS: The RMS value is the density of the minimum density + 1.2 with an aperture scanning area of 25
The standard of the variation in concentration value that occurs when scanning with a 0 μM microdecimometer (shown as 1000 times the t!! deviation).

1.1. E.

The prepared sample was placed in close contact with a wedge whose density was continuously changed, and exposed to white light, green light, and red light respectively.
Evaluation was made by comparing the obtained sensitometry gamma values. (Sample *t, expressed as a relative value with 0).

As is clear from Tables 3 and 4 below, when diffusive DIR is carried out with the layer structure of the present invention, a photosensitive material with extremely good MTF not only on the low frequency side but also on the high frequency side can be obtained. I know that it will happen. Furthermore, it can be seen that the samples according to the examples of the present invention are also extremely good in RMS. And 1.1. It can be seen that E is also extremely good, and the color reproducibility is excellent. Sample magnets 7 to 11 are particularly good.

Visual evaluation of the prints obtained by printing these samples onto paper revealed the same excellent effects as described above.

〔Effect of the invention〕

As described above, according to the present invention, it is possible to obtain a silver halide color photographic material having excellent sharpness and graininess as well as excellent color reproducibility.

Patent applicant: Konishiroku Photo Industry Co., Ltd., agent patent attorney
Takatsuki 7 Procedures Written by Chief Ho Masaru (self-motivated) January 20, 1985 Commissioner of the Patent Office Kuro 1) Akio Yu 1, Indication of the case 1986 Patent side No. 048263 2, Name of the invention New layer structure Silver halide color photographic light-sensitive material 3, relationship with the amended person case Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photo Industry Co., Ltd. 4, Agent 6, Contents of amendment As attached! 11 Change rlcJ on page 54, line 11 of the specification to rlL
Correct it with J.

(2) "Kishi)," in line 5 of page 64 of the same book is amended to "Kishi)."

(3) "Flow jet mixer" on page 86, lines 13 and 14 of the same book is corrected to "flow jet mixer."

(4) Correct the true chemical formula rUV-2J in No. 114 of the same book as follows.

``CzHs J (5) ``Made by a company'' in line 8 of page 120 of the same book is corrected to ``Made by ■''.

that's all

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. 1. A silver halide color photographic light-sensitive material having a novel layer structure, characterized in that the light-sensitive material has a higher sensitivity than the other layer, and the light-sensitive material contains a compound that releases a diffusive development inhibitor during development.