JPH02105146A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve sharpness and graininess by providing photosensitive silver halide emulsion layers adjacently to a black colloid silver-contg. layer and incorporating a specific compd. into at least one layer of the photograph constituting layers. CONSTITUTION:Any of the photosensitive silver halide emulsion layers is provided adjacently to the black colloid silver-contg. layer of the silver halide photographic sensitive material having the photograph constituting layers including the red-photosensitive silver halide emulsion layer, the green-photosensitive silver halide emulsion layer and the blue-photosensitive silver halide emulsion layer as well as the black colloid silver-contg. layer on a base and the compd. which scavenges the oxide of a developing agent by reacting with the oxidation product of the developing agent or releases the precursor thereof is incorporated into at least one layer of the photograph constituting layers. The silver halide color photographic sensitive material having the excellent sharpness, graininess, etc., is obtd. in this way.

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 particularly to improvement of graininess and sharpness of a silver halide color light-sensitive material. .

[Background of the invention]

In recent years, silver halide color photographic light-sensitive materials have made remarkable progress, and light-sensitive materials with higher sensitivity and higher image quality have been released one after another. ) However, it has become possible to obtain good photographs. Aiming for even higher image quality, U.S. Patent No. 3.402.046 describes a technique for specifying silver halide emulsion grains with low light scattering, and U.S. Pat. No. 3.658,536 In order to improve the sharpness, we mainly utilize effective optical methods such as changing the layer arrangement of silver halide emulsion layers with different color sensitivities, which are unique to silver halide color photographic light-sensitive materials, on the support. The technology is described. On the other hand, U.S. Patent No. 3
．． No. 227,554 discloses DIR couplers, D.I.
A technique using R compounds is described, U.S. Patent No. 2.08
3.640 discloses a technique using a coupler that produces a mobile dye, and JP-A-60-1284 discloses a technique using a coupler that produces a mobile dye.
Publication No. 43 discloses a technique using silver halide having a high average silver iodide content, and proposes to improve graininess using these techniques.

It is believed that with the construction of such new technology, higher image quality of silver halide color photographic light-sensitive materials will be achieved. The method of use is naturally limited, and the synthesis route for the compound is complicated, which results in an impact on product cost, which is undesirable.

Furthermore, the method of changing the arrangement of the photographic constituent layers of the support reduces operational efficiency in preparing, coating and drying coating solutions with different color sensitivities for each silver halide emulsion layer, and The number of coatings increases, making it necessary to use a manufacturing method that involves coating and drying a plurality of coatings on a support, which is unsatisfactory from the standpoint of product cost.

On the other hand, JP-A-58-145941 describes an example in which the non-photosensitive colloid layer between the black colloidal silver-containing layer and the photosensitive silver halide emulsion layer is removed, and the sharpness is improved. However, it is still not satisfactory. Also,
U.S. Patent No. 2.688.541, U.S. Patent No. 3.206,31
No. 0, No. 969.045, and No. 1,554,573 describe that contact fog occurs when a black colloidal silver-containing layer is adjacent to a light-sensitive silver halide emulsion layer, and Providing a light-sensitive silver halide emulsion layer (intermediate layer) has been considered a matter of course in the art.

[Purpose of the invention]

The object of the present invention is to provide a silver halide color photographic material with excellent sharpness and graininess, and an object of the present invention is to provide a silver halide color photographic material that is furthermore inexpensive.

[Structure of the invention]

The object of the present invention is to have photographic constituent layers on a support, including a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a front window light-sensitive silver halide emulsion layer, and a black colloid-containing layer. The silver halide photographic light-sensitive material has any of the above photosensitive silver halide emulsion layers adjacent to the black colloidal silver-containing layer, and at least one of the photographic constituent layers contains an oxidation product of a developing agent. This was achieved by a silver halide color photographic light-sensitive material characterized by containing a compound capable of reacting to scavenge the oxide or a compound capable of releasing its precursor.

Next, details of the present invention will be described.

In the present invention, the compound capable of reacting with the oxidation product of the developing agent to scavenge the oxide or the compound capable of releasing its precursor (hereinafter referred to as "rDSR compound") is:
It is preferably represented by the general formula CD5R-I).

In the general formula CD5R-I) Coup-(Time)g-Sc above-formula CD5R-I), Coup can release (Time)Q-5c by reaction with the oxidized color developing agent. represents a coupler residue, Time is Time-S
After c is released from Coup, it represents a timing group that can release Sc, where Sc is Coup or Tim
It represents a scavenger of oxidized color developing agent that can scavenge the oxidized color developing agent by redox reaction or coupling reaction after being released from e-Sc, and a represents 0 or 1.

Further specifically explaining the compound represented by the general formula (DSR-I), the coupler residue represented by Coup is generally a yellow coupler residue, a magenta coupler residue, a cyan coupler residue, or a substantially image-containing coupler residue. A coupler residue that does not form a color-forming dye, and preferably has the following formula (
It is a coupler residue represented by Ia) or Ih).

General formula (Ia) - Formula (Ib) - Formula (Ie) - Formula (If) - Formula (Ig) - Formula (Ih) above - In formula (Ia), %R1 is an alkyl group, an aryl group, an arylamino group and R2 represents an aryl group or an alkyl group.

In the above formula (Ib), R represents an alkyl group or an aryl group, R4 represents an alkyl group, an acylamino group,
Represents an arylamino group, an arylureido group, or an alkylureido group.

Above - In the formula (I c), R1 is the general formula (Ib)
R8 represents an acylamino group, a sulfonamide group, an alkyl group, an alkoxy group, or a halogen atom.

In the above-mentioned formulas (Id) and (Ie), R7 represents an alkyl group, an aryl group, an acylamino group, an arylamino group, an alkoxy group, an arylureido group, or an alkylureido group, and R6 represents an alkyl group or an aryl group.

In the above -fi formula (If), %RI represents an acylamino group, a carbamoyl group, an arylureido group, and R,
represents a halogen atom, an alkyl group, an alkoxy group, an acylamino group, or a sulfonamide group.

In the above formula [Ig], R1 is the general formula (If)
and R1° represents an amino group, a carbonic acid amide group, a sulfonamide group, or a hydroxyl group.

In the above formula (Ih), RII represents a nitro group, an acylamino group, a succinimide group, a sulfonamide group, an alkoxy group, an alkyl group, a halogen atom, or a cyano group.

In addition, in the above formula, a in (Ic) is θ~3, (
n in If) and (Ih) is θ~2, - Formula (I
■ in g) represents an integer of 0 or l, and (1, n is 2
In the above case, each of R5, R8 and R11 may be the same or different.

The above-mentioned polygroups include those having a substituent, and preferred substituents include a halogen atom, a nitro group, a cyano group, a sulfonamide group, a hydroxyl group, a carboxyl group, an alkyl group, an alkoxy group, a carbonyloxy group, and an acylamino group. , aryl groups, etc., so-called bis-type couplers,
Examples include those containing a coupler portion constituting a polymer coupler.

The lipophilicity exhibited by R I''-Rr in each of the above formulas can be arbitrarily selected depending on the purpose, and in the case of a normal image forming coupler, the total number of carbon atoms in R0 to R1° is
It is preferably 0 to 60, more preferably 15 to 30. In addition, in order to allow the dye produced by color development to move appropriately in the photosensitive material, the RI
The total number of carbon atoms in "'-Rto is preferably 15 or less.

In addition, couplers that do not substantially generate image-forming coloring dyes include those that do not generate coloring dyes, so-called run-off dye-forming couplers, in which the coloring dye flows out from the light-sensitive material into the processing solution, and couplers that do not substantially generate image-forming coloring dyes. Bleached by reacting with ingredients, so-called
Refers to bleaching dye-forming couplers that do not leave a color image after processing; in the case of run-off dye-forming couplers,
The total number of carbon atoms in R1-R1 is preferably 15 or less, and it is further preferred that R0 to R8° have at least one carboxyl group, arylsulfonamide group, or alkylsulfonamide group as a substituent.

In the above formula (CD5R-I), the timing group represented by Time is preferably represented by the following formula (I i)
, (Ij) or (Ik).

In the formula, B represents an atomic group necessary to complete the benzene ring or naphthalene ring, and Y is bonded to the active site of the 10-1 Coup (coupling component). R1! , R13 and R14 represent a hydrogen atom, an alkyl group or an aryl group.

and the other is the formula CD5R-I)S
It is connected to c.

In the formula, Y-R+*, R1, each represent the above-mentioned formula (I i
), R1 represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfonyl group, an alkoxycarbonyl group, or a heterocyclic residue, and R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic residue. group, alkoxy group, amino group, acid amide group, sulfonamide group, carboxyl group, alkoxycarbonyl group, carbamoyl group, or cyan group.

Moreover, the timing group represented by the above-mentioned formula (I j) is
Similar to the formula (I i) above, Y is the formula (DS
Coup (coupling component) of R-I) Next, as a Time group that releases Sc by an intramolecular nucleophilic substitution reaction, there is a group represented by the following formula (Ik).

General formula (Ik) -Nu-D-E- In the formula, Nu represents a nucleophilic group having an electron-rich oxygen, sulfur or nitrogen atom, It binds to the active site of the ring component). E represents an electrophilic group having an electron-poor carbonyl group, thiocarbonyl group, phosphinyl group, or thiophosphinyl group.

This electrophilic group E is bonded to the heteroatom of Sc, and D
is a steric relationship between Nu and E, and Coup (
After Nu is released from the coupling component), 3- to 7-membered
Breaking intramolecular nucleophilic substitution by a reaction accompanied by the formation of a membered ring,
and represents a binding group by which Sc can be released.

Further, scavengers for the oxidized color developing agent represented by Sc include redox type scavengers and coupling type scavengers.

In the general formula CD5R-1), when Sc scavenges the oxidized color developing agent through a redox reaction, the Sc is a group capable of reducing the oxidized color developing agent, such as Angew, Che+s.

Int, Ed, 17875-886 (1978)
, The Theory of the Photographer
aphic Process @ 4th edition (Mac Mil
Reducing agents described in Chapter 11 of LAN1977) and JP-A-59-5247 are preferred, and precursors capable of releasing such reducing agents during development may also be used. Specifically, -
An aryl group or a heterocyclic group having at least two 0H (in the formula, R and R' represent a hydrogen atom, alkyl, cycloalkyl, alkenyl, or aryl) is preferable, and an aryl group is especially preferable, and a phenyl group is preferable. More preferred.

The lipophilicity of Sc is arbitrarily selected depending on the purpose, similar to the couplers represented by formulas (Ia) to (Ih) above.
In order to maximize the effects of the present invention, the total number of carbon atoms in Sc is 6 to 50, preferably 6 to 30, and more preferably 6 to 20.

When the Sc scavenges the oxidized color developing agent through a coupling reaction, the Sc can be a variety of coupler residues, but is preferably a coupler residue that does not substantially form an image-forming color dye. The above-mentioned run-off dye-forming couplers, bleaching dye-forming couplers, and L1eiss couplers that have a non-leaving substituent at the reaction active site and do not form dyes can be used.

Specific examples of DSR compounds include, for example, British Patent No. 1546837, Japanese Patent Application Laid-open No. 150631/1983,
No. 7-111536, No. 57-11537, No. 57-
No. 138636, No. 60-185950, No. 60-2
No. 03943, No. 60-213944, No. 60-21
No. 4358, No. 61-53643, No. 61-8464
No. 6, No. 61-86751, No. 61-102646, No. 61-102647, No. 61-107245,
No. 61-113060, No. 61-231553, No. 61-233741, No. 61-236550, No. 6
No. 1-236551, No. 61-238057, No. 61
-240240, 61-249052, 62-
No. 81638, No. 62-205346, No. 62-28
There are those described in No. 7249, etc.

As Sc, a redox type scavenger can be preferably used, and in this case, the color developing agent can be reused by reducing the oxidized product of the color developing agent.

Next, DSR compounds represented by the general formula CD5R-I) will be illustrated, but the present invention is not limited to the exemplified compounds below.

DSR-I 5R-2 5R-3 5R-4 5R-5 5R-6 5R-7 5R-8 DSR-9 DSR-10 DSR-11 DSR-12 DSR-13 I DSR- 14 D S R-15 5R-16 D S R-18 D S R-19 5R-20 DSR-21 DSR-22 DSR-23 NH5O, CH3 5R-25 u 5R-26 5R-27 N)lsO*N( CH3)z 5R-28 5R-29 5R-30 H NH3O! N(C4B,)! 5R-31 5R-32 n 5R-33 n DSR-34 DSR-35 5R-36 5R-37 5R-38 5R-39 5R-40 O 5R-41 DSR-42 The black colloidal silver used in the present invention can be obtained from, for example, the United States. Patent No. 2
．． No. 688,601, German Patent No. 1, 096.19
It can be easily prepared by the conventionally known method described in No. 3. The black colloidal silver particles used in the present invention preferably consist of a polydisperse with a diameter of 30 to 20 μm, and the optical properties of the colloidal silver particles that can be used in the present invention vary depending on the preparation conditions of the colloidal silver. In terms of sharpness, the relative value at 450 μm is preferably 0.60 or more when the value at 550 μm is 1.00, and the spectral transmittance density value at 550 μm is preferably 1.00. 450μ when set to OO
The relative value in m is particularly preferably 1.00 or more in the range from 0.70 to 1.00.650 μm. If we express these values in concrete terms, the transmission density at 550 μm is 0.5
The value at 0-0.90.450 μm is 0.35-0.90
．． The value at 650 μm is particularly preferably 0.50 or more.

Further, the coating amount of black colloidal silver is preferably 0.50 to 0.40 g/cd, particularly preferably 0.10 to 0.30 g/cd in terms of silver. In terms of desilvering properties in the development process, anti-halation performance, and the clarity of data when forming the photographing date and time by optical exposure from the back side of silver halide color photographic light-sensitive materials, it is suitable for auto-date cameras. The ranges mentioned above are preferred.

The present inventors removed the non-photosensitive layer (intermediate layer), which has been coated for the purpose of preventing the conventionally known increase in fog, from between the black colloidal silver-containing layer and the photosensitive silver halide emulsion layer. The present inventors have discovered that the sharpness and graininess of the light-sensitive silver halide emulsion layer adjacent to the black colloidal silver-containing layer can be greatly improved by using a DSR compound in a structure in which the present invention is removed. In particular, remarkable effects can be obtained in silver halide color light-sensitive materials in which the black colloidal silver-containing layer contains a colored image-forming coupler (ie, a colored coupler) as a condition adjustment during printing by an automatic printer. Furthermore, it has been found that with the configuration of the present invention, contact fog, which was predicted from conventional knowledge, is extremely small.

Preferably, the black colloidal silver-containing layer is adjacent to the support side of the light-sensitive silver halide emulsion layer located closest to the support.

In the present invention, the DSR compound is contained in at least one arbitrary layer of the photographic constituent layers.

Preferably, it can be added to at least one layer of a group of light-sensitive silver halide emulsion layers having substantially the same color sensitivity adjacent to the black colloidal silver-containing layer and/or to the black colloidal silver-containing layer, In addition, a DSR compound that forms the same dye as the dye formed by campling reaction after color development processing, and/or a DSR compound that forms a colorless or colorless dye by coupling reaction, is placed adjacent to the black colloidal silver-containing layer. It is preferable to add it to a photosensitive silver halide emulsion layer.

In the present invention, two or more types of DSR compounds can be contained in the same layer. The same DSR compound can also be used with different
It may be included in more than one layer.

When these DSR compounds are contained in an emulsion layer, they generally contain 2XlO-' to 5X
10-' mol is preferred, more preferably 1 x 101 ~
I x 10-' moles are used.

When added to a non-photosensitive layer, 2X10-' to 5X10-' per mole of silver in an adjacent light-sensitive silver halide emulsion layer and an emulsion layer having the same color sensitivity as the emulsion layer.
molar is preferred, more preferably 1 x 10- to Ix
IQ-'mol.

In order to incorporate these DSR compounds into the silver halide emulsion layer of the light-sensitive material of the present invention or into the N layer of other photographic components, if the DSR compound is alkali-soluble, the emulsion or coating solution must be alkaline. It may be added as a solution, and if it is oil-soluble, e.g.
．． No. 027, No. 2.801.170, No. 2.80
1.171, 2,272.191 and 2.
DS according to the method described in each specification of No. 304.940.
It is preferable to dissolve the R compound in a high-boiling point solvent, optionally in combination with a low-boiling point solvent, and to disperse it in the form of fine particles and add it to a silver halide emulsion or the like.

The above DSR compound is disclosed in Japanese Patent Application Laid-Open No. 57-138638,
l No. 57-155537, No. 57-171334, No. 58-111941, No. 61-53643, No. 84646, No. 61-86751, No. 61-102
No. 646, No. 61-102647, No. 61-1072
It can be synthesized by the method described in No. 45, No. 61-113060, etc.

The silver halide emulsion used in the light-sensitive material of the present invention includes:
Any of the conventional silver halide emulsions can be used.

The emulsion can be chemically sensitized by conventional methods and optically enhanced to a desired wavelength range using an enhancement dye.

In the present invention, at least a portion of the silver halide grains may contain an Hg agent.

In order to obtain a wide exposure latitude, it is possible to mix and use silver halide grains with different average grain sizes, but silver halide grains containing a desensitizer can be used instead of low-sensitivity silver halide grains with small grain sizes. By using this method, it is possible to reduce the difference in average grain size without changing the sensitivity of the silver halide grains, and it is also possible to mix and use silver halide grains having the same average grain size and different sensitivities.

That is, by using silver halide grains containing a desensitizer, a wide exposure latitude can be obtained even if the coefficient of variation of the entire grain is made small.

These silver halide grains with a small coefficient of variation that are exposed to the same environment are preferred because their photographic performance is stabilized against changes over time and fluctuations in development processing.

Furthermore, from the viewpoint of production technology, it becomes possible to chemically sensitize a mixed system of silver halide grains having different sensitivities in the same batch.

As the K-sensitive material, various materials such as metal ions, antifoggants, stabilizers, desensitizing dyes, etc. can be used.

Among these, metal ion doping technology is preferred.

The metal ion used for doping is Cu.

Cd, Zn+Pb+Fe, Tj! , Rh, BitIr
, Au, Os, Pd, etc., and these metal ions can be used, for example, as halogeno complex salts, or can be used in combination of two or more kinds. Further, the pH of the silver halide suspension system during doping is preferably 5 or less.

The doping amount of these metal ions varies depending on the type of metal ion, the particle size of the silver halide particles, the doping position of the metal ion, the desired sensitivity, etc. 10-2 mol is preferred, particularly IQ-Is to 10-4 mol.

Further, when the metal ion is Rh ion, it is preferably 10-14 to 104 mol per mol of silver halide, particularly 1
0-1 to 10-4 mol is preferred.

Furthermore, by selecting the type of metal ion, the doping position and the doping amount, various different sensitivity qualities can be imparted to the silver halide grains.

If the doping amount is less than 10-8 mol/A g X mol, it will have little effect on particle growth.
Silver halide grains with a narrow grain size distribution can be prepared even if the grains are grown under the same grain growth conditions or even in the same batch.

It is also possible to prepare silver halide grains with different doping conditions so that they can be put to practical use, then mix them in a predetermined ratio to form the same batch and apply chemical sensitization. Each silver halide grain accepts exacerbating effects based on its qualities,
An emulsion with a wide latitude can be obtained depending on the sensitivity difference and mixture ratio.

Further, antifoggants, stabilizers, etc. can be added to the silver halide emulsion used in the present invention. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

A coupler is used in the emulsion layer of a light-sensitive material for color photography. That is, in the present invention, any coupler that develops a desired color can be used in the red-sensitive, green-sensitive, and blue-sensitive silver halide emulsion layers.

Furthermore, by coupling with colored couplers, competing couplers, and oxidized forms of developing agents, which have color correction effects, they can be used as development accelerators, developers, halogen reprinting solvents, toning agents, hardeners, fogging agents, and antifogging agents. Compounds that release photographically useful fragments such as agents, chemical sensitizers, spectral sensitizers, and desensitizers can be used.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are leached from the light-sensitive material or bleached during the development process.

A formalin scavenger-2 fluorescent whitening agent, a matting agent, a lubricant, an image stabilizer, a surfactant, a color fog preventive agent, a development accelerator, a development retarder, and a bleach accelerator can be added to the photosensitive material.

The present invention is particularly useful for color negative films, color reversal films, and the like.

As a support, paper laminated with polyethylene, etc.
Any material such as polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

To obtain a dye image using the photosensitive material of the present invention, after exposure,
Commonly known color photographic processing can be performed.

〔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 in the silver halide photographic material is expressed in grams per IM unless otherwise specified. Furthermore, silver halide and colloidal silver are shown in terms of silver.

Example 1 Multilayer color photographic element sample 101 was prepared by sequentially forming layers having the compositions shown below on a triacetyl cellulose film support from the support side.

Sample-101 (comparison) 1st layer; antihalation layer (HC-1) black colloidal silver 0.20 UV absorber (UV-1)
0.20 high boiling point solvent (Oi It -1)
0.20 gelatin
1.5 Second layer; Intermediate layer (rL-1) UV absorber (UV-1) 0.01 High boiling point solvent (Oi 1-1) 0.01 Gelatin
1.5 Third layer; low sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Em-1-■) 066 Silver iodobromide emulsion (Em-2-■) 0.2 Sensitizing dye (SD- 1) 4.0xlO-' (mol/silver 1 mol) Exacerbating dye (SD-2>4.0x10-' (mol/S 1 mol)
mol) Sensitizing dye (SD-3) 0.8X10-4 (mol/silver 1 mol) Cyan coupler (C-1) 0.65 Colored cyan coupler (CC-1) 0.06 DIR compound (D-1> 0.004 High boiling point solvent (Off-1) 0.6 Gelatin
1.5 4th N; High sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (F, m-3-■) 0.8 Enhanced dye (SD
-1) 3.5X10-' (mol/mol silver) Sensitizing dye (SD-2) 3.5X10-' (mol/mol silver) Sensitizing dye (SD-3) 0.2XIO-' (mol /silver 1 mole) Cyan coupler (C-2) 0.16 Cyan coupler (C-3) 0.02 Colored cyan coupler (CC, -1) 0.03 DIR compound (D-2) 0.007 High boiling point solvent (Oil-1) 0.2 gelatin
1.3 5th layer; middle layer (■L-2
) Gelatin 0.7 6th layer; low-sensitivity green-sensitive emulsion layer (OL) Silver iodobromide emulsion (Em-1-■) 0.6 Sensitizing dye (SD-4) 8.0xlO-' (mol/silver) 1 mol) Sensitizing dye (SD-5) 1.6X10-' (mol/1 mol of silver) Magenta coupler (M-1) 0.1 magenta coupler (M-2) 0.2 colored magenta coupler (CM-1 )0.1 DIR compound (D-3) 0.02 DIR compound (D-4>0.004 High boiling point solvent (
Oil-2) 0.3 gelatin
1.0 7th layer; high-range green-sensitive emulsion layer (GH) Silver iodobromide emulsion (Em-3-■) 0.7 Sensitizing dye (SD-6) 2.7X10-' (mol/G1 Mol) Exacerbating dye (SD-7) 4.5 x 10-' (mol/1 mole of silver) Exacerbating dye (SD-8) 1.0 x lO-' (mol/1 silver 1 mole)
Mole) Magenta coupler (M-2) 0.09 Colored magenta coupler (CM-2) 0.04 DIR compound (D-3') 0.006 High boiling point solvent (Oij!-2) 0.5 Gelatin
1.0 8th layer; yellow filter layer (YC) yellow colloidal silver 0
．． 1 color stain inhibitor (SC-1) 0.1 High boiling point solvent (Ofl-3) 0.1 Gelatin
0.8 9th layer: Low frequency blue emulsion layer (
BL) Silver iodobromide emulsion (Em-1-■) 0.25 Silver iodobromide emulsion (Em-2-■'') 0.10 Multiplying dye (SD
-10) 1.1X10-" (mol/1 mole) Yellow coupler (Y-1) 0.5 Yellow coupler (Y-2) 0.1 DIR compound (D-2
) 0.01 high boiling point solvent (Oif-3)
0.3 gelatin 1.0
10th layer: High-speed blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (
Em-3-■) 0.3 Silver iodobromide emulsion (Em-1-■) 0.1 Sensitizing dye (SD-9) IXIO-' (mol/silver 1 mol) Sensitizing dye (SD-10) 3X10-' (mol/silver 1 mol) Yellow coupler (Y-1) 0.30 Yellow coupler (Y-2) 0.05 High boiling point solvent (Oi
l-3) 0.07 gelatin
1.1 11th N: 1st protection 11 (PRO-1
) Fine grain silver iodobromide emulsion (average grain size 0.08.umAg I 2 mol%) 0.2
UV absorber (UV-1) 0.10 UV absorber (UV-2) 0.05 High boiling point solvent (Of
l-1) 0.1 high boiling point solvent (OijF-4)
0.1 formalin scavenger (H3-1
) 0.5 Formalin scavenger (H3-2) 0.2 Gelatin 1.0 12th layer; 2nd protective layer (PRO-2) Surfactant (SU-1) 0.005 Alkali-soluble matting agent (average Particle size: 2 μm) 0.05 Polymethyl methacrylate (average particle size: 3 μm) 0.05 Slip agent (WAX-1) 0.04 Gelatin 0.5 In addition to the above composition, each layer also contains coating aid 5u-2, Dispersion aid 5u-3, 5u-4
, hardeners H-1 and H-2, stabilizer 5T-1, and antifoggants AF-1 and AF-2 were added.

The emulsion used is as follows.

Em-1-■ Average particle size 0.46 μm.

Average silver iodide content 7.0 mol%.

Monodisperse (width of distribution 18%) surface Emulsion containing low silver iodide (2 mol%) Em-2-■ Average particle size 0.30 μm.

Average silver iodide content 2.0 mol%.

Monodisperse (width of distribution 18%) surface silver bromide emulsion Em-3-■ Average particle size 0.81 μm.

Average silver iodide content 7.0 mol%.

Monodisperse (width of distribution 16%) surface image emulsion containing silver iodide (1.0 mol %) The compounds used in the above sample are as follows.

D-I D-2 D-3 D-5 D-6 D-7 D-8 D-9 D-10 C-3 C# C-1 0■ M-1 M-2 H 11+1 υi υV-2 Su -ISu-2 (Mount C) aN' CIFI? 5O1eNa02S-CH
COOCsH+tCIItCOOCJ+v When adding the DSR compound used in the sample described below to each copying layer, a high boiling point organic solvent of the same type as the compound (
Dissolved in tri□cresyl phosphate and ethyl acetate,
It was emulsified and dispersed together with a surfactant in a coid mill.

The black colloidal silver in the first layer was prepared according to Example 4 of U.S. Pat. No. 2,688.1. Photographic element samples 102-109 were also prepared as follows.

Samples 102 to 109 Sample 105 excluding the second layer of sample 101, and sample 1
01.105, the DSR compound shown in Table 1 (g
/rrr) Samples 102-104 and 106-1
09 was produced.

Each sample prepared in this manner was subjected to wedge exposure (square wave chart exposure) using white light, and then subjected to the following development treatment.

Processing process (38℃) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Fresh water washing 3 minutes 15 seconds Amount
Fixation 6 minutes 30 seconds) Water
Wash for 3 minutes and 15 seconds Stabilize
Dry for 1 minute and 30 seconds 60 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 4.75g Anhydrous sodium sulfite 4.25g Hydroxyamine 1/2 sulfate 2.0g anhydrous Potassium carbonate 37.5 g Sodium bromide
1.3g nitrilotriacetic acid trisodium salt (l hydrate) 2.5g potassium hydroxide 1.0g Add water to make 11.

Bleaching solution> Ethylenediaminetetraacetic acid iron (III) ammonium salt 100 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid
Add 10 ml water to bring the volume to 11, and adjust the pH to 6.0 using ammonium water.

Fixer> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.58 Sodium metasulfite 2.3 g Add water to make 11, and adjust to pH=6.0 using acetic acid.

Stabilizing liquid> Formalin (37% aqueous solution) 1.5 m/Konidanx (manufactured by Konica Corporation) 7.5 mj Add 2 water to make 11.

The obtained treated sample was treated with Capri and M in the following manner.
TF and RMS values were measured.

That is, regarding sharpness, a sample exposed to a rectangular chart was measured using a Sakura Microdensitometer Model PDM-5 Type AR (manufactured by Konica Corporation) with a slit width of 300 μm vertically.
, the density is measured using a slit with a width of 2 μm horizontally, the resolution for the input is determined as a percentage value, and M T F (Modu
ration Transfer Function.

n) value was determined. MTF at spatial frequency of 30 lines/mm
It is expressed as a relative value (Sample 11h101 is set as 100).

The RMS value is the density of the minimum density + 0.7 with the aperture scanning area 2
50μm! Find the value 1000 times the standard deviation of the variation in density value that occurs when scanning with a microdensitometer,
It is shown as a relative value of RMS with sample Na1O1 as 100.

Capri is the difference in minimum density between when the above-mentioned processing steps are applied to each sample and when color development is excluded (when the above-mentioned processing steps are applied), and is a relative value with the minimum density difference of comparative sample 101 as O. It was shown in

The results are shown in Table 1.

As is clear from Table 1, samples 106 to 10 of the present invention
It can be seen that in Sample No. 9, the fog MTF and RMS characteristics of the red-sensitive layer were improved compared to Comparative Samples Nos. 101 to 105. Comparative sample 105 shows fog and RMS deterioration due to the removal of the second layer from comparative sample 101, but
In Samples 106 to 109 according to the present invention, even if the second layer is excluded, the inclusion of the DR3 compound in the first layer suppresses fog and improves MTFSRMS.

Example-2 Samples 110-118 were prepared as follows.

(Samples 110 to 118) Colored couplers CC-1 and CM were added to the first layer of sample 101.
-1 was added in the amount shown in Table 2, and Samples 110 to 118 were prepared in the same manner as Samples 102 to 109. The same treatments and measurements as above were performed, and the results are shown in Table 2.

Table 2 shows that Samples 115 to 11B of the present invention have improved MTF compared to Comparative Samples 101 and 110 to 114, and in particular, the MTF improvement effect is remarkable by including the colored coupler in the first layer. Recognize.

Example-3 Samples 119 to 129 were prepared as follows.

(Samples 119 to 129) C- which is the main coupler in the 3rd and 4th layer of sample 101
Samples 119 to 129 were obtained by changing a part of 1, C-2, and C-3 to the amount of the DSR compound color species shown in Table 3 at the DSR compound/main coupler molar ratio, and further excluding the second layer. Created. The same treatments and measurements as above were performed, and the results are shown in Table 3.

As is clear from Table 3, samples 124 to 12 of the present invention
It can be seen that the Capri, MTF, and RMS characteristics of the red-sensitive layer of Sample No. 9 were significantly improved compared to Comparative Samples No. 101 and Nos. 119 to 123.

In particular, samples 124 to 129 of the present invention have a DSR compound in the first layer and/or the third layer in comparison samples having the second N.
Even if a colored coupler is added to the 4th layer in different amounts, and even if a colored coupler is used in the 1st layer, only a slight improvement in the properties of each red-sensitive layer is observed.
It can be seen that by excluding , each additive exhibits a more significant improvement effect.

〔Effect of the invention〕

As described above, according to the present invention, it is possible to provide a silver halide color photographic material with excellent sharpness, graininess, etc.

Claims (1)

[Claims] 1. A silver halide photosensitive material having photographic constituent layers on a support including a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a blue-sensitive silver halide emulsion layer, and a black colloidal silver-containing layer. The material has any of the above-mentioned photosensitive silver halide emulsion layers adjacent to the black colloidal silver-containing layer, and at least one of the photographic constituent layers reacts with an oxidation product of a developing agent to form the oxidation product. A silver halide color photographic light-sensitive material characterized by containing a compound capable of scavenging substances or a compound capable of releasing a precursor thereof.