JPH02256043A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the sharpness and graininess of an image by allowing silver halide particles in emulsions contained in an emulsion layer unit to satisfy specified conditions. CONSTITUTION:The relative standard deviation of the silver iodide contents of separate silver halide particles in all of emulsion contained in at least one emulsion layer unit is regulated to <=20% and singly dispersed flat platy silver halide particles having >=5 average aspect ratio are allowed to account for >=50% of the total projection area of silver halide particles in an emulsion contained in at least one emulsion layer of the emulsion layer unit. The sharpness and graininess of an image are improved.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material with improved image sharpness and graininess.

(Prior Art) Normally, in multilayer color photographic materials having blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers, light scattering by silver halide grains tends to reduce the sharpness of the underlying emulsion layer. It has been known.

U.S. Patent No. μ, 443 H. No. 22;

No. 32,120 describes a color photographic material in which sharpness, sensitivity, and graininess are improved by using tabular silver halide emulsion grains. U.S. Patent No. V, 4133.0≠j discloses that tabular grains in which the AgI distribution within the grain increases from the center to the surface have excellent sensitivity and
It is disclosed that the size ratio is shown.

Further, in JP-A-62-1111j, the silver halide grains contained in all the silver halide emulsion layers are each composed of silver iodobromide containing silver iodide of less than φ molar ratio. It is also disclosed that color reversal photographic materials containing tabular silver halide grains in at least seven layers have excellent color reproducibility.

On the other hand, JP-A-42-/r! ! The issue also states that photosensitive materials using monodisperse tabular silver halide grains have superior image sharpness and graininess compared to those using polydisperse tabular grains, and that JP-A-Sho tJ -isitir discloses a method for preparing the above-mentioned monodisperse tabular grains.

(Problems to be Solved by the Invention) However, the degree of improvement in both image sharpness and graininess is still insufficient by making the emulsion grains monodisperse1. No response has yet been made.

Therefore, an object of the present invention is to provide a silver halide color photographic light-sensitive material that has excellent image sharpness and graininess.

(Means for solving all problems) In a photographic light-sensitive material having at least one silver halide emulsion layer unit having different color sensitivities on a support, all contained in the at least one emulsion layer unit. The relative standard deviation of the silver iodide content of individual silver halogenide grains in the emulsion is 20 inches or less, and the halogenation in the emulsion contained in at least one emulsion layer in the emulsion layer unit is A silver halide color photographic material characterized in that 10% or more of the total projected area of silver grains is occupied by monodisperse tabular silver halide grains having an average aspect ratio of 5 or more.

As described above, by using tabular silver halide grains and adjusting the silver iodide content distribution of all emulsion grains in the emulsion layer unit containing the tabular silver halide grains, the development speed of each silver halide grain can be made uniform. As a result, it has become possible to obtain good image sharpness and graininess that were previously unattainable.

The content of the present invention will be explained in detail below.

The tabular silver halide grains used in at least one emulsion layer in the present invention have one parallel surface.

In the present invention, the "thickness" of a grain is expressed by the distance between the above-mentioned λ parallel planes constituting the tabular silver halide grain.

In the present invention, the aspect ratio of a tabular silver halide grain means the ratio between the diameter and thickness of the grain, and the diameter of a silver halide grain here means the diameter of a circle with an area equal to the projected area of the grain. do.

The tabular grains used in the present invention have an aspect ratio of 5 or more, preferably! ~50, preferably!
~r.

Regarding the proportion of the tabular silver halide grains in the emulsion containing the tabular silver halide grains of the present invention, it is preferably jO% or more (8) and 70% or more, particularly 70% or more, based on the total projected area. It is preferably 20% or more.

The above-mentioned tabular silver halide grains are manufactured by JP-A-4J-/jltI.
By the method described in No. I, it is possible to make the dispersibility state of the grain size and/or thickness of silver norogenide grains monodisperse.

Monodisperse tabular/X silver halide grains in the present invention have a grain size distribution defined by the following formula. In other words, the standard deviation S of the particle size distribution is the average particle size 7
When divided by , the value, that is, the coefficient of variation, is 50% or less.

2 n 1 r In the case of spherical silver halide grains, the average grain size referred to here means the average diameter of the grains, and in the case of grains with shapes other than cubic or spherical, the projected image of the same area is The average value of the diameter when converted into a circular image, where the individual grain size is ri) and the number is J, the above grains with 7 defined by the following formula The diameter can be measured by various methods commonly used in the art. A typical method is Loveland (L
``Particle Size Analysis Method JA, S.

T, M, Symposium on Ride Microscopy /ri! ! It is described in Chapter 2 of ``Theory of Photographic Processes'', co-authored by Haas and James, 3rd edition, published by Macmillan Publishing Co., Ltd. (1946). The particle size can be measured using the projected area of the particle or an approximate diameter. The coefficient of variation value is preferably less than or equal to 2j.

The halogen composition of the tabular grains is preferably silver iodobromide, silver chloroiodobromide, or silver iodochloride. Silver iodobromide, silver chlorobromoiodide, or a mixture thereof is particularly preferred for use in high-sensitivity light-sensitive materials. In this case, the silver iodide content is usually 4c
It is not more than O molti, preferably not more than 0 molti, more preferably not more than /-/Q molti.

The tabular grains may have a uniform halogen composition or may consist of two or more phases having different halogen compositions.

For example, when silver iodobromide is used, the silver iodobromide tabular grains may have a layered structure consisting of a plurality of phases each having a different iodide content. Tokukai Shoj I-//
J, W27, Tokukai Sho! t-//J, No. 921, JP-A-ShojF-49. IIJJ issue, JP-A-Shojter 1/? , Jll
-Hiroshi, Tokukai Akira! Preferred examples of the halogen composition of tabular silver norodanide grains and the intragrain distribution of norodanide are described in No. 3-layer No. 0, etc.

The tabular grains may be formed from (1,11) planes, (too) planes, or a mixture of (///) planes and (100) planes.

In the present invention, the diameter of the tabular silver halide grains is 3.0
It should be less than μm, preferably Q,! ~3°Oμ drop. The thickness is O0≠μm0 layer, preferably 0.3μm or less, OSμm or more, preferably 0.2μm or less.
, or μm or more.

Regarding the formation site of the latent image, the particles may be such that the latent image is mainly formed on the surface of the particle, or the particle may be such that the latent image is mainly formed inside the particle. Furthermore, particles may be used in which a latent image is formed both on the particle surface and inside the particle. Particles in which a latent image is formed inside the particles can be preferably used in the present invention.

The coating amount of tabular silver halide grains is o, i ~ 6° ()
g/m2, preferably 0.3-J, 0g7m2.

Further, the thickness of the layer containing tabular silver halide grains is 0.
3”t, Ofim% especially 0, jM-Hiroshi, Qllm
It is preferable that

Preferred silver halides used in addition to the tabular grains in the photographic emulsion layer of the photographic light-sensitive material of the present invention include silver iodobromide, silver iodochloride, or silver iodochloride, which contains silver iodide of about 4A0 molt or less. It is chemical silver. Particularly preferred is silver iodobromide containing from about 1 mole percent to about 21 mole percent silver iodide.

The above-mentioned silver halide grains include those having regular crystals such as cubes, octahedrons, and dodecahedrons, those having irregular crystal shapes such as spherical and plate shapes, and those having crystal defects such as twin planes. or a combination thereof.

The grain size of the silver halide may be fine grains of about 0.2 μm or less, or large grains with a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion, but it has regular crystals. A monodisperse emulsion having a coefficient of variation of 20% or less is particularly preferable for those with twin crystals, and a coefficient of variation of 3Q% or less for those containing twins.

The crystal structure may be --like, the inside and outside may have different halogen compositions, or it may have a layered structure. Furthermore, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded.

In the present invention, a plurality of emulsions can be mixed in the same emulsion layer, and when a monodisperse emulsion is used, it is easy to create excellent gradations by mixing and using a plurality of emulsions.

In the present invention, the relative standard deviation of the silver iodide content of individual silver halide grains in all emulsions in at least 1 emulsion layer units is 20% or less in each emulsion.

In the present invention, the term "color-sensitive emulsion layer unit" refers to a group of emulsion layers having specific color sensitivities, specifically, red sensitivity, green sensitivity, and blue sensitivity, respectively. The emulsion layer group may consist of one layer or may have two or more layers, but it is preferable to have two or more layers from the viewpoint of improving image quality and controlling gradation.

It is preferable that the relative standard deviation of the silver iodide content of the emulsion contained in the emulsion layer constituting the above-mentioned color-sensitive unit is 20% or less in all of the plurality of color-sensitive units, and that all of the silver iodide contents in the photographic light-sensitive material are It is preferable that the amount of the emulsion constituting the color-sensitive unit is 20% or less.

If the relative standard deviation value exceeds 20%, image sharpness and graininess tend to deteriorate, which is not preferable.

A specific method for measuring the silver iodide content of each grain is as follows. First, dilute the sample emulsion 3 times with distilled water, add proteolytic enzymes such as pronase, and
-00CK Keep for 3 hours to decompose gelatin. Next, the sample is centrifuged to sediment the emulsion particles, and after removing the supernatant, distilled water is added again to redisperse the emulsion particles in the distilled water. After repeating this water washing operation twice, the sample is dispersed on the sample stage. After drying, carbon evaporation is performed and the sample is subjected to measurement using an X-ray microanalyzer. As the X-ray microanalyzer, a commercially available general device may be used, and no special specifications are required. For example, an X-ray micro analyzer EMX-8M manufactured by Takasu Seisakusho can be used. The measurement is carried out by irradiating each particle with an electron beam and measuring the characteristic X-ray intensity of the element in the particle excited by the electron beam using a wavelength-dispersive X-ray detector. The spectroscopic crystal used for the analysis of each element and the wavelength of the characteristic X-ray of each element are as shown in Table 1. In order to determine the silver iodide content of a grain from the characteristic X-ray intensity of each element, a similar measurement is performed on grains with a known silver iodide content, and a calibration curve as shown in Figure 1 is prepared. It is sufficient to prepare a calibration curve in advance and calculate it from the calibration curve.

The relative standard deviation of the silver iodide content of individual silver halide grains in at least/the emulsion layer unit of the present invention is 20
% or less, more preferably 11% or less, particularly preferably io% or less.

Table 1 *2 Rubidium Phthalate Methods for preparing emulsions with a small relative standard deviation of intergrain silver iodide content used in the present invention include the following methods, but are not limited to these methods.

Emulsions consisting essentially of cubic or dodecahedral crystal grains which are mainly (200) planes are disclosed, for example, in JP-A-60-1433.
As disclosed in No. 32, in the presence of a certain amount of silver halide emulsion, the pAg was reduced to 7. It is obtained by mixing aqueous solutions of a water-soluble silver salt and an alkali metal halide by a double jet method to form particles while keeping the particle size constant within the range of 0 to 8.3.

In the more general method of reducing the relative standard deviation of intergrain silver iodide content, so-called core grains made of silver bromide are formed in advance, and then a required amount of a phase containing silver iodide is added as a shell. One example is the method of forming. Of course, a plurality of shell layers may be formed on the outside depending on necessity. In particular, when tabular grains are formed to meet the requirements of the present invention, monodisperse tabular grains as disclosed in JP-A-63-151618 are used as cores.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are subject to research disclosure restrictions17.
643 and 18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

RD17643 RD18716 1 Chemical sensitizer page 23 Page 648 right column 2 Sensitivity enhancer Same as above 3 Spectral enhancer,
Pages 23-24 Page 648 Right column - Super sensitizers Brighteners Antifoggants and stabilizers Light absorbers, filter dyes Ultraviolet absorbers Anti-stain agents Dye image stabilizers Hardeners Binder Plasticizers, lubricants Coating aids surfactant, static inhibitor 24 pages 24-25 pages 25-26 pages 25 pages right column 25 pages 26 pages 26 pages 27 pages 26-27 pages 27 pages 649 right column 649 pages right column ~ 649 pages right column ~ Page 650 Left column 650 Page 50 Right column Page 651 Left column Same as above Page 650 Right column Same as above Same as above Various color couplers can be used in the present invention.
RD) Mukai 17643, ■-C to G.

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4,022,620, No. 4.3
No. 26.024, No. 4.401゜752, Special Publication No. 5
B-10739, British Patent No. 1,425,020,
Same 1st. 476, 760, etc. are preferred.

As magenta couplers, 5-pyrazolone compounds and pyrazoloazole compounds represented by the following general formula (1) are preferred.

General formula (where R1 represents a hydrogen atom or a substituent, X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer, Za, Zb and Zc is methine, substituted methine, =N- or -NH-
, one of the Za-zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. When Zb-ZC is a carbon-carbon double bond, it includes the case where it is a part of an aromatic ring, and it also includes the case where R+ or X forms a dimer or more multimer, and 7. When a, zb or Zc is a substituted methine, the substituted methine may form a dimer or more multimer) General formula [! The compound represented by ] will be explained in detail.

In the general formula (1), the multimer means one having two or more groups represented by the general formula (1) in one molecule, and includes bis forms and polymer couplers. Here, the polymer coupler may be a homopolymer consisting only of a monomer having a moiety represented by the general formula (1) (preferably one having a vinyl group, hereinafter referred to as vinyl monomer), or an aromatic-class amine Copolymers may be made with non-chromogenic ethylene-like monomers that do not couple with the oxidation products of the developer.

The compound represented by the general formula (1) is a 5-membered ring-5-membered ring fused nitrogen heterocyclic coupler, and its color-forming nucleus exhibits isoelectronic aromaticity with naphthalene, which is generally referred to as azapentalene. It has a structure. Among the couplers represented by the general formula (1), preferred compounds are IH-imidine (1', 2b) pyrazoles, IH-pyrazolo [1,
5b] Pyrazole, IH-pyrazolo (5,1-c) (
1,2,4) Triazoles, IH-pyrazolo (1
,5-b)(1,2,4)) riazoles, IH-pyrazolo(1,5-d)tetrazoles and IH-pyrazolo(1,5-a)benzimidazoles, each having the general formula ], (III), (rV), (V), [■]
, and [■]. Among these, particularly preferred compounds are (II) and (V).

(II) (III) (IV) (Vl Substituents Rx, Rs, and R4 in general formulas (n) to [■] are hydrogen atoms, halogen atoms, alkyl groups, aryl groups, heterocyclic groups, cyano groups, and alkoxy groups. , aryloxy group,
Heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imido group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group group, alkoxycarbonylamino group, aryloxycarbonylamino group,
Represents a sulfonamide group, carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group, alkoxycarbonyl group, oryloxycarbonyl group, and X is a hydrogen atom, a halogen atom, a carboxyl group 1, or an oxygen atom or nitrogen Represents a group that bonds to the carbon at the coupling position via an atom or a sulfur atom, and is a group that is decoupled.

The case where RX, Rs, R4 or X becomes a divalent group and forms a bis body is also included. In addition, general formula (If) ~
When the moiety represented by [■] is present in the vinyl monomer, Rt, Rs, or R4 represents a simple bond or linking group, via which the general formula CI! The moiety represented by 3 to [■] and the vinyl group are bonded.

When the compounds represented by general formulas (II) to [■] are present in the vinyl monomer, the linking group represented by Rz, Rx or R4 is an alkylene group (substituted or unsubstituted alkylene, for example, methylene , ethylene, 1.10-decylene, CHz CH* OCHt CHt-1), phenylene group (substituted or unsubstituted phenylene group, for example, 1,
4-phenylene, 1,3-phenylene, -NHCO--
CONH--0- Includes groups formed by combining CO and aralkylene groups (for example, those selected from).

In addition, the vinyl group in the vinyl monomer has the general formula (II)
Preferred substituents, including those having substituents other than those represented by [■], are hydrogen atoms, chlorine atoms, or lower alkyl groups having 1 to 4 carbon atoms.

Acrylic acid, α
- chloroacrylic acid, α-alacrylic acid, and esters or amides derived from these acrylic acids;
Methylene dibis acrylamide, vinyl ester, acrylonitrile, methacrylonitrile, aromatic vinyl compound, itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether, maleic acid,
Maleic anhydride, maleic ester, N-vinyl-2
- and lolidone, N-vinylpyridine, and 2- and 4-vinylpyridine.

It also includes cases where two or more of the non-color-forming ethylenically unsaturated monomers used herein are used together.

Compound examples and synthesis methods of couplers represented by the general formulas [[] to [■] above are described in the documents listed below.

Compounds of the general formula [■] are described in JP-A-59-162548, etc., and compounds of the general formula (II) are described in JP-A-60-436.
No. 59 etc., the compound of general formula (IV) is
No. 27411 etc., the compound of general formula (V) is disclosed in JP-A No. 5
No. 9-171956 and No. 60-172982, etc.
The compound of the general formula (Vr) is disclosed in JP-A-60-33552, etc., and the compound of the -general formula [■] is disclosed in U.S. Pat.
No. 64,432, etc., respectively.

Also, JP-A No. 58-42045, No. 59-214854
, No. 59-177553, No. 59-177554 and No. 59-177557, etc., are applicable to any of the compounds of the above general formulas (n) to [■].

Specific examples of pyrazoloazole couplers preferably used in the present invention are shown below.

(M-3) (M-4) (M-7) (M-8) rlls (M-6) (n)CnH*+ (n)C4H+! (n) C4H* (M-10) (M-12) (M (M-16) (M-17) (n) C* I[+s Hs (M (M (M-18) (M-19) 5Hs (n)C+*Hx+ (M-20) (M-21) (M-24) (MHs (M-22>(M-23> (M-29) Hs Hx (M (M-34) x:y=50:50 These couplers are generally used in an amount per mole of silver in the emulsion layer. 2.times.10" moles to 5.times.10" moles are added, preferably I.times.10" moles to 5.times.10" moles.

In order to satisfy the characteristics required of a photosensitive material, two or more types of the couplers and the like may be used in the same layer, or the same compound may be added to two or more different layers.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052,212.
No. 4,146.396, No. 4,228.23
No. 3, No. 4. 296. 200, No. 2,369.
No. 929, No. 2,801゜171, No. 2,772,
No. 162, No. 2゜895.826, No. 3,772
, No. 002, No. 3.758,508, No. 4. 3
34. No. 011, No. 4,327.173, West German Patent Publication No. 3,329,729, European Patent No. 121゜3
65A, U.S. Patent No. 3,446,622, U.S. Patent No. 4,
No. 333.999, same No. 4. 451. No. 559, No. 4,427,767, European Patent No. 161.626A
Preferably, those described in No.

Colored couplers for correcting unnecessary absorption of coloring dyes are described in Research Disclosure Arashi 17643.
- Section G, U.S. Patent No. 4.163゜670, Special Publication No. 1983
-39413, U.S. Patent No. 4.004,929, U.S. Patent No. 4. 138. No. 258, British Patent No. 1,146,
The one described in No. 368 is preferred.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
．． 570, EP 96,570 and DE 3,234,533 are preferred.

Typical examples of polymerized absorption-forming couplers are U.S. Pat. No. 3,451.820, U.S. Pat. No. 4.080.211, U.S. Pat.
It is described in No. 173, etc.

The molecular weight of the polymer coupler used in the present invention is preferably 10,000 or more, and those from 20,000 to 100,000 are particularly preferably used.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers releasing development inhibitors include the aforementioned RD17643,
Patents listed in Sections ■-F, Japanese Patent Application Laid-Open No. 57-151944
Preferred are those described in No. 57-154234, No. 60-184248, and U.S. Pat.

As a coupler that releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2.097.140;
No. 2.131,188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,150,427, U.S. Pat. , a multi-equivalent coupler described in JP-A No. 4.310.618, a DIR redox compound releasing coupler described in JP-A-60-185950, etc., and a dye that recolors after separation as described in European Patent No. 173.502A. In addition, redox type DIR compounds are also preferably used in the present invention. DIR hydroquinones preferred in combination with the present invention include US Pat. No. 336,402 and US Pat. No. 3,379.
Particularly preferred are JP-A-50-62435, JP-A-50-133833, JP-A-50-119631, JP-A-51-51941, and JP-A-52-57828. This is a compound described in No.

In the present invention, a bleach accelerator-releasing compound represented by the following general formula (II) (hereinafter referred to as a BAR compound) can also be used.

General formula (II) A (TI)! ! (B (Tz)-)-Z In the general formula (n), A is a group whose bond with (TI) 6 or less is cleaved by reaction with the oxidized product of an aromatic primary amine developer, T1 and T, is the timing group and B is (TI)I! After the bond with the above is cleaved, the bond with (Tz)- or less is cleaved by reaction with the oxidized product of the aromatic primary amine developer, and Z is CB-(Tt), , )- or more. l, m and n each represent 0 or 1;

In general formula (n), A specifically represents a coupler residue or a reducing agent residue.

As the coupler residue represented by A, known ones can be used. For example, yellow coupler residues (e.g. open-chain ketomethylene type), magenta coupler residues (e.g. 5-pyrazolone type, pyrazoloimidazole type, pyrazolotriazole type), cyan coupler residues (e.g. phenol type, naphthol type, etc.) ), and colorless coupler residues (eg, indanone type, acetonephenone type). Further, the heterobarber coupler residue described in European Patent No. 249453, U.S. Patent No. 4,315,070, U.S. Pat. No. 4,183.752, U.S. Pat. It may be a base.

When A represents a coupler residue in general formula (II), preferred examples of A are the following general formulas (Cp-1), (Cp-2
) , (Cp-3) , (Cp-4) , (Cp
-5), (Cp-6>, (Cp-7), (Cp-8
), (Cp-9) or (Cp-10). These couplers are preferred because of their high coupling speed.

General formula (Cp-1) Rs lCCHCN HR5! General formula (Cp-2> RsiN HCCHCN HR53 General formula (Cp-3) SS General formula (Cp-4) General formula (Cp-5) General formula (Cp-9) General formula (Cp-6) General formula (Cp -10) General formula (Cp-7) In the above formula, the free bond derived from the coupling position represents the bonding position of the coupling-off group.

In the above formula, Rs+-, R5zs Rs3, R54, R
55sR3 R5? , R5I, Rse, R6 R1+,
If Rhg or Ro contains a diffusion-resistant group, it is selected such that the total number of carbon atoms is from 8 to 40, preferably from 10 to 50; otherwise the total number of carbon atoms is 15.
In the case of a bis-type, telomer-type or polymer-type coupler, the following are preferred, any of the above substituents represents a divalent group and connects repeating units, etc. In this case, the range of carbon numbers may be outside the specified range.

R5I""R6ff, d and e will be explained below. In the following, R4 represents an aliphatic group, an aromatic group or a heterocyclic group, and Raa represents an aromatic group or a heterocyclic group,
R41, R44 and Ras represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

R5I has the same meaning as R41, R3, and Rs
Each a represents the same meaning as R4. R54 is R41R
as R43 Ra + S Ot Represents an N- group, R4,S- group, R4,〇- group, R,5NCON- group, or NmiC- group.

R43R4a Rss represents the same group as R61, Ro and R
8? each has the same meaning as R43, Ra+S- group, R4
30- group, Ra + CON- group, or Raa R,, SO! Represents an N-group. R51l is the same group as R41 and represents the taste group *R59 is a group with the same meaning as R41, 4M Ras Raa R4s group, R4 direct S
- group, halogen atom, or RalN- group,
d represents 0 to 3; when d is multiple, multiple RS
, represent the same substituent or different substituents, and each Rsq may become a divalent group and connect to form a cyclic structure. Examples of divalent groups for forming a cyclic structure include: Here f is an integer from 0 to 4,
g represents an integer from 0 to 2.

R4゜represents a group with the same meaning as R4, S R&+ is R
A group with the same meaning as R41, R1 is a group with the same meaning as R41, R
,, C0NH- group, R410CON H- group, R,, R
4゜R44R4S Represents a halogen atom or Ra + N- group, R4,
represents a group having the same meaning as 4ff R41, a Ra s CON- group, a Raa R,,0-3o□- group, a halogen atom, a nitro group, a cyano group, or a Ra s CO- group. e represents an integer from 0 to 4, and when a plurality of R1 or R63 are present, each represents the same or different.

In the above, the aliphatic group is a saturated or unsaturated, chain or cyclic, straight chain or branched, substituted or unsubstituted aliphatic hydrocarbon group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms.

The aromatic group is preferably substituted or unsubstituted phenyl having 6 to 20 carbon atoms, or substituted or unsubstituted naphthyl.

A heterocyclic group is a substituted or unsubstituted heterocyclic group having 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms, preferably a 3- to 8-membered ring selected from a nitrogen atom, an oxygen atom, or a sulfur atom. It is.

When the aliphatic hydrocarbon group, aromatic group and heterocyclic group have a substituent, typical substituents include halogen atom, R4,〇- group, RahS- group, Ra + S O
! - group, R450GO- group, R4゜R4嘗Ras R4'1 RnqNSO! - group, R1,5Ot- group, Ras
A group having the meaning R4Q, a cyano group or a nitro group can be mentioned. Here Ra
h represents an aliphatic group, an aromatic group, or a heterocyclic group, and R
4? , R41 and R4? are an aliphatic group, an aromatic group, and
The meanings of aliphatic, aromatic or heterocyclic groups representing heterocyclic groups or hydrogen atoms have the same meanings as defined above.

The coupler residue represented by the general formula (Cp-1) is, for example, US Pat. No. 3.933.501, US Pat.
No. 20, No. 4,326,024, No. 4,401.
No. 752, Special Publication No. 58-10739, British Patent No. 1,
No. 425,020, No. 1.476.760, No. 2
It is specifically described in No. 49.473 etc.

-a coupler residues represented by formula (Cp-2) are, for example, U.S. Pat. No. 4,149,886, British Patent No. 1,204;
, No. 680, JP-A-52-154631, etc.

The coupler residue represented by formula (Cp-3) is, for example, JP-A-49-111631, JP-A-54-48540,
No. 55-62454, No. 55-118034, No. 5
No. 6-38045, No. 56-80045, No. 56-1
No. 26833, No. 57-4044, No. 57-3585
No. 8, No. 57-94752, No. 58-17440,
No. 58-50537, No. 58-85432, No. 58
-117546, 58-126550, 58-
No. 145944, No. 58-205151, Japanese Unexamined Patent Publication No. 1973
-170, 54-10491, 54-2125
No. 8, No. 53-46452, No. 53-46453,
No. 57-36577, Japanese Patent Application No. 58-110596,
US Patent No. 58-132134, US Patent No. 59-26729, US Patent No. 3,227.554, US Patent No. 3,432,521, US Patent No. 4.310.618, US Patent No. 4,351.897
It is specifically stated in the number etc.

Coupler residues represented by general formulas (Cp-4) and (Cp-5) are, for example, International Patent Publication No. WO 36101915, International Patent Publication No. WO 86102467, European Patent Publication (EP) 182
No. 617, U.S. Patent No. 3゜061.432, U.S. Patent No. 3,7
No. 05,896, No. 3.725.067, No. 4,50
No. 0,650, No. 4,540,654, No. 4.548
．． No. 89'9, No. 4,581,326, No. 4. 60
No. 7.002, No. 4,621,046, No. 4,675
゜280, JP-A-59-228252, JP-A No. 60-3
No. 3552, No. 60-43659, No. 60-5534
No. 3, No. 60-57838, No. 60-98434,
No. 60-107032, No. 61-53644, No. 6
No. 1-65243, No. 61-65245, No. 61-6
No. 5246, No. 61-65247, No. 61-1201
No. 46, No. 61-120147, No. 61-12014
No. 8, No. 61-120149, No. 61-120150
No. 61-120151, No. 61-120152, No. 61-120153, No. 61-120154,
No. 61-141446, No. 61-144647, No. 61-147254, No. 61-151648, No. 6
No. l-18C1243, No. 61-228444, No. 6
No. 1-250146, No. 61-250147, No. 61
-292143 etc. specifically described.

Coupler residues represented by general formulas (Cp-6), (Cp-7) and (Cp-8) are used, for example, in U.S. Pat.
, No. 212, No. 4,146,396, No. 4,22
No. 8,233, No. 4,296.200, No. 2 and 3
No. 69,929, No. 2,801,171, No. 2.
772. No. 162, No. 2,895,826, No. 3,772.002, No. 3,758,508,
4.334,011, 4.327,173, West German Patent Publication No. 3,329,729, European Patent No. 1
No. 21.365A, U.S. Pat. No. 3,446.622;
4,333.999, 4.451.559, 4.427.767, 4,554,244
European Patent No. 161.626A, European Patent No. 175.573
No. 250゜201, etc.

The coupler residue represented by the general formula (Cp-9) is disclosed in, for example, U.S. Pat. Nos. 3.932,185 and 4.063.9.
It is specifically described in No. 50 etc.

The coupler residue represented by formula (Cp-10) is specifically described in, for example, US Pat. No. 4,429,035.

A typical example of the coupler residue represented by the general formula (Cp-1) is the compound example (Y-
1) to (Y-34) and similarly represented by general formula (Cp-3), compounds (M-1) to (M-56) disclose general formula (Cp-3).
Regarding the coupler residues represented by 4) and (Cp-5), coupler residues represented by the general formulas (Cp-6) and (Cp-7) are determined according to compound examples (M-57) to (M-108). For example compounds (C-1) to (C-56), the coupler residues represented by general formula (Cp-8) are represented by compound examples (C-57) to (C-86), respectively. Examples are disclosed.

The compound represented by the general formula (RI) may be a dimeric or polymeric compound that is bonded to each other at a portion other than Z (preferably A), and specific examples thereof are described in Japanese Patent Application No. 62-90442. has been done.

As the reducing agent residue represented by A, for example, Japanese Patent Application No. 62-2
No. 03997, No. 78 true general formula (II) to page 85 Reducing agent residues represented by general formula (IV) (for example, having the structure of a derivative such as hydroquinone, naphthohydroquinone, catechol, pyrogallol, aminophenol, gallic acid, etc.) residue) is - boat fishing.

The timing groups represented by T and T2 in general formula (I) are used for various purposes (e.g., regulation of coupling activity).
Used as appropriate. Examples of these timing groups include those shown in items (11 to (5) and (7)) from pages 23 to 36 of Japanese Patent Application No. 186939/1982, and among these, the general formula ( Timing groups represented by T-1), (T-2) and (T-3) are preferred.

In the general formula (1), the group represented by B is a group of (TI)J or higher, that is, after separation from T1 or A, a coupler or reducing agent (e.g., hydroquinone, naphthohydroquinone, catechol, pyrogallol, aminophenol, gallic acid, etc.) represents a group that functions as a derivative of T2 or less and releases T2 or less by a coupling reaction or redox reaction.

For example, US Pat. No. 4,438,193, US Pat. No. 461.85
No. 71, JP-A-60-203943, JP-A No. 60-213
There is a description in No. 944 and No. 61-236551, etc.
Specific examples include the following groups.

Here, the umbrella represents the bonding position with T, and ** represents the bonding position with T.

T, 'rz and B are used as appropriate depending on the purpose, but
It is generally preferable not to use it.

Examples of the group represented by 2 in the general formula (fl) include known bleach accelerator residues.For example, U.S. Pat.
893,858, British Patent No. 1138842, JP-A-53-141623, JP-A-53-956;
Compounds having disulfide bonds as described in Japanese Patent Publication No. 53-9854, thiazolidine derivatives as described in Japanese Patent Publication No. 53-94927, isothiourea derivatives as described in Japanese Patent Publication No. 53-94927, Thiourea derivatives such as those described in Japanese Patent Publication No. 45-8506 and Japanese Patent Publication No. 49-26586, Japanese Patent Publication No. 49-498
Thioamide compounds as described in JP-A No. 2349, dithiocarbamates as described in JP-A No. 55-26506, di-diamine compounds as described in U.S. Pat. No. 4,552,834, etc. It is. These compounds have A-(
A preferred example is bonding to T+)4- (El-(T, ), ), -.

The group represented by Z is more preferably represented by the following general formula (Z-
1), (Z-2), (Z-3), (Z-4) or (Z
−5).

General formula (Z-1) -3-L, -(X,).

In general formula (Z-1), a is an integer of 1 to 4, and a
+1-valent linear or branched alkylene group having 1 to 8 carbon atoms; Xl is a hydroxyl group, carboxyl group, cyano group, amino group having θ to 10 carbon atoms, or Acyl group, carbamoyl group having 1 to 10 carbon atoms, sulfonyl group having 1 to 10 carbon atoms, sulfamoyl group having 0 to 10 carbon atoms, carbonamide group having 1 to 10 carbon atoms, 3 to 12 carbon atoms ammonium mil group, ureido group having 1 to 10 carbon atoms, sulfamoylamino group having 0 to 10 carbon atoms, 1 to 6 carbon atoms
represents an alkoxy group, amidino group, guanidino group, or amidinothio group, etc., respectively; however, when a is plural, the plurality of Xl may be the same or different, and Ll is not a cycloalkylene group, and specific examples include Methylene, ethylene, trimethylene, ethylidene, isopropylidene, propylene, 1. 2. 3-7” lopanetriyl, etc.

General formula (Z-2) C is an integer of 0 to 7, and L is an integer of 1 to 3 carbon atoms.
a linear or branched alkylene group of X, and
, has the same meaning as Xl in general formula (Z-1), Yl
is-o--s--5o--coo--oco--oco
o- (However, R1 and R8 are hydrogen atoms or carbon atoms 1 to
Each represents 10 alkyl groups, provided that when b is plural, the plural Ys and -L3 may be the same or different (however, not all Y's are -S-)
In addition, when C is other than O, Xt can be replaced by 2, Y
It can be substituted with either l or Y.

General formula (Z-3) In general formula (Z-2), b is an integer of 1 to 6, W
L, s (S-Ls)b X general formula (Z-4
) In general formula (Z-3), b-, C% Lz, Ll,
Xl and X are Su, C-, L in general formula (Z-2)
The same meaning as l, Ls, XH and X, respectively, W
は-o--s--oco-OS Oz OS O
where R represents N- or -W, -L4-N-, respectively.

R has the same meaning as R8 in the general formula (Z-2>, L4 has the same meaning as L2, Wl has the same meaning as 10-OCOOS Oz
OS represents O- or -N-, respectively, and b
When fJ<plurality, multiple SL3s may be the same or different, and when C is other than 0, Xg is replaceable, W,
Both L□ and □ can be substituted. However, when W is -8-, b is never 1.

In the general formula (Z-4), WSXI and x8 are represented by the general formula (
d is an integer from 0 to 6, and L4 and Ls have the same meaning as W, X, and
~16 linking groups (e.g. alkylene, 10--3--N
- represents an alkylene bonded to each other, where R.

represents the same meaning as R in general formula (Z-2),
When d is other than 0, X can be replaced with any of W, L, and, if possible.

General formula (Z-5) -3-L& -(Xl)β In the general formula (Z-5), represents a cycloalkylene group having 3 to 12 carbon atoms, an arylene group having 6 to 10 carbon atoms, a carbon It represents an unsaturated heterocyclic group having 1 to 10 atoms or a saturated heterocyclic group having 2 to 10 carbon atoms, which may be partially saturated.

In general formula (Z-5), X represents a hydrophilic substituent, preferably a substituent having a π substituent constant of 0.5 or less, more preferably a negative value. What is the π substituent constant?1 Substituent Constant Fore Correlation Analysis in Chemistry and Biology
ts for CorrelationAnalysis
s in Chemistry and Biolog
y), C, Hansch and A, Leo, John Wiley.
This is the value calculated for Xl by the method described in Wiley (1979).

Examples include the following: The π substituent constant is shown in parentheses.

C0NHz (1,49), Cot H (0,32),
C0CH2(-0,55), -NHCOCHa (
-0,97), CH2CH2Co, H(-0,29),
CH2CH2NH! (-0,08), -3CH2c
ot H(-0,31), -CHz cot H(
-0,72), -3CH* C0NJ (-0
,97) ,5GHz C-CHz (0-43
> , -3CHx cHt Cot H(-0
,01), -OH(-0,67), -CONf
(OH(-0,38), -CH,OH(-1,03
), -CN (-0,57), -CH,CN
(-0,57), CH2NH! (-1,0
4) , NHx (1,23), NHCHON
HC0NHz (1,50), -NHCHs
(-0,47), -NH50g CHs (-
1,18) , (-0,98) -OCONHz (-1,05) , -0COCH
3(-0,64), OCH 0,02), 0CHt C0OH(0°87), Sol N+-12(-1,82), -3CH.

Ht Oh.

OCHz CON Hz (1, 37), C
HI CH.

CH.

So.

Na.

In general formula (Z-5), e is O-5, preferably 1-3
represents an integer.

Examples of the group represented by general formula (Z-1) are shown below.

S G Hz G Hz CO□H 3G Hz CH NHz.

S CHZ CHZ CHCOOH1H2 S CHI CHZ N HCHI,Sol(
tCHzNHCOOCHs, SCHt CHl P (ONa)z, CH
l-3CHCOOH.

5CHx CHl SOs K.

S CHz CHz CHz OH--a formula (Z
Examples of the group represented by -2) are shown below.

S CHt CHt S CHz CHz OH.

S CHz CHt S CHz CHz COOH-
3CHHz CHz OCHz CHx OH.

SCHg CHz 0CHz CHz 0H-3CHx
CON HCHz COOH.

Examples of the group represented by -3CHoCHtN (CHzC00H)t and general formula (Z-3) are shown below.

CH1 NH (CHl CHz S) 3 CHI CH
z OH.

0CHt CHt NCHz CHt S CH
l CHl OH.

H5 -NH(CHx CHz S)s CHz C
Examples of the group represented by the general formula (Z-4) are shown below.

OCH!　CHz　S　S　CH＊　CHz　OH.

general formula Below are examples of groups represented by show.

CHt CH.

CH Hz HI O2 Hz (B-2) -N shistt+1 Among the groups represented by general formula (Z-5):

is a heterocyclic group is preferred.

In the compound represented by the general formula (U), A is preferably a coupler residue, T+, Tx and B are preferably not used, and Z is a general formula (Z-1), (Z4), and (Z-5). The groups represented by these are preferred, and the groups represented by (Z-1) are more preferred.

Next, specific examples of the bleach accelerator-releasing compound used in the present invention will be shown.

(B-4) (B-5) CH (B H (B (B (B (B (B) (n) CIz H!S (B-10> CHz CHz 5CHi CHCHz O! (H (B-12) B-16) (B (B-18) (B-21) H3 -N (B-22) (B-23) The bleach accelerator-releasing compound used in the present invention is disclosed in, for example, JP-A-61-201247. , 62-173
No. 467, No. 62-247363, Patent Application No. 61-25
No. 2847, No. 61-268870, No. 61-268
No. 871, No. 61-268872, No. 62-4908
No. 1, No. 62-90442 and No. 62-186939
It can be synthesized by the method described in No.

Bleach accelerator releasing compound (BAR compound) according to the present invention
The amount added to the photosensitive material is lXl0 per 1rf of the photosensitive material.
-' mol to I X I O-' mol is preferred, especially l
Xl 0-mol to 5 X 10"" mol is preferred.

The bleach accelerator-releasing compound according to the present invention can be added to all layers of a light-sensitive material, but it is preferable to add it to a light-sensitive emulsion layer, and furthermore, when it is added to more light-sensitive emulsion layers, it becomes more effective. becomes significant.

The couplers and other organic compounds used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

The steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat. It is written in the number etc.

The light-sensitive material produced using the present invention contains hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol m4, ascorbic acid derivatives, colorless fog,
It may also contain sulfonamide phenol derivatives and the like.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones,
6-hydroxychromans, 5-hydroxycoumarans, spirochroman groups, p-alkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and these Typical examples include ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each compound. Also, (bissalicylaldoximado) nickel complex and (bis-N,N-dialkyldithiocarbamide)
Metal complexes such as nickel complexes can also be used.

The preferred layer arrangement order for the present invention is red sensitivity, green sensitivity, and blue sensitivity from the support side, or blue sensitivity, red sensitivity, and green sensitivity from the support side. Furthermore, each of the above emulsion layers may be made up of two or more emulsion layers having different sensitivities, and a non-light-sensitive layer may exist between two or more emulsion layers having the same sensitivity. Usually, the sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler.
Different combinations may be used depending on the case.

The light-sensitive material according to the present invention includes, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, antihalation layer,
It is preferable to appropriately provide an auxiliary layer such as a back layer.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, Arashi 17643, page 28, and Arashi 18716, 6
It is described from the right column on page 47 to the left column on page 648.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline, 3- Methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methoxyethylaniline and their sulfates, hydrochlorides, and I)-toluenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains pHJl balancers such as alkali metal carbonates, borates or phosphates, and development inhibitors such as bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. Or it is tactile to contain anti-capri agents and the like. Also, if necessary,
Hydroxylamine, diethylhydroxylamine, sulfite hydrazines/phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo[2°2.2]
various preservatives such as octane), ethylene glycol,
m'1B agents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, fogging agents such as the competitive coupler sodium boron hydride, 1-phenyl-3 - of pyrazolidone,
auxiliary developing agents, viscosity-imparting agents, various lactic agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, and diethylenetriamine. Pentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1 diphosphonic acid, nitrilo-N, N, N
-1-rimethylenephosphonic acid, ethylenediamine-N,
N.

Representative examples include N',N'-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. In this black and white developer, known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as -phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol are used alone or Can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, but in general it is 31 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be increased to 500 or less.
It can also be less than mJt. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, it is possible to use a processing method in which bleaching is followed by bleach-fixing, furthermore, processing in two consecutive bleach-fixing baths, fixing before bleach-fixing, or bleach-fixing. A post-bleaching treatment can also be optionally carried out depending on the purpose. Examples of bleaching agents include iron (■), Kobal) (I
Compounds of polyvalent metals such as ff), chromium (Vl), and 14 (II), peracids, quinones, nitro compounds, and the like are used.

Typical bleaching agents include ferricyanide; dichromate; iron(III) or Kobal! -(III), such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or citric acid. , complex salts such as tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. Can be used for As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnalof the 5ociety of Mo
tion Picture and Televisi
on Engineers Volume 64, P, 248-25
3 (May 1955 issue).

The pH of the washing water in the processing of the photosensitive material of the present invention is 4.
-9, preferably 5-8. The washing water temperature and washing time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc.
Generally, a range of 20 seconds to 10 minutes at 15-45°C is selected, preferably 50 seconds = 5 minutes at 25-40°C. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C. Normally, the temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time, or vice versa. It is possible to improve the image quality and the stability of the processing solution by lowering the temperature.

(Example) The present invention will be explained in detail below using examples.

Example I Sample 1 of EM-1 to EM-6 A cubic silver iodobromide emulsion having an average silver iodide content of 5 mol % was prepared using the solutions shown in Table 2.

Solution AKpAg is 1. ．． Solution B and solution Cf were added for 1 minute while adjusting the flow rate of solution C to be 2r.

Furthermore, while adjusting the flow rate of solution E so that pAg was r, 21, the solution and solution E were added for 0 minutes. The obtained emulsion is designated as EM-/.

Solution B and solution C were added to solution A over 3 minutes while adjusting the flow rate of solution C so that pAg was r and cot. Furthermore, the solution and solution E were added over 2Q minutes while adjusting the flow rate of solution E so that pAg was 7.03. The obtained emulsion was designated as EM-2.

Solution B and solution C were added over 3 minutes while adjusting the flow rate of solution C so that solution AKpAg was t, 21. Sara K
While adjusting the flow rate of solution E so that pAg becomes j, jK,
Solution and solution E were added over 2Q minutes. The obtained emulsion is designated as EM-J.

For emulsions EM-/%λ and JK, the nine-average grain size and grain size distribution (indicated by the coefficient of variation above) measured with a Coulter counter, and the intergrain silver iodide content measured with an X-ray i micro analyzer. The distribution is shown in Table 3. The average grain size and coefficient of variation are almost the same for emulsions EM-/, λ, and 3, but the intergrain silver iodide distribution is EM-/, λ,
It increases in the order of 3.

(Relative standard deviation of AgI content) = (Standard deviation of AgI content of individual particles) / (Average Ag
I content ') xio.

The emulsions EM-/, 3 and 3 were desalted and washed with water in a conventional manner, and the pH was adjusted to 6.0 at 43°C. ! , pAgri.

After adjusting to Q, each emulsion was mixed with an aqueous chloroauric acid solution of 7. Oyd, 0. / Sodium thiothiosulfate was added, and chemical ripening was performed at 63 °C for 0 minutes.

Next, by reducing the amount of silver iodide and keeping the temperature at 4A10 (:) when forming grains of EM-/, C, and 3, the average grain size was 0°14m, the coefficient of variation, and the AgI content. Monodisperse emulsions EM-≠, j, and A were obtained in which the relative standard deviations were approximately equal to each other and the average silver iodide amounts were ≠Morti.

Preparation of EM-7 Potassium bromide jugs 50 g of inert gelatin 3 tablespoons of distilled water
．． While thoroughly stirring the aqueous solution dissolved in 71, the double jet method was added to 9. /l/-% potassium bromide aqueous solution and λ0chi silver nitrate aqueous solution were touched for 1 minute at a constant flow rate, ulr 'C, pBr/.

(This addition (I) added 2°4r of the total silver amount
% consumed). Gelatin aqueous solution (77%, 500%)
After stirring at 4I-t"c, -0% silver nitrate aqueous solution was added at a constant flow rate until pBr reached 7.0% (this addition (n) consumed 1.0% of the total silver amount). did)
. Furthermore, potassium iodide t.

A λQ potassium bromide solution containing potassium iodide and a 33% silver nitrate aqueous solution were added over a period of 10 minutes using a double jet method so that 3 g of potassium iodide was added. % consumed). During this time the temperature was maintained at 4Ar 0Q% pBr/IO. The amount of silver nitrate used in this emulsion was 4 c, 27 g, and after desalting by the usual 70 curing method, gold and sulfur sensitization was performed optimally, resulting in an average aspect ratio of t8.2.
, a comparative plate-shaped AgBr with a spherical diameter of 0.1 μm.
I (tJ, Q mol % containing AgI) emulsion EM-y was v! 4#
! did. The relative standard deviation of the intergrain silver iodide content of EM-7 was 7%, and the coefficient of variation was 3r%.

Preparation of EM-I Potassium iodide used for addition ① in EM-7 //,
Subtract 2Q and add an equal amount of potassium iodide ■ Add to potassium bromide and the particle formation temperature! By making it 10C,
The average ascent ratio is 7. A tabular AgBr I (AgI content λ, Q mol %) emulsion EM-1 having an r1 sphere equivalent diameter of 0.6 am was prepared as v14, and the other steps were carried out in the same manner as EM-7 to obtain EM-r. The relative standard deviation of the intergrain silver iodide content of EM-4 was 17%, and the coefficient of variation was 31%.

Preparation of EM-7 Potassium iodide using 111C added in EM-7
By reducing /lO, adding an equal amount of potassium iodide to the potassium bromide in Addition I, and setting the particle formation temperature to 2°C, an average aspect ratio of 7. Tabular AgBrI (AgI content: 2.0 mol) emulsion EM with an equivalent sphere diameter of 0.4 pm
Other steps were carried out in the same manner as for EM-7 to obtain EM-ta. The relative standard deviation of the intergrain silver iodide content of EM-ta was λj%, and the coefficient of variation was 37%.

Preparation of EM-10 o, 0% by weight gelatin solution containing potassium bromide 1. A silver nitrate solution of o, zyl, a 0.4 gM potassium bromide solution, and a 0.1M potassium iodide solution were added to each JQCC in 50 seconds using a double jet method while stirring the mixture. During this period, the temperature was maintained at J (7'C). After the addition, the temperature was raised to 7!0C. Then, 10% of the 1.0M silver nitrate solution was slowly added, and an additional 110g of silver nitrate was added in 10 minutes. It was added at an accelerated flow rate (the flow rate at the end was / times the flow rate at the start).
A KBr solution containing 4g of pBr has a pBr of 2. ! ! It was added to maintain the

Thereafter, the emulsion was cooled to J10C, washed with water by a conventional curing method at 70°C, and pHj was adjusted to 4Ao 0c.

After adjusting the pAgr to 4, the sample was optimally chemically sensitized using sodium thiosulfate, potassium chloroaurate, and potassium thiocyanate.

The obtained nine EM-io has a sphere equivalent diameter o, t μm.

The grains consisted of tabular grains with an average asquite ratio r, i, a coefficient of variation λ1%, and a relative standard deviation of silver iodide content.

Preparation of EM-// In the preparation of EM-10, the amount of potassium iodide solution when adding halogen in the double jet/stage is 1/co, and the temperature after the temperature rise after the first stage is AJ'C. EM-io
Similarly, the equivalent sphere diameter Q is calculated.

1 μm, average aspect ratio r, J, coefficient of variation Ko! E consisting of tabular grains with a silver iodide content relative standard deviation of 11%
M-tt was obtained.

Preparation of EM-/λ In the preparation of EM-10, the amount of potassium iodide solution at the time of halogen addition in the first stage of the double jet is O, and the temperature after the temperature rise after the 7th stage is! ! Same as EM-10 except that the spherical phase diameter was 0°6μm1 average asquite ratio t
EM-/2 was obtained, which consisted of tabular grains with a coefficient of variation of 4c1 and a silver iodide content relative standard deviation of 1.

An emulsion layer having the composition shown below was coated on a cellulose triacetate support which had been subjected to mb to prepare sample 10/, and samples 102 to 10 shown in Table 1 were prepared in the same manner.

1st layer: Antihalation layer Black colloidal silver 0.21 g/m2 Ultraviolet absorber U-10-/g/''2 Ultraviolet absorber U20,/g/m
2 High boiling point organic solvent Oi 1-/0, /CO
/m"Gelatin 1.g/m"
2nd layer: Intermediate layer-7 Cp d -D High boiling point organic solvent 0i1-J Gelatin 3rd layer: Intermediate layer-Co-fogged fine grain silver iodobromide emulsion (average grain size 0.0 μμ, AgI content 1 Mol%) io da/m2 4comisaki/folding 20, reference g/@2 Silver amount 0.01g7m" Gelatin O1μg/m" 1st≠ layer: 1st red-sensitive emulsion layer sensitizing dye S-/and S- Silver iodobromide emulsion EM-/silver amount spectrally sensitized with EM-2 Coupler C-70,2 g/horse2 C20,0 gg/m" High-boiling organic solvent Oi 1/0, /CO
/ m2 gelatin o, r g
/rn" 1st layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-/ and S-2 EM-≠ Silver amount 0, II g/m" 0.2 g/ m2 0, 2 g/expletive 2 0.0! g/lips 20, / cc/folding 2 0.1g7m" Coupler C-/-j C-co high boiling point organic solvent 0il-/ Gelatin 6th layer: 3rd red-sensitive emulsion layer sensitizing dye S-/and S - Silver iodobromide emulsion EM-7 spectrally sensitized with silver amount o, pg/rg2 Coupler C-JO, 7g/drop2 Coupler B-/0, 3 g/s2
Gelatin t, / g/m2
7th layer: Intermediate layer-3 Dye D-10,02 g/m2 Gelatin 0,4 g/m2 1st layer: Intermediate layer-V Overlaid silver iodobromide emulsion (average grain size o-otμ layer, Ag
I content 0.3 mol%) Compound Cpd A O, 2g/Book 2 Gelatin/Ogl door 2 2nd 2nd 1st green emulsion layer spectrally sensitized with sensitizing dyes S-3 and S-p Silver iodobromide emulsion EM-/Amount of silver 0. , tg/rn2 coupler C-≠ o, 10g/□2 coupler (knee 7 0./117g7 field coupler M-/yO,/Og7m2 compound Cpd-B
o, osg/tile 2 gelatin
0, j g /712th io layer: second green-sensitive emulsion layer silver iodobromide emulsion EM containing sensitizing dyes S-J and S-≠
−≠ Silver amount Q, ≠ g/ns” coupler C-4
0, / Og, /z2 Coupler C70, 10g7m2 Cub? -M-/tao, tog/island 2 compound Cpd B O, OJ g/m2 gelatin o, 6g7m2 11th layer:
Third green-sensitive emulsion layer Silver iodobromide emulsion EM-7 containing sensitized colors 51ES-j and S-≠ Silver amount o, s g/coupler C-≠
a, 1g7m" Coupler C-79, Cog/m" Coupler M 15' 0.2g/yn
"Compound Cp d B O, 01g/
m"gelatin / , 0g7m"
12th layer: Middle layer-! Dye D-20.0! g/fold 2 gelatin o, 4 g/shoulder 2
13th layer: yellow filter layer yellow colloidal silver o, ig/door 2 compound Cpd-A 0001g7m2 gelatin
/ , / g/m" 1st layer: 7th blue-sensitive emulsion layer Silver iodobromide emulsion EM containing sensitizing dye 3- and S-j
-/Amount of silver o, Ag/Shoulder 2 coupler C-j
□, 6 g/yx” gelatin
0, r g/shoulder 2 first! layer:
First green-sensitive emulsion layer Silver iodobromide emulsion EM containing sensitizing dyes S-Y and S-A
-4 Silver amount 0.41 g/m2 coupler Cj
O,3g7m"C-40,j g/m" Gelatin 0.9g/m2 Seventh layer: Third blue-sensitive emulsion layer Silver iodobromide emulsion EM containing sensitizing dyes S- and S-4
-7 Silver amount 0,17g 7m” coupler c-go, 7g
/Door 2 Gelatin 1.2g/m2 No. 17
Layer: 1st protective layer UV absorber U-/-J U-Hiro compound Cpd-C dye D-J Gelatin 7th layer: Silver iodobromide emulsion covered with λth protective layer (average grain size 0.04 μm .

0, OAg/m"0.03g7m" o, osg/m2 0.0. tg/yn" 0.0!g/door 2 0, r g/na2 0.0!g/door 2 0.7g/m2 AgI content 1 mol%) Silver amount 0./g/7Fi" gelatin 0, ug/m 1st layer: 3rd protective layer Polymethyl methacrylate (average particle size/--tμrn) 0.1g7m2 Copolymer of methyl methacrylate and acrylic acid (average particle size/,!μm) ) o,/g/yn2 silicone oil 0. OJgl island 2 fluorine-containing surfactant W-/Jg/m” gelatin
o, ag/rI%'' In addition to the above composition, gelatin hardener H-7 and a surfactant were added to each layer.

-j C-san C-/ (t)CSH11 1l-1 0il-dibutyl ophthalate tricresyl phosphate pct-A pa-B cpa-D U-/ -J S-Hiro U-Hiro-g S-/ 1)- / Samples 10i-iio were subjected to the following development treatment after exposure, and the results shown in Table 1 were obtained. Here, the sharpness is the MTF value (λO lines/parrot value), and the granularity (RMS granularity) is the density obtained by scanning with a microdensitometer/1000 times the standard deviation of density fluctuation at 0. was used.

Processing process Step Time Temperature First development Minutes Jr'C water washing
1 minute reversal 2 minutes color development adjustment 1 minute bleaching
Set for 1 minute
Good luck! Washing with water
Stable for 1 minute Dry at room temperature The following composition was used for the treatment solution.

No.-Developer water Nitriro N, N, N-)ri Methylenephosphonic acid thorium salt sodium sulfite Hydroquinone monosulfate onate Sodium carbonate (-water salt) /-phenyl-≠-methyl- ≠-Hydroxymethyl-3 Pyrazolidone potassium bromide potassium thiocyanate Potassium iodide (O, /% solution) liquid) add water reversal liquid water Nitrilo-N, N, N Nitri 00m1 2g 0g 50g 50g 2g λ, jg /, 2g Kod 000m1 00yxl Methylenephosphonic acid thorium salt Stannous chloride (industrial water salt) p-amine phenol Sodium hydroxide glacial acetic acid add water Color developer water Nitrilo-N,N,N-tri Methylenephosphonic acid thorium salt sodium sulfite Sodium triphosphate (/J water salt) potassium bromide Potassium iodide (Q, 7% solution) Sodium hydroxide Citrazic acid N-ethyl-N-(β-meta g /g o, i g g /! d 000x1 700x! g g (sulfonamitoethyl) -3-methyl-hiro-amino Aniline/sulfate j, J-dithiaoctane-/.

! - Add diol water to adjust solution Water Sodium sulfite Sodium ethylenediaminetetraacetate (technical water salt) Add thioglycerin glacial acetic acid water to make ul/g Oyd g/, 1g Bleach solution Water Sodium ethylenediaminetetraacetate (technical water salt) Ethylenediamine tetraacetate Iron(III) ammonium acetate (technical water 11g/g 1000ys1 700g 72g g O, ≠d g o out oost g salt) Add potassium bromide water, fixer water, sodium thiosulfate, sodium bisulfite water Stabilized liquid water formalin (37 weight jIk) Fuji Drywell (surfactant manufactured by Fuji Photo Film) Add water to 720g On a subbed cellulose triacetate film support,
A multilayer color photosensitive material sample was prepared with each layer having the composition shown below.

(Composition of photosensitive layer) The coating amount is the amount expressed in g/m2 of silver for silver halide and colloidal silver, and the amount expressed in g/m2 for couplers, additives and gelatin.
The sensitizing dyes are expressed in moles per mole of silver halide in the same layer.

1st layer (antihalation agent) Black colloidal silver O, cogelatin
1.3ExM-ta
Q, 06UV-10, 0J UV-Co o, otUV-50
, It Solv-/0. /j501v
-λ o, 1zSolv-J
O, 0! 3rd layer (intermediate layer) Gelatin UV-/ ExC-≠ E x p -/ 501v-/ 5olv-λ 3rd layer (low-sensitivity red-sensitive emulsion layer) Emulsion EM-A Coated silver amount Gelatin Ex S -/ ExS -λ Ex C-/ ExC-2 ExC-j ExC-HiroE x C-1 Third layer (high-sensitivity red-sensitive emulsion layer) Emulsion EM-ta Coated silver amount Gelatin l ,O O,03 0,Q Co 0.00 ≠ 0.1 1 l / , r l , O HiroX/ 0-' j×10-5 0.02 0.20 0, OJ O,/λ 0.01 0. 7 / , Q Ex S -1 ExS-CoCo Ex C-A Ex C-7 ExC-HiroSolv-7 Solv-J 5th layer (middle layer) Gelatin cpci-/ 501v-/ 6th layer ( Low-sensitivity green-sensitive emulsion layer) Emulsion EM-j Coated silver amount Gelatin ExS-j ExS-≠ ExS-1 ExM-1 ExM-ta ExM-i.

! ×10−'J×10' θ , /1 0.02 0, OI O, OJ 0.02 Q , j 0.1 0.0! 0,j! l, Q! ×/ 0'-'! ×/ 0-'/x10' O,4L O,07 Q, Q CoExY-//501v-/5olv-≠ 7th layer (high-sensitivity green-sensitive emulsion layer) Emulsion EM-ta Coated silver amount Gelatin Ex S -j ExS-HiroE x S -1 ExM -1 ExM-taExY-// ExC-2 ExM -/≠ Solv-i S01v-≠ th layer (middle layer) Gelatin Cp d -/ 01v -1 0,Q3 0,J O,0! Q, to,! Jxlo-'j' Effect donor layer) Silver iodobromide emulsion (A g I 2 molti, core-shell ratio 22 l internal high Ag I type, equivalent sphere diameter/.

0 μm, coefficient of variation of equivalent sphere diameter lj%, plate-like particle, diameter
Thickness ratio 6.0) Coated silver amount Q,! ! Q,! rxi o-' 0, /1 0, Q3 0.10 0.20 Gelatin ExS-j ExY-/J ExM-/J ExM-14A S01v-/ IO layer (yellow filter layer) Yellow colloidal silver gelatin pd-2 S01v-/ cpci-/ 11th layer (low-sensitivity blue-sensitive emulsion layer) Emulsion EM-A Coated silver amount, Q! ,! , / 3 , l 3 , 7 Q Q , Gu J Gelatin ExS-6 ExC-it ExC-CoExC-J ExY-/j ExY-/j Solv-/ 72nd layer (high sensitivity blue-sensitive emulsion layer) Emulsion EM -ta Coated silver amount gelatin/E x S -6 EXY-/j ExY-/j Solv-/ 13th layer (first protective layer) Gelatin UV-Hiroshi UV-1 501v-/ 7.6 λX/ 0-' 0.0! o,i.

O,02 0,07 /, O O, 2Q Q, j O,j iXio’ 0.2　θ o,oi o,i.

/ j l 501v-20,0/ 7th layer (protective layer) Fine grain silver iodobromide emulsion (AgI comolti, homogeneous AgI type,
Equivalent sphere diameter 0.07 pm) j gelatin o, tr polymethyl methacrylate particle diameter/,! μm 0.2H-70 Protection Cpd-j O, ICpd-4
o, z In addition to the above components, each layer contains emulsion stabilizer CPCT-3.
(0,0 referenceg/expletive 2) Surfactant Cpd-≠(0,0λ
g/m ) was added as a coating aid.

UV-2 UV-Hiroshi UV-/ UV-1 501v-/ 501v-ko tricresyl phosphate dibutyl phthalate 5olv-,y pct-7 Cpd-Hiroshi 501v-da Cp d −j Cpd-/ Cpd-j ExC-co ExC-j ExC-≠ ExC-1 ExM-1 ExM-ta E x M-/ko EXY-/J m01. wt, about ko o, oo.

ExM-10 EXY-// ExM-/4t ExY-/j CHl α EX S -/ ExS-coH-/ ExF-1 il Butyl phthalate (Jl-1 ExS-j ExS-j ExS-4 paB pciD Next, samples 0-07 were prepared in the same manner as sample 07, except that the emulsion used in each emulsion layer was changed as shown in j77.

After exposure, Samples 20/-11O were developed according to the processing steps shown below, and the results shown in Table 5 were obtained. Here, the sharpness is the MTF value (value of 2θ lines/frame), and the granularity (RMS granularity) is the density of the unexposed area obtained by scanning with a microdensitometer, 10! It is expressed as a value 7000 times the standard deviation of the concentration fluctuation at the concentration of .

Processing process Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes liter! Second jf'c ≠! Endurance 7
00m bleaching 1 minute oo seconds JroC20yd
700d bleach fixing 3 minutes/! Second 3t0CJOd
700w1 water wash (2) 1 minute oo seconds jj'c
JOm 7001 stable ≠〇 seconds j
f'c Oxd 700m drying 1
Min/! Seconds! 50C refill amount is 3! ■Width/m Length Next, write down the composition of the treatment liquid.

Color developing solution> Mother solution (g) Replenisher (ω diethylenetriaminepentaacetic acid t, o i, il-hydroxyaminethene-1,/-diphosphonic acid λ, 0 1.2 Sodium sulfite 1.O≠, potassium carbonate
50.0 4A2.0 Potassium Bromide
/, j - potassium iodide
2.0 ■ -Hydroxyamine λ4
Jj da(N-ethyl-N-β-hydroxyethylamine)-2-methylaniline sulfate 1.0 7. J
Add water /l /73p
Hio, oo io, os Bleach solution>Mother solution/replenisher common ethylenediaminetetraacetic acid ferric 7 ammonicum salt /20. Og Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium nitrate 10.011 Ammonium bromide 100.0g Bleach accelerator j X / 0-3 mol Add ammonia water pH 4.3 Add water 1. Bleach-fix solution> Both mother liquor and replenisher are ethylenediaminetetraacetic acid ferric ammonium salt jO, Og ethylenediaminetetraacetic acid disodium salt z, og sodium sulfite l, og ammonium thiosulfate aqueous solution (70 t) λ≠0d ammonia water Add I) H7, J water
If〈Wash water〉 Use tap water with Hffiff cation exchange resin (Mitsubishi Kasei ■
After passing water through a mixed-bed column packed with Diaion SK-/B) and an OH-type strong basic anion exchange resin (Diaion 5A-jO) to obtain the following water quality,
Sodium isocyanurate dichloride cooq as a disinfectant
/l was added.

Calcium ion /, /da/l Magnesium ion 0, ! q/1 pH 4,2 Stabilizing solution> Both mother liquor and replenisher formalin (37% w/v), Od polyoxyethylene-p-soninylphenyl ether (average degree of polymerization/0) 0.3 ethylenediami/tetraacetic acid Conodium salt 0.0! add water
l nor H about t,.

(Effects of the Invention) According to the present invention, a silver halide color photographic material that provides significantly improved image sharpness and graininess can be obtained.

The above effects can be obtained in both color negative and color reversal light-sensitive materials, and the present invention has great practical advantages.

[Brief explanation of drawings]

FIG. 7 shows a calibration curve for measuring the silver iodide content of silver iodobromide grains using an X-ray microanalyzer. The horizontal axis represents the silver iodide-containing group, and the vertical axis represents the characteristic X-ray intensity ratio between iodine and silver. Patent applicant: Fuji Photo Film Co., Ltd. g1ol

Claims (1)

[Claims] In a photographic light-sensitive material having at least one silver halide emulsion layer unit having different color sensitivities on a support, the individual silver halide grains in all the emulsions contained in the at least one emulsion layer unit are The relative standard deviation of the silver iodide content is 20% or less, and 50% or more of the total projected area of the silver halide grains in the emulsion contained in at least one emulsion layer in the emulsion layer unit has an average aspect ratio. A silver halide color photographic light-sensitive material characterized in that it is dominated by 5 or more monodisperse tabular silver halide grains.