JPS6028652A - Photosensitive material comprising silver halide - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material having high sensitivity and improved graininess by specifying density portion and arragement of emulsion layer both having most important relation to the graininess, further specifying distribution of density of developed color to be afforded to each emulsion layer by assingning it positively to each emulsion layer. CONSTITUTION:In at least four emulsion layer Emi having equal color sensitiveness and different sensitivity, if the sensitivity Si of each emulsion layer Emi is S1>S2>S3...Sn, the higher the sensitivity of the layer, the further the layer is arranged from the substrate. Furthermore, with regard to effective highest developed color density Dei generated by color development of the emulsion layer (1), the effective highest developed color density of an emulsion layer having the highest sensitivity S1 is denoted by De1, and De1 is regulated to be <=0.5, (2) Summation of Dei (i=2,3,...,n-1), i.e. SIGMADei of emulsion layer excluding De1, for Emi having highest sensitivity S1, and Den for Emm having lowest sensitivity Sn, is regulated to >0.6, and (3) summation of Dei (i=1,2,3,...,n-1), i.e. SIGMADei of emulsion layer excluding Den for Emn having lowest sensitivity Sn, is regulated to <=1.4.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material having a laminated structure. More specifically, the present invention relates to improving the graininess of dye images when an internal color development method is applied to the light-sensitive material.

(Prior Art) The graininess of a dye image depends on the size and grain distribution of silver halide grains in the emulsion used, the type of coupler, development conditions, and local factors.

Among these, the size of the silver halide grains has the greatest influence, and generally the larger the grains, the worse the graininess. Therefore, it is extremely effective in making grains finer and improving graininess, but on the other hand, when the silver halide composition of grains is the same, sensitivity generally increases with grain size, so high sensitivity is required. In such cases, it is not appropriate to rely solely on grain refinement to improve graininess.

In order to improve graininess with couplers, attention is paid to the reaction equivalent ratio of the coupler, reaction rate, or the use of a colorless coupler, but if couplers are selected by focusing only on graininess, the hue of the dye image and color development are improved. Image gradation is lost due to density formation,
This causes problems in the overall balance of photographic characteristics.

In this way, photographic characteristics are created by the complex interaction of various factors, so it is difficult to improve some of the photographic characteristics, such as graininess, by controlling a single factor, and it is difficult to improve some of the photographic characteristics such as graininess by controlling a single factor. From this point of view, for example, West German Patent No. 1,121,470 @ British Patent No. 923,045
The issue uses a two-layer structure of high and low sensitivity emulsion layers (silver halide emulsion layers), along with coupler selection and control of the amount added, to create separate high and low sensitivity emulsions with the same color sensitivity. The maximum color density of the high-sensitivity emulsion layer is reduced by coating in layers, reducing the amount of coupler added to the high-speed emulsion layer, and using a colorless coupler in combination, and controlling the coloring speed of the coupler to a low level. This paper discloses a method of increasing the sensitivity and keeping the graininess within a range that is not inconvenient in the concentration range that is important for practical use by suppressing the graininess to a much lower value (0.2 to 0.60). In this method, graininess can be further improved by reducing the amount of coupler added to the low-speed emulsion layer, but - large color density and gradation are lost, making this method impractical.

In addition, when applying the high-speed and low-sensitivity emulsion layers as separate layers following the disclosed technique @Tic, oxidation of the color developing agent generated by the development of large silver halide grains in the high-sensitivity emulsion layer is required. The compound (oxidant) diffuses into the low-speed emulsion layer containing a large amount of coupler and develops color, thereby transferring the shadows of the large grains, which is a factor in deteriorating graininess.

In addition, as higher sensitivity is increasingly required, there is a tendency to raise the sensitivity level of the low-speed emulsion layer, that is, to increase the grain size of the silver halide grains in this layer.
The difference between the low-speed emulsion layers is lost, and the disclosed technique is weakened.

With the aim of getting out of this predicament, at least one color-sensitive emulsion layer in the middle of the blue, green, and red-sensitive emulsion layers is made up of three layers: upper, middle, and lower, and the sensitivities are arranged in the order of high, medium, and low. year,
Japanese Patent Publication No. 49-15495 discloses a method for adjusting the maximum color density of the upper and middle layers of the emulsion to 0.6 or less. In this method, between the high-speed emulsion layer containing coarse grains and the low-speed emulsion layer with a high coupler degree, a third emulsion layer having an intermediate sensitive case, an emulsion layer containing no coupler, a simple gelatin layer, and a further layer are added. By inserting a fourth emulsion layer, etc., the interval between the high-sensitivity emulsion layers is widened, and the diffusion spheres of the oxidized product of the color developing agent centering on the coarse particles of the high-sensitivity emulsion layer are diffused as they spread. The concentration of the oxidant in the sphere is diluted, and the contour of the interface of the diffusion sphere is measured, so that the diffusion sphere comes into contact with a low-speed emulsion layer in which graininess is noticeable due to the high coupler placement, and is printed as a color density. This obscures the traces of the diffuse sphere. Therefore, it is not necessary to generate a third emulsion layer or an additional fourth emulsion layer, which is originally introduced, but rather eliminates the coloring contribution of these intermediate-sensitivity emulsion layers. Furthermore, this method forces an increase in film thickness that is unrelated to the color density. Therefore, for the reasons mentioned above, it tends to cause irregularities in the characteristic curve, lack of effective sensitivity, and impair image sharpness.

On the other hand, the demand for higher sensitivity remains high, and small formance requires improved image sharpness, graininess, and faithful tone reproducibility. Demand nine is becoming difficult to deal with.

(Object of the Invention) Therefore, an object of the invention is to provide a silver halide photographic light-sensitive material which is highly sensitive and has improved graininess, particularly in areas where the film is important for practical use.

(Structure of the Invention) The present inventors have conducted various studies for the above-mentioned purpose, and have particularly determined the temperature area that is most involved in graininess, the emulsion layer arrangement, and the color density distribution that should be actively assigned to each emulsion layer. Focusing on this, we proceeded with our research and constructed the non-invention as described below to achieve the object of the present invention.

That is, at least 4 colors having substantially the same 1c color sensitivity and different sensitivities
Emulsion layer Eml (sensitivity 81. i=1.2, 3.
・・・・・・．

In the set of photographic elements of the silver halide photographic light-sensitive material, which comprises at least one set of photographic elements having n≧4) and containing a color-forming coupler provided on a support, in the set of photographic elements of the emulsion layer Em1. Regarding the sensitivity S1, S > st > ss >
...>In the arrangement of the emulsion layers in the photographic element of the set of Sn, (a) 1 ml of the emulsion layer P with high sensitivity S1 is n
In addition, in the effective maximum color density pet generated by the emulsion layer Eml by color development, (b) Regarding the effective maximum color density Del of the emulsion layer Em1 having the highest sensitivity of 81, if Del≦0.5. Yes, (c)
Emulsion layer Emt with maximum sensitivity 81 and minimum sensitivity Sn
The effective maximum color density DeI and D of the emulsion layer Emn having
Effective maximum color density D@1 (1=2.3......, n-1) of emulsion layer EmI with sensitivity Bs excluding en)
In addition, a silver halide photographic light-sensitive material was obtained in which the effective maximum color density D@n of the emulsion layer Emn having the lowest sensitivity Sn is excluded. Maximum color development density Dmi expressed by each layer-1 and each non-photosensitive development density gF+
The difference between them is determined as Dei = (Dmi - Fi).

In the case of non-invention, between the effective maximum coloring density De1, De<=Dez<=Do3<=...<De(n-1
Preferably, it is Den.

Also, at least 18! of a compound (hereinafter sometimes referred to by the symbol D-DIR) that reacts with the oxidized form of a color developing agent to release a diffusible development inhibitor. Emulsion layer EmtiC of the highest sensitivity [St, and a compound (hereinafter referred to as ND-DI) which produces a diffusion-resistant development inhibitor in the same manner as above
It is preferable that at least one of the following (sometimes represented by the symbol R) be contained in at least the emulsion layer Emn having the lowest density DI S n.

Furthermore, it is desirable that at least the emulsion layer ErrIIVc with the highest sensitivity S1 contains a monodisperse emulsion, and the silver iodide grains of the monodisperse emulsion contain silver iodide in the core and shell portions. A core/shell type with different ratios is preferred.

In the present invention, optical conditions during exposure, intra-layer and interlayer interactions during development processing, or interactions from a developing processing solution in a photographic element incorporated in a silver halide photographic light-sensitive material (hereinafter abbreviated as "photosensitive material") are disclosed. In addition, the degree of color development that actually occurs due to the addition and withdrawal of factors that affect the photographic properties of l- is a problem, so
Solubility measurements for dropping point determination of conditions given to photographic elements are
Each layer of the photosensitive material processed under the formula conditions is carefully punctured and measured.

That is, first, a sample of the photographic material prepared according to the present invention is subjected to the following processing steps by applying an intervening exposure source and using the following developing solution, and then measuring the transmission density with a densitometer while sequentially peeling off the constituent layers of the photographic element. The density of each emulsion F is measured, and the non-photosensitive development density, such as the blade support density, fog density, mask density, etc., is left unchanged from the unexposed original and processed in the same manner as above, and each emulsion F! jErns
r Em2+ Em3+ --+ Each D for each Emn
ml, Dmz, Dm3. --, pmn and F
” r F2HF3 , ..., Fn, each Dmi and Fi (1=1.2゜3, -.= , n
) was claimed as Del = (Dmi - Fi).

The maximum color development in the invention is the maximum density of the layer obtained in 1G after the development process described below.

The light source during exposure is light in a wavelength range that matches the color sensitivity of the emulsion layer through a filter, and the Tt exposure amount is set so as to obtain the maximum density.The densitometer is a Macbeth model. Concentration 9p (using S tntusM filter)
0'il''I: h'5 samples were exposed to 4 clouds through a stepped gray wedge with a density difference of 0.15, and then processed according to the processing steps below.

Processing process (38℃) 9114 Physical time color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Fixation 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Stabilization 1 minute 30 seconds Used in each processing step The composition of the treatment solution was as follows.

Color Developer Composition: Footprint Solution Composition: Stabilizing Solution Composition: In a non-inventive practical embodiment, photographic elements of said set of photographic elements having substantially the same color sensitivity and high sensitivity (Sl ), medium (82183; 8z, > S3
) has a sensitivity of s low (S4) and contains a coupler,
The photographic element includes four layers of high sensitivity emulsion layer Em1, medium sensitivity emulsion layer Emz p Em3, and low sensitivity emulsion layer Em4, and the four emulsion layers are is Em+ −Em2− Em from the side farther from the support.
An example is an emulsion layer arrangement in the order of 3-Em4.

The emulsion layer arrangement (Eml-Emz-Ema-Em4
) and Em+ −Emz + Emz −Ems
p E+n++ -Em4 each (7) fh There is no problem in providing an auxiliary layer between the agent layers to assist or supplement the photographic function, such as a scavenger layer.0 Also, it has sufficient color sensitivity of blue sensitivity, edge sensitivity, and red sensitivity. Color-forming couplers having a complementary color relationship for each color-sensitive wavelength range may be assigned to each set of photographic elements in the usual manner, or the combination of color sensitivity and color-forming hue of the color-forming coupler may be determined using the photographic material. It may be changed as appropriate depending on the aspect. A colored coupler may also be used if necessary.

Next 1. The thickness of each emulsion layer, interlayer gap, and amount of color coupler added should be determined by taking into consideration the diffusion behavior of the oxidized color developing agent, effective concentration, developability, sharpness, etc., which greatly affect graininess.

The layer thickness of the emulsion layer Emi is such that a colored mass with an unclear outline (hereinafter referred to as a dye cloud) is formed in the diffusion sphere of the oxidized product of the color developing agent.
The thicker the VC is, the better.

It also varies depending on the type and amount of coupler added, and sharpness and developability require a thin layer.

For example, EII+1 (
+ = 1.2.3.4) for each EmiO layer thickness: Em1'13.0''-4,0 μm Em2 j 1.5-2.5 tt E+n3; 1.5 ~2.5 N Em4 ; 2.0 ~ 3.0 /1 is preferred, and a 5 & C auxiliary layer may be added as described above. The total layer thickness of the set of photographic elements is 80 ~ 12.0 μm.
In the present invention, the emulsion layer Em
Although there are no particular restrictions on the type of color-forming coupler used for i, it is more effective to use a coupler with a slow color-forming rate to lower the probability of trapping the oxidized color developing agent as a measure to conveniently form the dye chiz. From the same point of view, it is more preferable to use a 4-equivalent coupler than a 2-equivalent coupler. However, the coupler is not limited to these couplers and should be selected based on comprehensive judgment.

Phenol compounds and naphthol compounds are preferable for the diffusion-resistant cyan coupler used in the present invention, such as U.S. Pat. No. 2,369,929, U.S. Pat. , No. 895, 826,
No. 3,253,924, No. 3,034,892, No. 3,311.476, No. 3,386,301, No. 3
．． No. 419,390, No. 3,458,315, No. 3,
No. 476.563, No. 3.591,383, etc., and methods for synthesizing these compounds are also described in the references.

Specific examples of cyan couplers particularly useful in the VC of the present invention will be described below.

C-11-hydroxy-N-[δ-(2,4-di-t-
amylphenoxy)butyl]-2-su7tamideC-21-hydroxy-N-(γ-(2,4-di-t-
amylphenoxy)propyl]-2-su7tamide C'3 2,4-dichloro-3-methyl-6-(2゜4
-di-t-amylphenoxyacetamide)phenol C-42,4-dichloro-3-methyl-6-[α-(2
,4-di-t-amylphenoxy)butyramide]phenol C-52-perfluorobutyramide-5-[α-(2
, 4-di-t-amylphenoxy)hexanamide] phenol C-61-'hydro-4-(octadecylsuccinimide)-N-ethyl-3/, 5/-dicarboxy-2-naphthamide C -71-hydroxy-4-anilinocarbonyloxy-N-[δ-(2,4-di-tert-amylphenoxy)butylcy-2-naphthamide C-81,2-bis-(4-hydroxy-3-[N- [
δ-(2,4-ditert-7-phenoxy)butyl]carbamoyl]-1-naphthyloxycarbamino)ethane C-91-Hydroxy-4-(ethoxycarbonylmethoxy)-N-[δ-(2, 4-G tert-
amyl)butyl]-2-su7tamideC-101-Hydroxy-4-[β-methoxyethylaminocarbonylmethoxy)-N-[β-(2,4-di-tert-amylphenoxy)butylcy2-naphthamideC- 112-chloro-3-methyl-4-carboxymethoxy-6-[β-(2,4-di-tart-amylphenolbutyroylamino]-phenol C-121-hydroxy-4-methoxycarbonyloxy-N- Dodecyl-2-naphthamide C-131-hydroxy-4-(4-)luenesulfonamide > -N-(:β-(2,4-tert-
amylphenoxy)butylcy2-naphthamideC-141-hydroxy-4-(1-(naphthylaminocarbonyloxy1-N-Cδ-(2,4-di-ta)
rt-amylphenoxy)butylcy2-naphthamide C-151-hydroxy-4-[α-(β-methoxyethoxycarbonyl)ethoxy]-N-(β-(2,4-
Di-tert-amiA, phenoxy)butylcy 2-naphthamide C-161-hydroxy-4-C4-(β-
carboxypropanamide)-phenoxy]-2-(N
-Cδ-(2,4-di-tart-amylphenoxy)butylamino]) naphthoic acid amide C-171-Hydroxy-4-(β-methylsulfonylmethoxyl-2-(N-hexadecyl)-naphthoic acid amide Diffusion-resistant colored cyan couplers used in US Pat.
No. 908, No. 3,034,892, British Patent No. 1.25
No. 5,111, JP-A-48-22028, JP-A No. 50-1
No. 23341, No. 50-10135, U.S. Patent No. 3, 4
It is described in No. 76.563 etc. together with the synthesis method.

Specific examples of colored cyan couplers advantageously used in the invention are as follows.

CC-11-hydroxy-4-(2-acetylphenylazo)-N-(:β-(2,4-di-t-amylphenoxy)butyl]-2-naphthamide CC-21-hydroxy-4-(2 -(β-phenylpropionyl)phenylazo)-N-[β-(2,4-di-t-amylphenoxy)butylcy2-naphthamide CC-31-hydroxy-4-phenylazo-41-(
4-tert-butylphenoxy)-2-naphthanilide CC-41-hydroxy-4-(4-(1-hydroxy-8-acetamido-3,6-disulfo-2-naphthylazo)phenoxy]-N-[β-( 2,4-di-t-amylphenoxybutyl]-2-naphthamide disodium salt CC-51-hydroxy-4-(4-(2-hydroxy-3,6-disulfo-1-naphthylazo)phenylcarbamoyloxy ]-N-(β-(2,4-di-t-amylphenoxy)butylcy 2-naphthamide disodium Hanawa CC-61-hydroxy-4-(2-ethoxycarbonylphenylazo)-N-Cδ- (2 ,4-di-t-amylphenoxy)butylcy2-
Diffusion-resistant magenta couplers used in the naphthamide invention include compounds such as pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, and indasilon threads. As pyrazolone magenta couplers, US Pat. No. 2,600°788 and US Pat.
No. 53, No. 3,127,269, No. 3,3] -1゜4
No. 76, No. 3,419,391, No. 3,519,42
No. 9, No. 3,558゜318, No. 3,684,514
No. 3,888,680, JP 11i149-29
No. 639, No. 49-111631, No. 49-1295
No. 38, No. 50-13041, Special Publication No. 54-1049
Compounds described in No. 1, No. 53-47167, and No. 55-30615: Described as birazolone triazole magenta couplers in U.S. Patent No. 1,247,493 and Belgian Patent No. 792.525 Compound: As a birazolinobenzimidazole magenta coupler, U.S. Patent No. 3,061,432, West German Patent No. 2
, No. 156,111 and Japanese Patent Publication No. 46-60479; and as an indashilon magenta coupler, the compound described in Berly Patent No. 769,116 can be advantageously used.

Specific examples of magenta couplers particularly useful in the present invention are described below.

M-11-(2,4,6-dolichlorophenyl)-3-
(3-(2,4-di-t-amylphenoxyacetamide)penzamidecy5-pyrazolone M-21-(2,4,6-)lichlorophenyl)-3-
(3-dodecylsuccinimidobenzamide)-5-pyrazolone M-34,4'-methylenebis(1-(2,4,6-dolychlorophenyl)-3-[:3-(2,4-di-t-
amylphenoxyacetamide) penzamide sea 5-
Pyrazolone 1M-41-(2,4,6-lichlorophenyl)-3-(2-chloro-5-octadecylsuccinimideanilino)-5-pyrazolone M-51-(2-chloro-4,6-dimethylphenyl)
-3-(3-(α-(3-pentadecylphenoxy)bunalamide]h7amide)-5-pyrazolone M-61-(2,4,6-)lichlorophenyl)-3-
(2-chloro-5-1tadecylcarbamoylanilino)-5-pyrazolone M-71-(2,4,6-)lichlorophenyl) -3-(3-(2,4-di-t-amylphenoxy) hexylamide)penzamidecy5-pyrazolone M-83-ethoxy-1-14-(α-(3-pentadecylphenoxy)butyramido]phenyl)-5-pyrazolo/M-9' 1- (2,4,6 −)lichlorophenyl)
=3- (2-chloro-5-tetradecanamide anilino) -5-pyrazolone M-101-(2,4,6-)lichlorophenyl) -
3-(2-chloro-5-[α-(3-butyl-4-
hydroxyphenoxy)tetradecanamide anilinone kabilazolone M-111,-(2,4,6-)lichlorophenyl)-
3-C3-(2,4-di-t-amylphenoxyacetamide)penzamidocou 4-acetoxy-5-pyrazolone M-121-(2,4,6-)lichlorophenyl)-3
-[:3-(2,4-di-t-amylphenoxyacetamide)penzamide-4-ethoxycarbonyloxy-5-pyrazolone M-131-(2,4,6-)rif'10phenyl)-
3-C3-(2,4-di-t-amylphenoxyacetamide)penzamide]-4-(4-chlorocinnamoyloxy)-5-pyrazolone M-141-(2,4,6-)lichlorophenyl-3 −
(3-(4-n-dodecylbenzenesulfonamide)petzamide)-5-pyrazolone M -154,4'-benzyldenbisC1-(2,4
,6-dolichlorophenyl)-3-(2-chloro-5-
[γ-(2,4-di-t-amylphenoxy)butyramide]anilino)-5-pyrazolone] M-164,4'-Benzyldenbis CI -(2,3
,4゜5.6-pentachlorophenyl)-3-(2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butyramide]anilinoto-5-pyrazolone) M -174,4'-( 2-chloro)penzyldenbisCI-(2,4,6-)lichlorophenyl)-3-
(2-chloro-5-dodecylsuccinimide anilino)
-5-pyrazolone]M-184,4'-methylenebis[
: 1- (2,4,6-)lichlorophenyl) -3
-13-(α-(2,4-di-t-amylphenoxy)
Butyramide [benzamide F-5-pyrazolone] As the diffusion-resistant colored magenta coupler used in the invention, generally a compound in which the coupling position of a colorless magenta coupler is substituted with arylazo is used. Patent No. 2.801,171, Patent No. 2,983,608, Patent No. 3,005,712, Patent No. 3
．． 684.514, British Patent No. 937.621, and JP-A-49-123625 and JP-A-49-31448. Furthermore, U.S. Patent No. 3,41
Colored magenta couplers of the type described in No. 9,391, in which the dye flows out into the processing solution by reaction with an oxidized form of a developing agent, can also be used. Specific representative examples can be listed below.

CM-11-(2,4,6-dolichlorophenyl)-4
-(4-methoxyphenylazo-3-(3-(2,4-
di-t-amylphenoxyacetamido)penzamide)-5-pyrazolone CM-21-(2,4,6-drichlorophenyl)-4
-(1-naphthylazo)-3-(2-chloro-5-octadecenylsuccinimidoanilino)-5-pyrazolone CM-31-(2,4,6-)lichlorophenyl)-4
-(4-hydroxy-3-methylphenylazo)-3-
(2-chloro-5-tetradecanamide anilino) -
5-Pyrazolone CM-41-(2,4,6-)RikuIrov-Nil)-4
-(4-hydroxy-3-methylphenylazo)-3-
(2-chloro-5-octadecenylsuccinimidoanilino)-5-pyrazolone CM-51-(2,4,6-dolichlorophenyl)-3
-(2-chloro-5-[α-(4-hydroxy-3-t
-butylphenoxy)tetradecanamide anilino)-
4-(1-naphthylazo)-5-pyrazolone CM-61-(
2,4,6-)lichlorophenyl)-3-(2-chloro-5-[α-(2,4-di-t-amylphenoxy)butyramide]anilino)-4-(4-methoxyphenylazo)- 5-Pyrazolone CM-71-(2,4,6-)lichlorophenyl)-3
-(2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butyramide]anilino)-4-(4-hydroxyphenylazo)-5-pyrazolo7 CM-81-(2,3 ,4,5,6-pentachlorophenyl)-3-(2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butyramide]
Anilino)-4-(4-hydroxyphenylazo)-5
-Pyrazolone As the diffusion-resistant yellow coupler used in the present invention, an open-chain ketomethylene compound has conventionally been used, and the generally widely used benzoylacetanilide type yellow coupler and pivaloylacetanilide type yellow coupler can be used. I can do it. Furthermore, second-generation yellow couplers in which the carbon atom at the coupling position is substituted with a substituent that can be removed during the coupling reaction are also advantageously used. Examples of these are U.S. Patent 2
, No. 875,057, No. 3,265,506, No. 3,
No. 664,841, No. 3,408,194, No. 3,4
No. 47,928, No. 3,277.155, No. 3.41
No. 5,652, Japanese Patent Publication No. 13576, 1973, Japanese Patent Publication No. 1973
-29432, 48-66834, 49-10
No. 736, No. 49-122335, No. 50-2883
No. 4, No. 50-132926, etc., along with the synthesis method.

Specific examples of yellow couplers that are particularly effective in the present invention are described below.

Y-1α-(4-carboxyphenogyo-α-bivalyl-2-chloro-5-[γ-(2,4-di-t-amylphenoxy]butyramide)
Acetanilide Y-2α-Bivalyl-2-chloro5-[γ-(2I4
-di-t-amylphenoxy)pudylamido]acetanilide Y-3α-benzoyl-2-chloro-5-[α-(dodecyloxycarbonyl)ethoxydicarbonyl]acetanilide Y-4α-(4-carboxyphenoxy)-α-piparyl 2-chloro5-[α-(3-pentadecylphenoquine)butyramide]acetanilide Y-5α-(1-benzyl-2,4-dioxo-3-imidazolidinyl)-α-bivalyl-2-chloro5-[
γ-(2,4-di-t~amylphenoxy]butyramide]acetanilide y-6α-C4-(1-benzyl-2-pheco-3.
5-dioxy-1,2,4-triazolicinyl)]-]
α-Vivarylu 2-chloro5-γ-(2,4-note
-amylphenoxy)butyramide]anidoanilide Y-7α-acetoxy-α-(3-[α-(2゜4-di-t-amylphenoxy)butyramide]benzoyl 1
-2-methoxyacetanilide Y-8α-(3-[α-(2,4-di-t-amylphenoxy)butyramide]benzoyl)-2-methoxyacetanilide Y-9α-(4-(4-benozylphenoxy) phenylsulfonyl phenoxy]-α-pivalyl 2-chloro 5-C
r-(2,4-not-amylphenoxy]butyramide]y -io α-pivalyl α-(4,5-dichloro-3(2H)-pyridazol-2-yl)-2=chloro-5-C( hexadecyloxycarbonyl)methoxycarbonyl]acetanilide Y-11α-bivalylα-(4-CP-chlorophenyl)-5-oxo-Δ2-tetrazolin-1-yl]-
2-Chloro-5-(α-dotecyloxycarbonyl)acetanilide Y-12α-(2,4-dioxo-5,5-dimethyloxazolidin-3-yl)-α-biparyl-2-chloro5-[α-( 2,4-di-t-amylphenoxy)butyramide]acetanilide Y-13α-vivalyl α-(4-(1-methyl-2-
Phenyl-3,5-dioxo-1,2゜4-triazodinyl〕-〕2-chloro5-γ-(2,4-di-t
-amylphenoxy)butyramide]acetanilide Y
-14α-Vivalyl α-C4-(p-ethylphenyl)-5-oxo-Δ2-tetrazolin-1-yl]-
2-chloro-5-Cr-C2,4-di-t-amylphenoxy)butyramide]acetanilide Y-15α-(4'-methoxybenzoyl)-α-pyrazolyl-2-chloro-5-dodecyloxycarbonylacetanilide Y -16α-Bivalyl α-(1-benzyl-2-7-enyl-3,5-dioxoimidacillin-4-yl)-2
'-Chloro-5'-[α-(dotecyloxycarbonyl)pentoxydicarbonyldiacetanilide] The amount of the above-mentioned diffusible coupler used in the present invention can be determined, for example, from the Emir listed in the Practical IL Embodiments section above.

In the photographic element consisting of 2, 3.4).

Emx; 0.005-0.016 mol/Agx mol Emz; 1), 005-0.026 Kma; 0
．． It is preferable that it is 005-0.030 Erxus O,030'-0,150.

Various methods can be used to disperse the diffusion-resistant coupler, such as the so-called alkaline aqueous dispersion method, solid dispersion method, latex dispersion method, oil-in-water emulsion dispersion method, etc. The chemical structure of the diffusion-resistant coupler, etc. It can be selected as appropriate.

Next, the compound CD-DIR)id which reacts with the oxidant of the color development main storage according to the present invention and releases a diffusible development inhibitory substance.
It is preferable to have a development-inhibiting group represented by the general formula [I].

Margin below General formula [1] J 1 In the formula, R' represents a haalkyl group.

The alkyl group represented by R1 is preferably an alkyl group having 1 to 4 carbon atoms, such as methyl group, ethyl group, 1-propyl group, n-propyl group, n-butyl group, 5ec-butyl group, tert -butyl group, etc., @
It may have a substituent, and examples of the substituent include preferably a methoxy group, an ethoxy group, a hydroxyl group, or a carboxy group.

Next, the D according to the above-mentioned FMw used in the present invention
- A specific representative example of DIR is shown.

Margin below [Exemplary compounds] -1 (J -2 N=N CH, CHOH -4 C, Hp (s) -5 C1H.

-6- 7 C,H.

-8 A-9 A-10 H -11 H3 -12 -13 N=N -14 l I N=N -15 TJ -16 A -17 C/ N2N -18 1 N=N -19 A -Additional It is preferable that at least one kind of D-DIR is contained in the emulsion layer Em1 having the highest sensitivity S, and furthermore, in the other emulsion layer Kmi (1=2.3."...
”.

It is most preferable to include it together with n).

D-DIR together with emulsion layer-1 (1=1.2. aS
+, il), the content should be determined in terms of its content.
It is preferable to put it in a relative relationship of mn.

Emulsion layer Eml (1=1.2.3....., n
) D-DIR total addition to a set of photographic elements consisting of ■
is 0.05 to 10 mol % based on silver halide, and taking as an example a photographic element consisting of emulsion layers Eml (1=1.2.3.4), the addition ratio to each emulsion layer Eml is:
Regarding the distribution of the total addition amount, Eml; 50-100% Em2; 0-30% m3z O-15% Em4; 0-15% preferably n Emx; 50-60%, Em2;
20-30%, Em3; 5-15%, ""4 z
It is 5-15%.

Next, the ND-DIR according to the present invention preferably has a development inhibiting group represented by the following general formula [■] or [decoy].

General formula [■] General formula [In the formula, R''t-j halogen atom, acylamino group C Example 3 Zolinylidene amino group (herein, R3U is an aryl group or an alkyl group having 1 to 4 carbon atoms, For example, it represents an alkoxy group (which may be substituted with an alkoxy group, a halogen atom, or an aryl group), an alkoxy group substituted with a phenyl group (eg, benzyloxy), and the like.

In addition, in the general formula [dish], X represents a group of nonmetallic atoms required to complete a 5- or 6-membered heterocycle; Those represented are particularly preferred.

General formula [In the related formula, R't- is a hydrogen atom, a halogen atom, a nitro group,
Alkoxy group (e.g. alkoxy group having 11 to 4 carbon atoms), alkyl group (e.g. alkyl group having 1 to 4 carbon atoms), ami7 group, acylamino group (e.g. alkylamino group having 1 to 4 carbon atoms) group), hydroxy,
Represents a carboxy, sulfo, or sulfamoyl group.

Next, specific representative examples of ND-DIR having a development inhibitor group represented by the above general formula [■] or [N] used in the present invention will be shown.

Margin below ”、−・′ -1 -2 ■ CH.

-3 -4 1 Hs -5 -6- 7 -8 -9 L amount CH3 -10 CH.

Hs -11 CH.

-13 -14 -15 -16 1 CH3 B-18 -20 ■ CH.

-21 H -N B - Jun p -25 ; - is R 1’J=N B-27 C/ B-column C,H.

B - concave -31 -32 C/ -N B - O C2H.

B-a Ri-a Ri-36 -N -37 -N B-40 B-41 -42 B - Seal −6 -46 -47 0 ■ −48 -49 R -50 l ― (J13 B-51 C/ -55 B - Seki t;uuc4u.

-57 ll -58 R B -■ The ND-DIR is preferably contained in an emulsion layer Emn having the lowest sensitivity Sn in a set of photographic elements; Emulsion layer Eml (1:1
+2.3. .=n-1) is more effective. Both ND-DIR and emulsion layer Eml (l
"1) 2 H3□...z n), the content is y Em+ < Emt < Ems < - < Km
−+)<Emn.

Further, the emulsion layer Eml (1=1, 2, 3, -, n
) The total amount of ND-DIR added to a photographic element consisting of emulsion layers Eml (1 = 1, 2, 3, 4) is 5 moles of 0, oi to 5 mils relative to silver halide. For example, N for each emulsion layer EmiK
The addition ratio of D-DIR is preferably set to Em+; 0 to 15% Ems; 0.-'JJ% Ems; 0 to 20% Em4 150 to 100% by distributing the total amount of addition; 5-15%, Er
f12: 10-20%, Ems: 10-20%,
Em4: 55 to 65% is more preferable.

The D-DIR and ND-DIR described above may be used in combination in a mutually complementary manner.

The above and ND-DIR are described in, for example, U.S. Pat.
No. 8.062, No. 3,227,554, British Patent 2
．． No. 010,818, JP-A No. 52-69624, and JP-A-135835, a compound which reacts with an oxidized product of a color developing agent to form a dye and release a development inhibitor, a U.S. patent No. 3,632,345, No. 3,95
No. 8,993, No. 3,938,996, No. 3゜928
．． No. 041, No. 3,961,959, Japanese Unexamined Patent Publication No. 1973-
No. 67628, No. 51-6724, JP-A No. 52-4
No. 9030, a compound which releases a development inhibitor upon reaction with an oxidized form of a color developing agent but does not form a dye; Compounds that release development inhibitors through a direct nuclear conversion reaction are known, and compounds that release development inhibitors through reaction with oxidized color developing agents are known.
No. 46 describes a compound that releases a development inhibitor by electron transfer along a conjugate term, and a compound that releases a development inhibitor by reaction with an oxidized product of a color developing agent.

As the silver halide emulsion used in the light-sensitive material of the present invention, any silver halide emulsion used in the art can be used. For example, it can contain crystals of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, or silver chloroiodobromide, or mixtures of these crystals. The silver halide emulsion may be large grain or small grain, and monodisperse or polydisperse. Further, the silver halide crystal may be cubic, octahedral, epitaxial hybrid crystal, or the like. The emulsion can be a negative emulsion or a direct positive emulsion. They are mainly surface latent image emulsions that form latent images on the surfaces of silver halogenide grains, internal latent image emulsions that form latent images inside silver halogenide grains, surface latent image emulsions, and internal latent image emulsions. Mixtures with latent image emulsions can be used. 1. The silver halide emulsion used in the present invention can be manufactured by various manufacturing methods including the usual manufacturing method, such as Japanese Patent Publication No. 46-77.
72, that is, forming an emulsion of silver salt grains consisting of at least some silver salts having higher solubility than silver bromide, and then at least some of these grains are mixed with silver bromide or silver bromide. It can be prepared by any method such as a so-called conversion emulsion method, such as conversion to silver iodide salt, or a Lippmann emulsion method consisting of fine-grained silver halide having an average grain size of 0.1 .mu.m or less.

When the silver halide used in the present invention is required to be a silver halide emulsion with high sensitivity in absolute value, silver iodobromide containing 1 to 10 mol% of silver iodide is used as the silver halide. It is preferable that the particle size is 0.5 to 3.0.
Preferably it is μm.

Further, the silver halide used in combination with the above high-sensitivity emulsion to form a low-sensitivity silver halide emulsion is preferably silver iodobromide containing 1 to 10 mol% of silver iodide, and has a grain size of 0.
It is preferable that it is 1-0.8 micrometer.

When the photographic element according to the present invention has a four-layer structure, the particle size is preferably within the following range.

Em, To, 5-3, Opm Em2; 0.5-2.0 Am Em3; 0.3-'1.3 μm Em4; 0.1-0.8 μm The photosensitive layer according to the present invention has the above-mentioned In the case of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities, specifically, for example, four silver halide emulsion layers having different sensitivities, each The sensitivity difference Δ1ogE between silver halide emulsion layers with different sensitivities is not determined in part, but it is generally 0.1 to 1.0, preferably 0.2.
~0.6.

In the photographic element according to the present invention, which has a laminated structure of four or more emulsion layers, the emulsion NEml with a sensitivity of Si is lower than the emulsion layer Ey with a sensitivity of S(1++) lower than that of Si located below Eml.
The amount of light received by r1 (1++) is limited, and this situation gradually spreads further down, and the low-sensitivity emulsion layers are exposed to a small amount of light, so at least the sensitivity [B+ of the top layer] is limited. It is desirable for the emulsion layer Emr to contain an emulsion consisting of monodisperse silver halide grains with little optical loss of light. More preferably, the following emulsion layers also contain monodisperse emulsions.

The content of the monodisperse emulsion in each emulsion layer is preferably such that 50% of the number of grains is accounted for by monodisperse grains, more preferably 70%, and most preferably 70%. is 100%.

The monodisperse particle group may be a mixture of two or more groups having different average particle diameters.

The monodispersity of the silver halide grains means that the value obtained by dividing the standard deviation S by the average grain size T is 0.20 mm or less, as defined by the following formula.

Formula (A) 1≦0.20 The average grain size here means the diameter in the case of spherical silver halogenide grains, or the projected image in the case of grains with shapes other than cubic or spherical. is the average value of the diameter when converted to a circle selected by the same side, where the individual particle size is rl and the number is nl, 7 is defined by the following formula. .

Σnl rl Σni The above particle size can be measured by various methods commonly used in the technical field for the above purpose. A typical method is Loveland's [Particle Size Analysis Method JA, s.

T.M., Symposium on Light Microscopy, 1955, pp. 94-122, or chapter 2 of ``Theory of the Photographic Process'' by Mies and James, 3rd edition, published by Macmillan (1966). ing.

The particle size can be measured using the projected area or approximate diameter of the particle. If the particles are of substantially uniform shape, the particle size distribution can be expressed fairly accurately as diameter or projected area.

The relationship between grain size distribution is "sensitome in photographic emulsion" I
"Empirical relationship between J-distribution and particle size distribution" The Photographic Journal, Volume LXXIX, (1949) 3
This can be done as described in the article by Trivelli and Smith, pages 30-338.

As a method for preparing monodisperse silver halide grains according to the present invention, grains of a desired size can be obtained by a double jet method while controlling pAg and pI.

In addition, silver halide emulsions with a high degree of monodispersity
The method described in No.-48521 can be applied. A preferred embodiment of the method is a method in which the gelatin is added as an aqueous gelatin solution containing rogogenated daughter particles, such as an aqueous gelatin solution and an ammoniacal nitric acid aqueous solution.

At this time, highly monodisperse silver halide can be obtained by appropriately selecting the time function of addition rate, pH, PAg, temperature, humidity, etc.

In the present invention, the monodisperse silver halide grains are
For example, silver bromide, silver iodide, silver iodobromide, silver chloroiodobromide, etc. may be used, and the crystal shape of the grains may be hexahedral, octahedral, or dodecahedral as long as they are monodisperse. Any other crystalline habit may be used, but octahedrons and dodecahedrons are most preferred. Furthermore, monodispersity preferably used in the present invention...
The silver halide grains may have a uniform silver halide composition, but may also be core/shell type grains.

Monodisperse core/sheet used in the present invention.

A type silver halide grain consists of a core made of monodisperse silver halide containing substantially silver iodide, and this core coated with silver bromide, silver chloride, silver iodobromide, or silver chlorobromide. Consists of a shell. In addition, the silver iodide content in the shell is
It is preferable that the silver iodide content is lower than that of the core. Further, the silver iodide content in the shell of the silver halide grains having the above composition is preferably as low as possible, preferably close to 0% I, and substantially silver bromide is preferred.

Furthermore, the core of the grain may be formed as 2 Ifi or more layers having different silver iodide contents.

The difference in content between the layer with a high silver iodide content and the layer with a low silver iodide content in the silver halide grains of the present invention may have a sharp boundary, or may have a continuous change in which the boundary is not necessarily clear. It may be.

The distribution state of silver iodide in the above silver halide grains is as follows:
It can be detected by various physical measurement methods, and can also be investigated by measuring luminescence at low temperatures, for example, as described in the Abstracts of the 1986 Annual Canine Society Lectures of the Photographic Society of Japan.

In the monodisperse core/shell type silver halide grains according to the present invention, the shell thickness is preferably 0.001 to 0.1 μm, and more preferably 0.0! -0.1 μm.

In a preferred embodiment of the silver halide grains of the present invention, the silver halide composition of the core contains 2 to i i of silver iodide.
The shell is a silver halide containing 5 mol % of silver iodide, and the shell is a silver halide containing 0 to 4 mol % of silver iodide. Further, it is preferable that the difference in silver iodide content between the shell and the core is 5 mol% or more. In the silver halide grains of the present invention, the silver halide composition other than the above-mentioned silver iodide is preferably mainly silver bromide, but may contain silver chloride as long as the effects of the present invention are not impaired.

Further, two or more kinds of core/shell type silver halide grains having different silver iodide contents can be preferably used as a mixture.

The average silver iodide content of the silver halide grains according to the present invention is 0
．． 5 mol% to 15 mol% is preferred. More preferably, it is in the range of 5 mol% to 12 mol%.

The silver halide emulsion containing core/shell type silver halide grains of the present invention can be produced by using monodisperse silver halide grains as a core and coating the core with a shell.

The monodisperse silver halide grains of the core may be produced by using the method for preparing monodisperse silver halide grains described above.

Next, the thickness of the shell covering the core must be such that it does not hide the desirable qualities of the core, and on the contrary, it must be thick enough to hide the unfavorable qualities of the core. Such a shell can be prepared by double diluting a soluble halogen compound solution and a soluble silver salt solution.8. It can be formed by depositing it on the core of monodisperse silver halide grains by the method.

Regarding the manufacturing method of the above-mentioned core/shell type silver halide grains, for example, West German Patent No. 1,169,290, British Patent No. 1,027,146, JP-A-57-154232, JP-B-Sho 51-1417, etc. It is also stated.

In a preferred embodiment of the present invention, the set of photographic elements is constructed from four emulsion layers having substantially the same color sensitivity but different sensitivities.

The silver halide emulsion used in the silver halide emulsion layer according to the present invention may be doped with various metal salts or metal complex salts at the time of silver halide precipitate formation, grain growth, or after growth. For example, gold, platinum, pasidicum, iridium, rhodium, bismuth, cadmium, mediating metal salts or complex salts and combinations thereof can be applied. In the above production method, the Tardel water washing method, dialysis method, or coagulation precipitation method, which is commonly used in general emulsions, can be appropriately used as a means for desalting.

Furthermore, the above silver halide emulsion may contain sulfur sensitizers such as allylthiocarbamide, thiourea, cystine, etc., active or inactive selenium sensitizers, and reduction sensitizers.
For example, stannous salts, polyamines, etc., noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-olsulfobenzothiazole methochloride, etc., or such as ruthenium, rhodium, iridium. Sensitizers of water-soluble salts such as ammonium chloroparadate, potassium chloroplathiate, sodium chloroparadite, etc. (these types can be used as sensitizers or fog suppressants depending on the amount) chemically sensitized either alone or in appropriate combination (for example, a combination of a gold sensitizer and a sulfur sensitizer, a combination of a gold sensitizer and a selenium sensitizer, etc.); It's okay.

Furthermore, this silver halide can be optically sensitized to a desired wavelength range, for example, by using an optical sensitizer such as a cyanine dye such as a zeromethine dye, a monomethine dye, a dimethine dye, a trimethine dye, or a merocyanine dye. Alternatively, optical sensitization can be achieved in combination (eg, super dye sensitization).

The hydrophilic colloids used in the present invention include not only gelatin but also various gelatin derivatives such as gelatin and aromatic sulfonyl chlorides, acid chlorides, acid anhydrides, isocyanates, l,4-diketones, etc. Gelatin derivatives produced by the reaction of gelatin with trimellitic anhydride, gelatin derivatives produced by the reaction of gelatin with an organic acid containing an active halogen, and the reaction of aromatic glycidiether with gelatin Gelatin derivatives obtained by the reaction of maleimide, maleamic acid, unsaturated aliphatic diamide, etc. with gelatin, Suluno-alkylated gelatin, polyoxyalkylene derivatives of gelatin, polymer graph F derivatives of gelatin, synthetic hydrophilic polymers Natural hydrophilic polymer substances other than gelatin, such as casein, agar, alginate polysaccharide, etc., can also be used alone or in combination.

The emulsion according to the present invention can contain various commonly used additives depending on the purpose. Examples of these additives include stabilizers and anti-capri agents such as azaindenes, triazoles, tetrazoles, imidazolium salts, tetrazolium salts, and polyhydroxy compounds; aldehyde-based, aziridine-based, inoxazole-based, vinylsulfone-based, Hardeners such as acryloyl, albodiimide, maleimide, methanesulfonic acid ester, and triazine; Development accelerators such as benzyl alcohol and polyoxyethylene compounds; Chroman, Claman, bisphenol, and phosphite esters image stabilizer; wax,
Examples include lubricants such as glycerides of higher fatty acids and higher alcohol esters of higher fatty acids. In addition, as surfactants, coating aids, permeability improvers for processing liquids, etc.
Anionic, cationic, nonionic, or amphoteric business cards are used as antifoaming agents or materials for controlling various physical properties of photosensitive materials.Y: Ki71
Effective antistatic agents include diacetyl cellulose, sterene perfluoroalkyl sodium maleate copolymers, and alkali salts of reaction products of styrene-maleic anhydride copolymers and p-aminobenzenesulfonic acid. Polymethacrylic acid methi as a matting agent? Examples include polystyrene and alkali-soluble polymers.

It is also possible to use colloidal silicon oxide.

Further, examples of the latex added to improve the physical properties of the film include copolymers of acrylic esters, vinyl esters, etc., and other monomers having ethylene groups.

Examples of gelatin plasticizers include glycerin and glycol compounds, and examples of thickeners include styrene-sodium maleate copolymers, alkyl vinyl ether-maleic acid copolymers, and the like.

Examples of the support according to the present invention include baryta paper,
Polyethylene coated paper, polypropylene synthetic paper, crow,
Supports include cellulose acetate, cellulose nitrate, polyvinyl acecool, polypropylene, polyester films such as polyethylene terephthalate, and polystyrene, and these supports are appropriately selected depending on the intended use of each photosensitive material.

These supports are subjected to undercoat processing if necessary.

Coating methods for the constituent layers of the light-sensitive material according to the present invention include dip coating, air knife coating, curtain coating, or extrusion coating using a hopper of the type described in U.S. Pat. No. 2,681,294. A variety of application methods may be used, including the following. Optionally, bilayers or multiple layers can be added as described in U.S. Patent 2,761.
, 791 and British Patent A37,095.

The aromatic primary amine color developing agent compound used in the photosensitive color development of the present invention is preferably a p-phenyl diamine color developing agent compound, for example, 4-
Amino-N, N-diethylaniline, 3-methyl-4-
Amino-N, N-dixthi/I/7niline, 4-aminol N-ethyl-β-hydroxyethylaniline, 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, 3-β-methanesulfonamidoethyl-
4-amino-N,N-diethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-hydroxyethylani') 13-methoxy-4-amino-N-ethyl-N
-β-methoxyethylaniline, 3-acetamide-4
-amino-N, N-diethylaniline, 4-amino-N
, N-di)f-ruaniline, bow-x=nil-N-β[β-
(β-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aminoaniline or N-ethyl-N-N
-β-(β-methoxyethoxy)ethyl-3-methyl-
4-aminoaniline and salts thereof, such as sulfate, hydrochloride, sulfite or p-toluenesulfonate.

These color-developed raw chestnuts generally have a developer le of about 0
．． concentration of 1 g to about 30 g, more preferably developer le
About 1 g to about 15 g per degree.

In addition, the above-mentioned color developing agent can be used alone or in combination of two or more, -1: If desired, black and white developed raw chestnuts such as phenidone 4-hydroxymethyl-4-methyl-1-phenyl-
It may be used in combination with 3-pyrazolidone, metol, etc.

(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples, and various embodiments are possible. In the following examples, the effect of improving image sharpness is determined by the MTF (Modulation TranlIfe) of the dye image.
r Function), and the MTF values in Kamoto/m were compared using relative values (with the comparison sample being 100).

In addition, the effect of improving image graininess is due to the variation in density value that occurs when a dye image with dye image densities of fog + 0.3 and fog') + 1.0 is scanned with a microdensitometer with a circular scanning aperture of 5 μm. Relative value (RMS value) with the control sample set as 100, which is 1000 times the standard deviation of
compared with.

The following couplers, DIR compounds, and antifouling agents were used in the examples below.

(Y-16) (M-1) (A-20) OH 2H11 (B-42) () [Q -1) OH f-1 Example-1 [Preparation of polydispersed emulsion] Silver nitrate aqueous solution and alkali halide aqueous solution Aqueous gelatin solution and excess halide were added in advance, and the gelatin was allowed to fall naturally into a reaction vessel maintained at ω°C. Next, an aqueous solution of Demol N manufactured by Kako Atlas Co., Ltd. and an aqueous magnesium sulfate solution were added to precipitate and desalt the gelatin. In addition, pAg7.8, p
An emulsion of H6,0 was obtained. Furthermore, chemical ripening was performed using sodium thiosulfate, chloroauric acid, and rhodan ammonium, and 4-hydroxy-6-methyl-1,3,3a,? −
Tetrazaindene and 6-nidropentimidazole were added, and gelatin was further added to obtain a 10 polydisperse silver bromide emulsion. The silver iodide mole % was changed by changing the alkali halide composition, and the average particle size and particle size distribution were changed by changing the addition time of the silver nitrate aqueous solution and the alkali halide aqueous solution.

Here, the width of the particle size distribution indicated by the coefficient of variation CV of each particle was 27 to 32%. The coefficient of variation is CV■)=-
It is expressed as X100.

[Preparation of photosensitive material]

Samples 1 to 3 were prepared by sequentially coating the following layers on a transparent support made of subbed cellulose triacetate film. (In all the examples below, the amount of -\ added in the silver halide color photographic light-sensitive material was 1 m
The correct value is shown, and silver rhodanide emulsion and colloidal silver are shown in terms of silver. ) (Sample 1) Layer 1: Antihalation layer containing black colloidal silver 0.311 and gelatin 2S.

Layer 2: 1.5y average grain size 0 containing 6 mol% silver iodide
, 4μ of silver iodobromide [1.5 g of gelatin and 0.7 g of magenta coupler (M-1), and o, 15 g of colored magenta coupler (CM -2) containing 0.8 g of tricresyl phosphate (hereinafter referred to as TCP) dissolved therein. ] Layer 3: 1.5F containing 8 mol% silver iodide, average grain size 0.
Medium-sensitivity green-sensitive silver iodobromide layer C1 containing 9μ of silver iodobromide
, 511 gelatin and 0.2 g of TCP in which 0.17I magenta coupler (M-1) and 0.0519 colored magenta coupler (CM-2) were dissolved. Layer 4: High-sensitivity bottle-sensitive silver iodobromide layer containing 1.5 g of silver iodobromide with an average grain size of 1.2 μm containing 8 mol % silver iodide (1.5 g of gelatin and 0.11 g of magenta) Contains 0.3 g of TCP in which coupler (M-1) and 0.03 F colored magenta coupler (CM-1) are dissolved.] Layer 5: Retention layer containing 1.5 g of gelatin.

(Sample-2) Layer 1: Layer 1 as described in sample 1 Layer 2: 1.0 g containing 6 mol% silver iodide with an average grain size of 0
．． A low-sensitivity green-sensitive silver iodobromide emulsion layer C1 containing 3μ of silver iodobromide, gelatin of Ofj and 0.7y of magenta coupler (M-1) and 0.15g of colored magenta coupler (CM-2). Contains dissolved 0,8JTCP. ] Layer 3: 1.0 g containing 8 mol % silver iodide, average grain size 0.
Medium green sensitive silver iodobromide emulsion layer c i,og gelatin containing 6μ of silver iodobromide and 0.11g of magenta coupler (M-1) and 0.05g of colored magenta coupler (CM-2) 0.2 g of TCP dissolved in
Contains. ] Layer 4: 1 containing 8 mol % silver iodide. The average particle size of Og is 0.
A medium green sensitive silver iodobromide emulsion layer containing 9μ of silver iodobromide c i,og of gelatin and 0.15g of magenta coupler (M-1) and 0.03. ! Contains 0.2 g of TCP in which il' colored coupler (M-2) is dissolved. Layer 5: High-sensitivity green-sensitive silver iodobromide emulsion layer containing 1.5 g of silver iodobromide with an average grain size of 1.2 μm containing 8 mol % silver iodide (1, 5, 9 gelatin and o, i
p magenta coupler (M-1) and 0.03 g of colored magenta coupler (CPvl-2) were dissolved.
, contains 3 g of TCP. ] Layer 6: Layer 5° as described in Sample IK (Sample-3) Except that the magenta coupler (M-1) in layer 3 was 0.15 g and the magenta coupler (M-1) in layer 4 was 0.4 y. was prepared in the same manner as Sample-2.

Each of the above samples was placed in close contact with a wedge, and a green light beam was applied to the wedge.
Each sample was developed using the following processing steps to obtain a sample having a dye image.

Development processing process (38℃) Development color development during processing・・・・・・・・・・・・・・・・・・・・・・・・
...Bleach for 3 minutes and 15 seconds...
・・・・・・・・・6 minutes, wash the blade with water for seconds・・・・・・・
・・・・・・・・・・・・3 minutes 15 seconds fixed...
・・・・・・・・・・・・・・・・・・・・・6 minutes (
9) Sand water washing・・・・・・・・・・・・・・・・・・
・・・・・・Stabilized bath for 3 minutes and 15 seconds・・・・・・・・・・・・
・・・・・・・・・・・・1 minute blade second In each processing process,
The composition of the treatment liquid used was as follows.

Color developing solution composition; Bleaching solution composition: Fixing solution composition; The sensitivity and RMS value of each image sample obtained were measured using green light, and the results are shown in Table 1. However, the sensitivity is a relative sensitivity with the sensitivity of sample 1 set as 100.

Table 1 As is clear from the above table, sample 3 of the present invention has improved graininess, particularly in the concentration range where the amount is important for practical use.

The effective maximum color density of Samples 2 and 3 at low green sensitivity, medium sensitivity, medium high sensitivity, and high sensitivity are shown in the table below.

Example-2 Samples 4 to 6 were prepared by further adding the following compounds to Samples 1 and 3 of Example-1.

(Sample-4) Layer 4, which is the high-sensitivity green-sensitive silver iodobromide emulsion layer of Sample-1, contains 0
．． 05. ! il DIR compound (A-20).

(Sample-5) Layer 5, which is the high-sensitivity green-sensitive silver iodobromide emulsion layer of Sample-3, contains 0.
．． Contains 05g of DIR compound (A-20).

(Sample-6) O
, ois y DIR compound (B-42) and a DIR of 0.059 in layer 5, which is a high-sensitivity green-sensitive silver iodobromide emulsion layer.
Contains compound (A-20).

The obtained sample was processed in the same processing steps as in Example-1 to obtain a sample having a dye image.

The sensitivity and graininess of the obtained dye image were measured and the results are shown in Table 2. However, the sensitivity of sample 4 is 10
It is expressed as a relative sensitivity set to 0.

Table 2 It is clear from the above table that Samples 5 and 6 according to the present invention have improved graininess, particularly in the concentration range that is important in practical terms, and Sample 6 has an even greater effect of improving graininess.

Example 3 [Preparation of monodisperse emulsion] Silver halide seed grains and an aqueous gelatin solution were placed in a reaction vessel in advance, and an ammoniacal silver nitrate aqueous solution and an iodine solution were added while controlling the pAg and pH in the reaction vessel. Potassium chloride and potassium bromide aqueous solution were added in proportion to the increase in surface area during particle growth. Next, a Demol N aqueous solution manufactured by Kako Atlas Co., Ltd. and a magnesium sulfate aqueous solution were added to perform precipitation and desalting, and gelatin was added to give a pAg of 7.8.
, milk MIJ with pH 6.0 was obtained. Furthermore, sodium thiosulfate, chloroauric acid, and rhodan ammonia! 74 pieces were added and chemically ripened to produce 4-hydroxy-6-methyl-1,3,3
a.

7-chitrazaindene and 6-nidrobenzimidazole were added, and gelatin was further added to obtain a monodisperse silver iodobromide emulsion. Here, the silver iodide mol% is changed by changing the ratio of potassium iodide and potassium bromide, and the grain size is changed by changing the amount of ammoniacal nitrate and potassium bromide. Emulsions E-1 to E-8
I got it.

The core/shell emulsion is disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 54-48521.
Manufactured by the method described in the issue.

Table 3 shows the physical properties of each silver iodobromide emulsion produced.

Table 3: The silver halide emulsion of each layer in Sample 6 of Example-2 was coated under the same conditions as Sample 6, except that the emulsion was changed as shown in Table 4 below. It was created.

Table 4: Here, the "polydisperse emulsion" is the same as that used in each layer of Sample 6.

Sample 6 of Example 2 and the obtained samples 7 to 1° were separately placed in close contact with a transparent rectangular wave chart, exposed to green light, and treated in the same process as in Example 1. A sample with a dye image was obtained.

The sensitivity, graininess and sharpness of the obtained dye image were measured and the results are shown in Table 5.

However, the sensitivity is expressed as a relative sensitivity with the sensitivity of sample A6 as 100.

Table 5 As is clear from the above results, with the layer structure of the present invention,
In particular, sensitivity and sharpness were improved when monodispersed emulsions were used in all layers, and image quality was further improved when core/shell emulsions were used as in sample 10.

Example 4 Sample 1, which is a multilayer silver halide photosensitive material, was prepared by sequentially coating the following layers on a transparent support made of subbed cellulose triacetate film.
1, 12 and 13 were created.

Here, the polydisperse emulsion prepared in Example 1 was used for Samples 11 and 12, and the core/shell emulsion prepared in Example 3 was used for Sample 13.

(Sample-11) r-1: Antihalation layer 2 of sample 1: Low-sensitivity red containing silver iodobromide with an average oton diameter of 0.4μ of 1.5y containing 6 mol% silver iodide. Sensitive silver iodobromide emulsion layer (: 1.5 g of gelatin and 0.6 g of cyan coupler (C-1), colored cyan coupler (cc-4) with L of 0.071/, and further 0.018 g of D
T of 0°69.9' in which IR compound (B-42) was dissolved
Contains CP. ] Layer 3: 1 containing 8 mol% silver iodide.
5 Medium-sensitivity red-sensitive silver iodobromide emulsion layer C1,5, containing silver iodobromide with an average grain size of 09 μm /j! i' of gelatin and O, 13 g of cyan coupler (C-1) and 00
Contains 0.2 g of TCP in which 4 g of colored cyan coupler (CC-4) is dissolved. Layer 4: High-sensitivity red-sensitive silver iodobromide emulsion layer containing 1.5 g of silver iodobromide with an average grain size of 12 μm containing 8 mol % of silver iodide [1.5 g of gelatin and 0.1 g of silver iodobromide] Cyan coupler (C-1) and 0.
03g of colored cyan coupler (CC-4) plus 0
．． 0,2 in which 0.5 g of DIR compound (A-8) was dissolved.
Contains f/TCP. Layer 5: Intermediate layer containing 0, On dioctyl phthalate (hereinafter referred to as DOP) and O, sg gelatin in which 0.07 g of antifouling agent (HQ-1) was dissolved.

Layer 6: In addition to the low-sensitivity green-sensitive silver iodobromide emulsion layer of sample 1, 0
．． Layer containing 018 g of DIR compound (B-42).

117: Medium-sensitivity green-sensitive silver iodobromide emulsion layer of Sample 1.

1 bag 8: Highly sensitive green-sensitive silver iodobromide emulsion layer of sample 4.

Layer 9: One yellow filter layer containing 0.1 g yellow colloidal silver, 0.06 g DOP dissolved in O.IJ stain inhibitor (HQ-1) and 1.5 g gelatin.

Layer 10: 0.7 g average grain size 0 containing 6 mol% silver iodide
．． A low-speed blue-sensitive silver iodobromide emulsion layer containing 4μ of silver iodobromide [1,0,! Contains 0.2 g of TCP in which i+ gelatin and 1.0 g of yellow coupler (Y-6) are dissolved. ] Layer 11: 1.0 g containing 8 mol% silver iodide
A medium-sensitive blue-sensitive silver iodobromide emulsion layer containing silver iodobromide with an average grain size of 0.9 μ [0.06 g of TC in which 10 g of gelatin and 0.3 g of yellow coupler (Y-6) were dissolved]
Contains P. ] Layer 12: 1 containing 8 mol % silver iodide.
High-sensitivity blue-sensitive silver iodobromide emulsion layer C1 containing silver iodobromide with an average grain size of 1.2 μm, gelatin of Og and
．． 0 in which 25g of yellow coupler (Y-6) was dissolved,
Contains 0.6g of TCP. ] Layer 13: Protective layer containing 1.5 g of gelatin.

(Sample-12) Layer 1: Antihalation layer of sample 1.

Two layers of 1.0 g containing 6 mol % silver iodide with an average grain size of 0.
A slow red-sensitive silver iodobromide emulsion layer containing 3μ of silver iodobromide [1.0 g of gelatin and 0.61 g of cyan coupler (ci) and 0.07 g of colored cyan coupler (CC-4) In addition, 0.018 g of DIR compound (
Contains 0.69g of dissolved B-42). ] Layer 3: 1 containing 8 mol % silver iodide. The average particle size of Og is 0.
Medium-sensitivity red-sensitive silver iodobromide emulsion layer containing 6μ of silver iodobromide [10 g of gelatin and 0.115 g of cyan coupler (c-i) and 0.04 g of colored cyan coupler (CC-4) were dissolved. Contains 0.2g of TCP. ] Layer 4: medium-sensitive blue-sensitive silver iodobromide emulsion layer containing 1.0 g of average grain size 0.9 g of silver iodobromide containing 8 mol % of silver iodide [1.0 g of gelatin and .1μ cyan coupler (C-1) and 0.0:l colored cyan coupler (CC-4) dissolved 0.2 f/T
Two layers containing CP 5: 1.5 containing 8 mol% silver iodide
High-sensitivity red-sensitive silver iodobromide emulsion layer C1 containing silver iodobromide with an average grain size of 1.2μ, 5g of gelatin and 0.0g of gelatin;
9g of cyan coupler (C-1) and o,o2gg of colored cyan coupler (cc-4) plus 0.05g
Dissolve DIR compound (A-8) at 0.29 TC
Contains P. ] Layer 6: Intermediate layer containing the antifouling agent of Sample 1.

Layer 7: Low-sensitivity green-sensitive silver iodobromide emulsion layer of Sample 6.

Layer 8: Medium-sensitivity green-sensitive silver iodobromide emulsion layer of Sample 6.

1i9: Medium-high sensitivity green-sensitive silver iodobromide emulsion layer of Sample 6.

Layer 10: Highly sensitive green-sensitive silver iodobromide layer of sample 6.

Layer 11: One layer of yellow filter of sample 11.

12 layers 0.4g average grain size 0 containing 6 mol% silver iodide
．． A slow blue-sensitive silver iodobromide emulsion layer containing 3μ of silver iodobromide [0.2g of TCP in which 0.6p of gelatin and 1.0g of yellow coupler (Y-6) was dissolved. ] Layer 13: A medium-sensitive blue-sensitive silver iodobromide emulsion layer containing 0.65 g of silver iodobromide with an average grain size of 0.6 μm containing 8 mol % of silver iodide (0.7 g of gelatin and 0.65 g of silver iodobromide with an average grain size of 0.6 μm). Contains 0.046 g of TCP in which 259 yellow coupler (Y-6) is dissolved.] Layer 14: Iodobromide with an average grain size of 0.65.9 and 0.9μ containing 8 mol % silver iodide. Medium-high sensitivity blue-sensitive silver iodobromide emulsion layer containing silver [0,7,!9 gelatin and 0.23 g yellow coupler (Y-6)
Contains 0.05g of TCP dissolved in. ]Layer 15:
High-sensitivity blue-sensitive silver iodobromide emulsion ffi containing 1.0 g of silver iodobromide with an average grain size of 1.2 μm containing 8 mol% silver iodide
Contains 0.0 On TCP in which C1.0 g of gelatin and 0.21 g of yellow coupler (Y-6) are dissolved. ] Layer 16: Protective layer containing 1.5g gelatin.

(Sample-13) Sample-12 except that the silver rodanide in each layer of Sample-12 was replaced with a monodisperse core/shell emulsion (see Table 3).
It was painted under the same conditions.

The obtained samples 11 to 13 were individually adhered to a transparent rectangular wave chart or wedge and exposed to white light, and each sample was processed in the same processing steps as in Example 1 to obtain a sample having a dye image.

As a result of measuring the sensitivity, graininess, and sharpness of the obtained images, it was found that the results obtained in Examples 1 to 3 were maintained even in the multilayer silver rodanide color photographic light-sensitive material, and the samples according to the present invention Bi and 13 are blue sensitive, green sensitive,
In all red-sensitive layers, the graininess in the density range, which is important for practical purposes, is improved, and Sample 13, which uses a monodisperse core/shell emulsion, has improved sharpness and image quality.

(Effects of the Invention) A technological base has become known which has achieved most of the objectives of the present invention and has improved all of the sensitivity, graininess, sharpness, and gradation (tone reproducibility).

Agent Yoshimi Kuwabara Procedural Amendment May 29, 1980 Patent Application No. 137295 of 1980 2 Title of invention Silver halide photographic light-sensitive material: (, Person making the amendment Relationship with 11 cases Patent applicant 11 - Location: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo, Meiso,
(+27) Roku Konishi Photo Industry Co., Ltd. 4, Generation: 1 ri, Address: 1-6 Sakura-cho, Hino-shi, Tokyo, 1-6 Sakura-cho, Hino-shi, Tokyo Subject of amendment: ``Detailed explanation of the invention, Column 7 of J, Contents of amendment: Detailed explanation of the invention. is corrected as follows.

(,) Page 10 tA lines 4 to 11 "Also...preferable. J is also a compound that reacts with the oxidized form of a color developing agent to release a development inhibitor (hereinafter referred to as l) I R At least one type of DIR compound having a development inhibiting group represented by the following general formula [1] is used to obtain at least the highest sensitivity t.
Similarly to the above, at least one DIR compound having a development inhibiting group represented by the following general formula [1(]) and general formula (III:l) was added to the 7L agent layer E+n of rvs. Emulsion F with lowest sensitivity S o, +o
It is preferable to include it in n. ” he corrected.

(IJ) Page 34, line f51 1-Correct "diffusibility" to "diffusion resistance".

(c) Page 34, lines 14 to 17, 1 - Next... Preferable. 4 [Next, the DIR compound of the present invention having a development inhibiting group represented by the general formula (1) according to the present invention will be described. ”.

(d) Correct the first line r (1-[111tJ) from directly below No. 35 to (DIR compound having a development inhibiting group represented by the general formula).

(e) 43iNffi line 1, line 5, line 110 1
-D-I) IIIJ is corrected to the current (DIR compound having one inhibitory group) represented by one general formula.

m Modify page 44 as follows.

First, the development inhibiting group represented by the general formula (U) or [■] will be described.

General formula (■) 2 In the formula, R2 is a halogen atom, 7 acylamino groups (for example, 13, 3 zolinyl amino group (where 3 is an aryl group, or an alkyl group having 1 to 4 carbon atoms, , for example, may be substituted with alkoxy, a halogen atom, or aryl), an alkoxy group substituted with a phenyl group (for example, a benzoxy group), etc. (8), page 45, No. 1
Delete lines 2 to 2 [General formula (III]...preferred.).

(11) Page 45, line 3 "General formula [■]" ] General formula (III) Corrected to J.

(1) 45th rt, line 14 1-ND-DJRJ [Correct the DIR compound compound section.

('') Page 66, lines 3, 7, and 13 “ND-D
IRJ is corrected to "DIR compound having a development inhibiting group represented by general formula [11] or [■]".

(k) Page 67, line 3 [ND-DIRJ is corrected to "DIR compound having a development inhibiting group represented by general formula (II) or (III)".

(+) Page 167, line 12 rD-DIR and N1)-DIRJ [Corrected to I) It Compound J according to the present invention.

(Part) No. 67r (line 14 l'l')-DIR and old]-DIRj is corrected to [old R compound according to the present invention].

Procedural amendment October 24, 1980 Director General of the Patent Office Manabu Shiga 1982 Patent IJ [No. 1,37295 2, Name of invention Silver halide photographic light-sensitive material 3, Person making amendment 4゜5゜6, Subject of amendment Compound A-3 on page 37 of Column 7 of Detailed Description of the Invention in the Specification, Contents of Amendment (]) is corrected as follows.

(2) Compound A-9 on page 39 is corrected as follows.

A11'l11 8-14 (4) Add "U particle size" before "Standard deviation" on the last line of page 71.

(5) Replace page 72 with the following.

Record “It refers to something whose value when divided is 0.20 or less.

Formula (8) S/r40,20.

Here, the particle size refers to the diameter in the case of spherical silver halide particles, and the diameter when the projected image is converted to a circular image of the same area in the case of particles with shapes other than cubes and spheres. and the average particle size 〒 is the average value, and when the individual particle size is the number and the number is ni, it is calculated by the following formula.

r = Σnir+/Σni The standard deviation S is used statistically and is calculated using a quintic equation.

The above particle diameter can be measured by various methods commonly used in the technical field for the above purpose. Typical methods include Loveland's "Particle Size Analysis Method 18, S, T, M, Symponium.
(6) Page 85, page 85] Replace lines 1 to 12 with the following.

Record

Claims (4)

[Claims] (1) At least four emulsion layers Kmi (sensitivity st, s = 1.213.-
1 n ; n≧4) and containing a color-forming coupler, in the set of photographic elements of a silver halide photographic light-sensitive material provided on a support, an emulsion layer Emi For the sensitivity Sl, Ss > at > Ss
>-> In the arrangement of the emulsion layers in the photo IX element of the above set, where S At the maximum effective color density D.1 generated by development, (b) Maximum sensitivity Ks! Regarding the effective maximum color density Del of the emulsion layer Eml having D(1!≦0.5, (c)
Emulsion layer having the highest sensitivity S1] Effective maximum color density D@t of the emulsion layer Eml with a sensitivity of 81 excluding ICmt and the effective maximum color density Del and Den of the emulsion layer Emn having the lowest sensitivity an (t = 2; 3. A silver halide photographic light-sensitive material characterized in that the emulsion layer Eml having the minimum effective color density Den of the emulsion layer Emn having the lowest sensitivity Sn is excluded. (2) In the set of photographic elements, between the effective maximum color density Di1 of the emulsion layer Emi, Del≦De2≦De3≦...group≦De(n-
1) The silver halide photographic material according to claim 1, which is (Den). (3) In said set of photographic elements, at least emulsion layer Em1 contains at least 1 m of a compound that reacts with the oxidized form of a color developing agent to release a diffusible development inhibitor. The silver halide photographic material according to item 1 or 2. (4) In the set of photographic elements, at least one emulsion layer Emn contains at least one compound that reacts with an oxidized color developing agent to form a diffusion-resistant development inhibitor. Silver halide photographic material 0(5) according to item 1, item 2 or item 3 In the set of photographic elements, a monodisperse emulsion is added to the emulsion layer Kml having at least the maximum sensitivity S. Claims 1, 2, and 3 containing
λ silver halide photographic material 0 (
6) Silver halide grain strength (core/
6. The silver iodide photographic material according to claim 5, which is shell-shaped and has different silver iodide contents in the core and shell of the grains.