JPS58144826A - Silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material giving a good interimage effect and highly improved in color reproductivity, by forming on a support, silver halide emulsion layers consisting of layers different in photosensitivity, contg. more iodine in layers nearer to a support, and different in color sensitivity. CONSTITUTION:A silver halide color photosensitive material consists of a support and plural photosensitive silver halide emulsion layers different in color sensitivity, and at least 2 photosensitive silver halide emulsion layers sensitive to the same color and yet different in sensitivity. An amt. of iodine contained in each photosensitive silver halide emulsion layer different in color sensitivity becomes highest in the layer nearest to the support, and it is made gradually lower as the layer becomes farther from the support. Said layer nearest to the support preferably contains a nondiffusible DIR compd. represented by some of formulaI-IV where A1 is a yellow coupler residue, or the like, and R1 is 1-5C alkyl or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a multilayer color silver halide photographic light-sensitive material (hereinafter referred to as color light-sensitive material) KR'v'. This invention relates to a color photographic material with improved color reproducibility and color sharpness compared to combination K. Color photographic light-sensitive materials L usually consist of two or more light-sensitive emulsion layer units, and each light-sensitive emulsion layer unit functions independently.

That is, a normal color photographic material has a cyan coupler built into the support and emits mainly red light (substantially 1 about 580 nm).
A photosensitive emulsion layer (R,
L), with a built-in magenta coupler, it mainly emits green light (visible light of about 1 about 500 nm to about 600 nm) Km
It consists of a light-sensitive emulsion layer (G, L) that emits light, a light-sensitive emulsion layer (B, L) that contains a built-in yellow coupler and emits mainly blue light (light with a wavelength shorter than approximately 1,500 nm), and the like. An intermediate layer (M, L), a filter layer for ultraviolet rays or light in a specific wavelength range (F, L), and an antihalation layer (A, H, L) are provided so that the functions of each of the above photosensitive emulsion layer units function independently. , an intermediate layer with a masking function (U,
Ml, L) and protective layers (P, L) are added.

For the purpose of improving color reproducibility, colored couplers such as so-called "DIR couplers, DIR quinone derivatives, and DIR colorless couplers" have been used. Regarding these K, for example, U.S. Pat.
No. 49,766, No. 2 455.170, No. 2,600,788, No. 2 428.054,
Same No. 3,148,062, Same No. 2゜983.608
No. 1,044,778 and related improvement patents, O. R. Barr, J. R. Th1rt
ls and P.W. Vittum, Photogra
phic 5aiena@anl Eng.

Magazine Vol. 13, pp. 74-80 (1969), Magazine 214-
217 pages (1969 U.S. Pat. No. 3,379,529)
No. 3,632,345, No. 3,622,32
It is written in No. 8 etc. Colored couplers have the major drawback that the coupler itself is colored.
Ru. DIR couplers themselves form color-forming dyes through color-forming properties; constraints, usage conditions constraints (
Furthermore, conventional DIR couplers have drawbacks such as chemical instability. The so-called "DIR-colorless couplers" have the disadvantage of weak coupling activity in the color-forming state.

The conventionally known so-called l'DIR-hydroginone derivatives have the advantage that they can be applied to any light-sensitive emulsion layer and colloid layer.
-Inhibitor Releasing Ac
tivity) is too low. In addition, it reacts with aromatic primary amines and current herbal medicines (for example, para-phenylene diamines and para-amino 7 ethers) to produce cyan dye as a by-product (this is called "abnormal coloring"). Also, DIR-
Hyde tetraquinone derivatives must be protected against certain photosensitive silver halide grains, but this is generally difficult. Otherwise, the r) I R--hydroquinone derivative position, the so-called i IRT) (Inhib
(Lton Releasing Developing)
It works as a co-worker and has a stable and strong interlayer effect (Interla
yer Into-ri”ags Effect)
There is no improvement in color sharpness or color sharpness.

In general, when a hydroquinone derivative is used in a photosensitive material with a multilayer structure and is insufficiently fixed to a specific colloid layer but is not protected from photosensitive silver halide grains, the interlayer effect that originally occurs between the photosensitive emulsion layers is It was found that this effect was significantly improved.

On the other hand, in conventional multilayer color light-sensitive materials, patents have been issued regarding various layer structures in order to improve sharpness or image quality. For example, Tokuko Sho 49-15495,
JP 51-80225, JP 49-3843, U.S. Patent No. 3.658.536, JP 51-49027
, U.S. Patent No. 3.402゜046, U.S. Patent No. 4,021
, No. 238, and JP-A-53-7230 aIfi. However, in all of these conventional emulsions, silver halide emulsions having a lower iodine content have been used because of their developability.

However, as it has become clear that the legal content has a great effect on the ability to suppress current workers, it has become clear that its usage can have unexpected multilayered effects.

It is an object of the present invention to improve these deficiencies. In particular, the first object is to provide a color photosensitive material that provides a good multilayer effect and highly improved color reproducibility.

The second object is to provide a color photosensitive material with good processing stability.

The third object is to provide a color photosensitive material in which the graininess of the photosensitive layer closest to the support is highly improved.

A fourth object is to provide a color photosensitive material in which the desilvering property of the photosensitive layer closest to the support is highly improved.

The above-mentioned objects of the present invention have been achieved as follows. That is, on the support, WI! , 1 with different luminosity
In a color photosensitive material comprising a plurality of photosensitive silver halide emulsion layers having the same photosensitive property, the normal content of silver halide contained in each of the photosensitive silver halide emulsion layers is , achieved by a color light-sensitive material characterized in that the light-sensitive silver halide emulsion layer on the side closest to the support is the largest, and the light-sensitive silver halide emulsion layers on the side further away from the support sequentially become smaller. It was done.

In the photosensitive layers of the present invention having the same color sensitivity, it is preferable that a plurality of layers having different photosensitivity are in contact with each other, and the photosensitive layers having different color sensitivities are separated by a non-silver halide emulsion layer. It is most preferable that the

The silver halide used in the present invention is most preferably a silver iodobromide emulsion, and the normal content of the light-sensitive silver halide emulsion layer closest to the support is most preferably 6 to 12ffio1%.

Moreover, the difference in preferred (-) legal content between a certain S-based layer with the same color sensitivity and another photosensitive layer with the same 1f color is 1
It is preferable that there is a difference in mo of 1% or more.

In the photosensitive layer having the highest legal content near the support according to the present invention, during the color development process, the development of silver halide is suppressed as a result of reaction with the oxidized form of the color developer. It is preferable to contain at least one type of non-diffusible so-called DIR compound capable of releasing a chemical substance. Examples of the DIR compound include, but are not limited to, the following compounds. It's not something you can do.

DIR compound example O N=N N=N C,H.

-35 -36 -37 Among the KDIRDIR compounds, DIR compounds represented by the following formulas (1) to (4) are most preferable.

This symbol represents A1's yellow coupler residue, magenta coupler residue, cyan coupler residue, malondiimide coupler residue, malon diester coupler residue, or indanone coupling compound residue. 81 Co., Ltd. Represents a bromine atom, an acylamino group, a penzothiazolidenamino group, or an aralkyloxy group. R1 represents a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, a cycloalkyl group, an alkenyl group, or a 5- to 6-membered heterocyclic residue.

Specific examples of these compounds are shown below, but the invention is not limited thereto.

D-Father CI! D-ω CI@Toco-CH-COOCt@H1y -66 D-69 The photosensitivity of the same color sensitivity according to the present invention may be composed of layers **, in which case, the photosensitivity of the same color sensitivity It is preferable that the upper layer (the layer on the side farther from the support) of the sensitive layers has higher sensitivity.

Examples of silver halide used in the silver halide emulsion layer of the color light-sensitive material according to the present invention include silver chloride, silver bromide, silver iodide,
Any of those used in conventional silver halide photographic emulsions, such as silver chlorobromide, silver iodobromide, and silver chloroiodobromide, are included.

These silver halide grains may be coarse or fine, and the grain size distribution may be narrow or wide. Further, the crystals of these silver halide grains may be normal crystals or twin crystals, and any ratio of the [1oo] plane to the (111) plane can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure with different inside and outside. Further, these silver halides may be of a type in which the latent layer is mainly formed on the surface or may be of a type in which the latent layer is formed inside the grain. These silver halide grains can be prepared by known methods commonly used in the art. The dried silver halide is generally dispersed in gelatin, but in addition to gelatin, polymers such as polyvinyl alcohol are also used as a substitute for gelatin or mixed with gelatin. Silver halide emulsions in which the silver halide is dispersed in a suitable binder can be chemically sensitized. They can be done by any conventional method. Namely, active gelatin, noble metal sensitizers such as water-soluble gold salts, water-soluble platinum salts, water-soluble palladium salts, water-soluble rhodium salts, and water-soluble iridium salts; sulfur sensitizers; selenium sensitizers; polyamines, primary chloride Chemical sensitization can be carried out using chemical sensitizers such as reduction sensitizers such as tin alone or in combination. Further, 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, or a trimethine dye, or an optical sensitizer such as a merocyanine dye, alone or in combination. It can be optically sensitized (eg, by superchromatic S).

Further, known 2-equivalent and 4-equivalent couplers can be used in the silver halide color photographic light-sensitive material according to the invention 1111.

As the yellow coupler, open-chain tettomethylene couplers can be used, and among these, benzoylacetanilide type and pivaloylacetanilide type yellow couplers are advantageous.2 Specific examples of yellow couplers that can be used are: : No. 2.8'78,057, fHj@
No. 3,265,506, No. 3.277.155, No. 3,408,194, No. 3.415,652,
No. 3,447,928, No. 3,664,841, Japanese Patent Publication No. 13576-1976, Japanese Patent Publication No. 29432-1973
No. 48-66834, No. 49-10736, No. 49-122335, No. 50-28834, No. 50
-132926, Japanese Patent Application No. 53-145024, etc.

As the magenta coupler, compounds such as pyrazolone type, pyrazolotriazole type, pyrazolinobenzimidazole type, indash type, cyanoacetyl thread, etc. are used. Specific examples of magenta couplers that can be used include U.S. Pat.
No. 600,788, No. 3.061,432, No. 3
, No. 062,653, No. 3.127,267, No. 1
No. 113,311,476, No. 3,419,391, No. 3,519,429, No. 3,558,319
No. 3,684,514, No. 3.888,68
0, British Patent No. 1,247,493, British Patent No. 1,53
No. 4,349, West German Patent Application (OL8) 2.156,1
No. 11, Belgian Patent No. 769,116, Belgian Patent No. 792
．． No. 525, JP 46-60479, JP 49
-29639, 49-111631, 49-1
No. 29538, No. 50-13041, No. 50-122
No. 935, No. 51-20826, No. 52-58533
No. 52-80027, Japanese Patent Application No. 52-98876, No. 52-101247, 1HJ52-104437
It is written in the number etc.

As a colored magenta coupler as a masking coupler, a compound in which the active site of a colorless magenta coupler is substituted with a luazo group is generally used.
For example, U.S. Patent No. 2.801°171; -9
No. 83,608, No. 3,005゜712, No. 3,
Examples include compounds described in British Patent No. 684,514, British Patent No. 937.621, and Japanese Patent Application Laid-open Nos. 49-123625 and 49-131448.

Additionally, colored magenta couplers of the type described in U.S. Pat. No. 3,419,391, in which the dye is leached into the processing bath by reaction with the oxidation products of the color developing agent, may also be used. Ru.

Phenol or narratol derivatives are generally used as cyan couplers. Specific examples include US Patent No. 2,423,730, US Patent No. 12,474°293,
Same No. 2,801,171, Same No. 2,895゜826, Same No. 3,476.563, Same No. 3.737゜316
No. 3,758,308, No. 3.839゜04
No. 4, No. 3,998,642, Japanese Unexamined Patent Publication No. 47-37
No. 425, No. 50-10135, No. 50-25228
No. 50-112038, No. 50-117422, No. 50-130441, No. 51-21828, No. 52-18315, No. 53-52423, No. 53-
No. 105226, No. 53-109630, No. 56-6
No. 5134, Japanese Patent Application No. 56-903348-6 and No. 5
It is written in 6-1313124, etc.

As a colored cyan coupler as a masking coupler, a compound in which an arylazo group is substituted at the active site of a colorless cyan coupler is used, such as U.S. Pat. No. 2,521,908, U.S. Pat. No. 3,034,693, British Patent No. 1,255,111, Japanese Unexamined Patent Publication No. 48-22
Examples include compounds described in No. 028 and the like.

Furthermore, U.S. Patent No. 3,476.563 and Japanese Patent Application Laid-open No. 1987-1
Colored cyan couplers of the type in which the dye flows out into the processing bath by reaction with the oxidation product of a color developing agent, such as those described in No. 0135 and No. 50-123341, can also be used.

Further, in order to improve photographic properties, a so-called combining coupler, which forms a colorless dye, may be included.

The DIR compound and coupler according to the present invention can be used separately dispersed, or any two
They can be mixed and dispersed in combination, or F1a can be mixed and dispersed at the same time. Most preferably, it is effective to mix and disperse the three at the same time. In addition, if a low boiling point solvent is used, U.S. Patent No. 2,801,171 or Butterfly Patent Publication
It is also possible to remove the low boiling point solvent from the dispersion by the method described in Japanese Patent No. 8099.

Particularly preferred among the applicable solvents are high boiling point solvents such as dibutyl phthalate, dioctyl 7-thalate, diisodecyl phthalate, triphenyl phosphate, tricresyl phosphate, diethyl laurylamide, dibutyl laurylamide, benzyl phthalate, monophenyl -p-1-butylphenyl phosphate, phenoxyethanol, diethylene glycol monophenyl ether, di-methoxyethyl-7-talate, hexamethylphosphoramide, and US Pat. No. 3.779,
No. 765, Japanese Unexamined Patent Publication No. 49-90523, Japanese Patent Publication No. 1973
Examples include high-boiling organic solvents that are immiscible with water and are described in Japanese Patent No.-29060. In addition, examples of low boiling point solvents include methyl isobutyl naton, β-ethoxyethyl acetate, methoxy triglycol acetate, acetone, methyl acetone, methanol, ethanol, acetonitrile, dioxane, dimethyl formamide, dimethyl sulfoxide, ethyl acetate, butyl acetate, isopropyl Examples include acetate, -butanol, chloroform, cyclohexane, cyclohexanol, fluorinated alcohol, etc. These low boiling point solvents can be used in place of high boiling point solvents, and can also be used in combination with high boiling point solvents. However, each of these solvents can be used alone or in combination of two or more.

Further, the silver halide color photographic light-sensitive material according to the present invention includes:
The photosensitive layer and/or other constituent layers (eg, intermediate layer, undercoat layer, filter layer, protective layer, scratched layer, etc.) may contain various other photographic additives depending on the purpose.

For example, stabilizers and antifoggants such as azaindenes, triazoles, tetrazoles, imidazolium clay, tetrazolium salt polyhydroxy compounds, etc.; aldehyde-based, aziridine-based, isoxazo-/I/-1hs vinylsulfone-based, aquisulfone-based, Hardening agents such as albodiimide, maleimide, methanesulfone ester, and triazine; tone adjusting agents such as group 8 metals (e.g. rhidium, ruthenium) or cadmiellium, thallium; benzyl alcohol, polyoxyethylene Image stabilizers for chroman, claman, bisphenol, and phosphite yarns; wax,
There are lubricants such as glycerides of higher fatty acids and higher alcohol esters of higher fatty acids. In addition, anionic, cationic and non-ionic surfactants are used as coating aids, emulsifiers, permeability improvers for processing solutions, decolorants, and materials for controlling various physical properties of photosensitive materials. Ionic or amphoteric steels can be used. As the mordant, N-guanylhydrazone compounds, quaternary onium salt compounds, etc. are effective. Effective antistatic agents include diacetyl cellulose, styrene perfluoroalkyl rhidium maleate copolymer, and an alkaline solution of a reaction product of maleic anhydride copolymer and p-aminobenzenesulfonic acid. Examples of the color turbidity inhibitor include polymers containing vinylpyridone monomers, polymers containing vinylimidazole monomers, and the like.

Examples of matting agents include 4-polymethyl methacrylate, polystyrene, and alkali-soluble polymers. Furthermore, it is also possible to use colloidal silicon oxides.

Further, examples of the latex added to improve the physical properties of the film include copolymers of acrylic esters, vinyl esters, and other monomers having ethylene groups. Examples of gelatin plasticizers include glycerin and glycol compounds, and examples of thickeners include styrene.
Sodium maleate copolymer, alkyl vinyl ether
Examples include maleic acid copolymers.

The silver halide color photographic light-sensitive material according to the present invention is produced by coating a support with a silver halide emulsion layer and other constituent layers containing the various photographic additives as described above as necessary. Advantageously used supports include wires, such as baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass paper, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate, polystyrene, etc. These supports are appropriately selected depending on the intended use of the silver halide photographic material.

These supports are subjected to undercoat processing as necessary.

After exposure, the silver halide color photographic material of the present invention can be developed by a commonly used known method.

For example, color development can be carried out by a commonly used color development method. In the reversal method, the process is first developed with a black-and-white negative developing solution, then exposed to white light, or treated with a bath containing a capri agent, and then processed with an alkali solution containing a color developing agent.
Develop color with solution II. There are no particular restrictions on the processing method, and any processing method can be applied, but typical examples include a method in which after color development, bleach-fixing is performed, and if necessary, further washing with water and stabilization treatment are performed, or after color development. , bleaching and fixing are carried out separately (if necessary, further washing with water and stabilization treatment are carried out). It is also known to process silver halide photosensitive materials, and these methods can also be used to process them.Also, these processes are sometimes carried out at high temperatures for rapid processing, and can be carried out at room temperature or in special cases. may be carried out at lower temperatures. When performing high-temperature rapid processing, pre-I! membrane treatment can also be performed. Also, depending on the type of processing agent used, auxiliary baths such as various neutralization towers may be required. These auxiliary baths may be used as necessary.

A particularly useful color-forming active ingredient used for color-forming the silver halide color photographic light-sensitive material according to the present invention is the first color-forming active ingredient.
Typical examples of the class phinidine diamines and derivatives thereof include the following.

4-Amino-N, N-diethylaniline, 3-methyl-
4-amino-N, N-diethyl aulis 4-amino-N
-ethyl-'-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfona Considered doethyl aerin, 3-methyl-4-atno-N-ethyl-N-β-methoxyethylaniline, 3-β-methanesulfonamidoethyl-4
-7 no N, N-diethylaniline, 3-methoxy-
4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N=ethyl-N-β
-Methoxyethylaniline, 3-acedodate-4-amino-N,N-diethylaniline, 4-amino-N,N
-dimethylaniline, N-ethyl-N-β-[β-(β
-methoxyethoxy]ethoxy]ethyl-3-methyl-
4-ami/aniline, N-ethyl-N-β(β-methoxyethoxy)ethyl-3-methyl-4-ami/aniline and salts thereof, such as sulfate, hydrochloride, sulfite WIt11
, P-) luenesulfonic acid.

Next, the present invention will be illustrated by giving Examples.
It is not more limited.

Example-1 The following layers were sequentially layered on a support made of transparent cellulose triacetate film from the support side, and sample A1 was prepared.
Color negative photosensitive materials Nos. 01 to 107 were produced.

1st layer: antihalation layer Black 5% aqueous gelatin solution containing colloidal silver 1 and 9 were coated on a 5K cloth using 1 g of a hardening agent (T()) to give a dry film thickness of 1 μm.

2nd layer: Intermediate layer 2.50 g of 5-di-t-octylno
d and dissolved in 10% aqueous gelatin solution.
Emulsion (I) 2509 obtained by emulsifying and dispersing 5 g of 1-Lou OT (manufactured by American Cyanamid Co., Ltd.) was
1kl of 0% gelatin solution? Mix with hardener ()(
) 1 g to give a dry film thickness of 2 μm.

Third layer: red-sensitive emulsion layer Silver iodobromide emulsion prepared by a conventional method (silver content: 20.
6 mol, astringent skin content: Table 1, average particle size 0.6μ)
k 4X10-' moles of sensitizing dye A and lXl of sensitizing dye B
0-'' mole of 1-hydroquine-N-(δ-(2,4-di-t-amylphenoxy)methyl)-2-su7tamide as a cyan coupler for spectrally sensitization.
Ii was dissolved in 100 co of dibutyl phthalate and 200 oo of ethyl acetate, 420.9 g of emulsion (2) obtained in the same manner as emulsion (i) was added, and a hardening agent (H
) 0.8F to give a dry film thickness of 4.5μ.

4th layer; intermediate layer; 5th layer, same as the 2nd layer; green-sensitive emulsion layer; silver iodobromide emulsion prepared by a conventional method; silver content: 0.
6 mol, legal content; Table-1. Average particle size 0.6μ)
2X10-' moles of Ic sensitizing dye C and 6X of sensitizing dye C
1-(2,4,6-trichlorophenyl)- as magenta coupler.
80 g of 3-(3-(2,4-di-monoamylphenoxyacetamide)benzamide-5-pyrazolone) was mixed with 100 co of tricresyl phosphate and 2 co of ethyl vinegar.
00 cc and added 600 g of emulsion @) obtained in the same manner as emulsion (1), and further added 1 l of hardener (H).
The film was coated using I to give a dry film thickness of 4 μm.

6th layer: Add 200 g of the yellow filter single layer emulsion ([) to 1 part 9 of an aqueous gelatin solution containing yellow colloidal silver, and further add K and 19 hardening agent (H) to a dry film thickness of 1 μm. I applied it to Naruyo 5.
- 7th layer: blue-sensitive emulsion layer 1 kg of silver iodobromide emulsion (silver content: 0
．． 6 mol, astringent skin content Table 2-1, average particle size 0.6
μ) K yellow coupler α-pivaloyl-α-(
1-hensyl-2-phenyl-3゜5-dioxo-1,
2,4-)Ryasiridin-4-yl)-2'-chloro-
Dissolve 100I of 5'-[α-(dodecyloxycarbonyl)ethoxycarbonyl]acetanilide in 200d of 100117 ethyl acetate of dibutyl phthalate to create an emulsion (emulsion obtained in the same manner as above (g)).
Add KIII agent CH) III, film thickness when dry 3. I applied it diligently to make it aK.

8th layer: Protective layer 10% gelatin aqueous solution 1kllK Hardener (H) 1g
The film was applied to a dry film thickness of 1 μm.

Hardener CH): 2,6-dichloro-4-oxytriazine sodium salt (added as a 2% aqueous solution) Sensitizing dye A
-D is as follows.

Sensitizing dye C: anhydro 5,5'-dichloro-3,3
'-Disulfoprobyl-9-ethyl-thiacarbocyanine hydroxide pyridinium salt Dye B: anhydro-9-ethyl-3,3'-')
-(3-sulfopropyl) 4,5.4', di-benzothiacarbocyanine hydroxide triethylamine salt sensitizing dye C: anhydro9'-2f-5,5'-cyclo3,3'-di Sulfoglopyruoxacarpocyanine sodium salt sensitizing dye D: Anhydro 5.6.5', 6'-tetrachloro-1,1'-3,3'-disulfoglopoxyethoxyethyl'imidazolocarbocyanine hydroxyside The coated samples thus obtained were given 101-107 K Nutosil wedge exposures. Similarly, samples 101-1
Blue using Wratten filter for 07 K
, Green, and Red. Wedge exposure is performed using decomposition exposure. After the sample thus obtained was subjected to the following treatments, it was sensitized. The interlayer effect was measured by taking the ratio of each γ characteristic value by IJ-of those subjected to neutral exposure and those subjected to decomposition exposure as shown in Table 1-2.

Treatment step: Treatment was performed at 43.3°C.

1. Color development 3 minutes 15 seconds 2. Bleaching white 6 minutes 30 seconds 3. Wash with water for 3 minutes 15 seconds 4. Arrive 6 minutes 30 seconds 5. Wash with water for 3 minutes 15 seconds 6. Stability 3 minutes 15 seconds The treatment compositions used for each IK were as follows.

Color developer Sodium nitrotriacetate 1.0.9 Sodium sulfite 4. O,p Sodium carbonate 30.0p Potassium bromide
1.4g Hydroxylamine sulfur Fl*
2.4. p4-(N-ethyl-N-β-hydroxyethylamino)-2-methyl-7 disinosulfate
4.5I water Ammonium bromide bleach solution 160.0. p Aqueous ammonia (28%) 25.0 mg Ethylenediamine-tetraacetic acid sodium salt 130 g Wood vinegar 11
with 14v water
1! Fixer Sodium Tetrapolyphosphate 2.09 Sodium Sulfite 4.0. p-thiosulfate 72% chive A (70%) 275.011/sodium bisulfite 4.6g in water
1! Stabilized liquid formalin (40%) with 8.0m water
l1 Table 1-2 Here, γ represents gradation, and for details, refer to "Photochemistry".
(Author: Makoto Kikuchi) Represents photographic characteristics as described on page 90.

As can be seen from Table 1-2, in the sample according to the present invention, effective multilayer effects were confirmed for all photosensitive layers.

Example 2 The following layers were sequentially formed on a transparent polyethylene terephthalate support from the support side to prepare multilayer color negative light-sensitive materials (sample numbers 201 to 210).

1st layer: antihalation layer black gelatin aqueous solution containing colloidal silver
# cloth was applied at a ratio of d so that the dry film thickness was 30 μm.

2nd layer: intermediate layer gelatin aqueous solution dried film thickness: 1. I applied it to OaK Naruyo 5.

3rd layer: Red-sensitive, low-sensitivity silver halide emulsion layer Silver iodobromide emulsion (average grain size 0.5μ, silver iodobromide emulsion containing silver iodide (Table 2), gold and sulfur sensitizers) and then chemically sensitized with anhydrous 9-ethyl-3,3'- as a red-sensitive sensitizing dye.
Di(3-sulfopropyl)-4,5,,4', 5
'-dibenzothiacarbocyanine hydroxide; anhydrous 5
,5'-dichloro-9-ethyl-3,3'-di(3-
sulfobutyl)thiacarbocyanine hydroxide; and anhydrous 2-[2-((5-chloro-3-ethyl-2(3
H)-penzothiazolidene)methyl)-1-butenyl-
After adding 5-chloro-3-(4-sulfobutyl)benzoxacilium, 4-hydroxy-6-methyl-
1,3,3a,7tetrazaindene 1.09.20.011v of 1-phenyl-5-mercaptotetrazole was added to prepare a red-sensitive low-sensitivity emulsion. Furthermore, 1 hydroxy-N-(δ
-(2,4-di-t-amylphenoxy)butyl2
- naradamide 59 g, as colored cyan coupler 1-hydroxy-4-(4-(1-hydroxy-8-acetamido-3,6-disulfo-2-naphthylazo)phenoxy)-N-[4-(2,4-di -t-amylphenoxy)butyl]-2-naphthochloride sodium salt 4
g, also dodecyl gallate 0.5 Ii Mira addition, tricresyl phosphate 65,91 ethyl acetate 136
The mixture of WLl was dissolved by heating, added to 550 liters of a 7.5% aqueous gelatin solution containing sodium triisopropylnaphthalene sulfonate 5II, and the dispersion (1) emulsified and dispersed in a colloid mill was added to form a red-sensitive low-sensitivity emulsion. was prepared and coated to a dry film thickness of 4.0 μm. (Contains 160 g of gelatin per mole of silver halide) Fourth layer: Anhydrous 9-ethyl-3,3'-di(3-sulfopropyl) as a red-sensitive sensitizing dye in the red-sensitive high-sensitivity silver halide emulsion layer. -4,5,4', 5'-dipenzothialocyanine hydroxide, anhydrous 3,3-dichloro-
9-ethyl-3,3'-di(3-sulfobutyl)thiacarbocyanine hydroxide; and anhydrous 2-(2-(
(3-chloro-3-ethyl-2(3)1)-benzothiazoliden)methyl)-1-butenyl-3-chloro-3-
After addition of (4-sulfoptyl)benzoxacilium, 4-hydroxy-6-methyl-1,3,3&.

7tetrazaindene 1.0g and 1-phenyl-5-
10.0 Njp of mercaptotetrazole was added to prepare a red-sensitive emulsion.

Furthermore, 1- as cyan coupler per mole of silver halide.
Hydroxy-N-(J-(2,4-di-t-amylphenoxy)phthyl]-2-naphthamide 17.p, 1-hydroxy-4-[4 as colored cyan coupler)
-(1-Hydroxy-δ-acetamido-3,6-disulfo-2-naphthylazo)phenoxy)-N-(δ-(
4 g of 2,4-di-t-amylphenoxy)tetyl]-2-naphthoide disodium salt and 0.51 g of dodecyl gallate were added, and 20 g of tricresyl phosphate was added.
A mixture of I and ethyl acetate 60 was dissolved by heating and added to a 7.5-layer gelatin aqueous solution 3011 containing 1.5 g of sodium triisopropylnaphthalene sulfonate, and the dispersion (2) emulsified and dispersed using a colloid mill was added. A red-sensitive high-sensitivity emulsion was prepared and coated to a dry film thickness of 2.0 μm. (Contains 160g of gelatin per mole of silver halide) 5th layer: Intermediate layer 6th layer same as the 2nd layer:! A silver iodobromide emulsion having an average grain size of 0.6μ and containing the amounts shown in Silver Iodide-2 was chemically sensitized with gold and sulfur sensitizers, and further #
As a sensitizing dye, anhydrous 5,5'-dichloro-9-ethyl-3,3'-di(3-sulfobutyl)oxacarbocyanine human o + cytoI anhydrous s 1 s'-diphenyl-9-: L + sil- , 3'-di(3-sulfobutyl)oxacarbocyanine hydroxide and anhydride 9
-ethyl-3,3'-di(3-sulfopropyl)-5
, 6° 5', 6'-dibenzooxalpocyanine hydroxide was added, and then 4-hydroxy-6-methyl 1° 3.3a, 7 tetrazaindene 1. Oli and 1-phenyl-5-mercaptotetrazole 20.0~
was added and adjusted in the usual manner. The two types of silver halide emulsions thus obtained were mixed at a ratio of 1=1 to prepare a green-sensitive and low-sensitivity silver halide emulsion.

1 mole of WK octahegenide as magenta coupler
-(2,4,6-)lichlorophenyl)-3-(3-(
4-dodecyloxyphenyl)sulfonamidobenzamido)-pyrazolin-5-one 100.9, 1-(2,4,6-)lichlorophenyl)-4-(1-naphthylazo)-3-(2 as colored magenta coupler) -Chloro-5-octadecenylsuccinimide anilino)-
5-pyrazolone 2.5.9, also dodecyl gallate 0
．． 52 and tricresyl phosphate 120.9]
A mixture of 240-ethyl acetate was dissolved by heating, added to an aqueous gelatin solution containing sodium triisopropylnaphthalenesulfonate, and emulsified and dispersed in a colloid mill to obtain a dispersion (3
) to prepare a green-sensitive low-sensitivity emulsion.

The coating was applied to a dry film thickness of 4.0 μm. , (containing 160 g of gelatin per mole of silver halide) 7th layer: Green-sensitive, high-sensitivity silver halide emulsion layer Silver iodobromide emulsion (average grain size 1.2μ, silver iodide in the amount shown in Table 2) ) was chemically sensitized with gold and sulfur sensitizers, and K was anhydrous 5,5'-dichloro0-9-ethyl-3,3' as a green-sensitive sensitizing dye.
-di(3-sulfobutyl)oxacarbocyanine hydroxide: anhydrous 5+5'-diphenyl-9-ethyl-3
,3'-di(3-sulfobutyl)oxacarbocyanine hydroxide and anhydrous-9-ethyl-3,3'-di(3-sulfopropyl)-5,6°5',6'-dibenzoxacarbocyanine After adding hydroxide, 1.0 g of 4-hydroxy-6-methyl-1,3,3a,7tetrazaindene and 1-phenyl-5-mercaptotetrazole io, o~ were added to produce green-sensitive, high-sensitivity silver halide. An emulsion was prepared.

Furthermore, as a magenta coupler, 80 g of 1-(2,4,6-trichlorophenyl)-3-(3-(2,4-di-tert-alphenoxyacetamide)benzamide)-pyrazolin-5-one, a colored magenta coupler. as 1-(2,4,6-1-lichlorophenyl)-4-(1
-naphthylaso)-3-(2-104-5-ttadecenylsuccinidoanilino)-5-pyrazolone 2.5
g, 2゜5-di-t-octylhydroquinone 1.5g
and tricresyl phosphate 120
A mixture of g and ethyl acetate 240-g was dissolved by heating, added to an aqueous gelatin solution containing sodium triisopropylnaphthalene sulfonate, and the dispersion (4) emulsified and dispersed in a colloid mill was added to prepare an S-sensitive high-sensitivity emulsion. Dry film thickness 2
．． (Contains 160.p of gelatin per mole of silver halide) 8th layer: Intermediate layer Same as 2nd layer. 9th layer: One layer of yellow filter.

2, in an aqueous gelatin solution in which yellow colloidal silver is dispersed.
5-di-t-octylhydroquinone 39 and di-2-ethylhexyl phthalate 1.51i ethyl acetate 101
Add a dispersion prepared by dissolving 0.1j of sodium triisopropylnaphthalene sulfonate in an aqueous gelatin solution containing 0.3.9% of sodium triisopropylnaphthalene sulfonate;
5-di-t-octylnoidowaquinone 0.10g/@
'' to give a dry film thickness of 1.2 μm.

10th layer: blue-sensitive, low-sensitivity silver halide emulsion layer Silver iodobromide emulsion (average grain size 0.6μ, containing silver iodide (amount shown in Table 2)) is sensitized with gold and sulfur. Chemically sensitized and further anhydrous 5゜5'-dimethoxy-3,3 as a sensitizing dye.
'-di(3-sulfopropyl)thiacyanine hydroxide and then 4-hydroxy-6-methyl-1,3
, 31L, 7tetrazaindene 1. OII, I-phenyl-5-mercaptotetrazo-/I/20.01111
was added and adjusted in a conventional manner to prepare a blue-sensitive, low-sensitivity silver halide emulsion.

Additionally, α-piparoyl-α-(1-benzyl-2-phenyl-
3,5-dioxo-1,2,,4-)riasilidine-4
-yl)-2゛-chloro-5゛-[α-(dodecyloxycarbonyl)ethoxycarbonyl]acetanilide 1
20g of α-13-[α-(2,4-di-t-amylphenoxy)butyramide))benzoyl-2-methoxyacetanilide, and dibutyl phthalate x
A mixture of 2o9 and 300 sI of ethyl acetate was dissolved by heating, added to an aqueous gelatin solution containing sodium triisopropylnaphthalene sulfonate, and emulsified and dispersed in a colloid mill.The dispersion (5) was added to form a blue-sensitive, low-sensitivity 7% logeyl. A silver emulsion was prepared and coated to give a dry film thickness of 4.0 μm.

(Contains 16011 gelatin per mole of silver halide) 11th layer: Blue-sensitive, high-sensitivity silver halide emulsion layer Silver iodobromide emulsion (average grain size 1.2μ, nF iodide amount shown in Table 2) ) is chemically sensitized with gold and sulfur sensitizers, and further K
Anhydrous 5゜5゛-dimethoxy-3 as l/i sensitizing dye,
Add 3'-di(3-sulfopropyl)thiacyanine hydroxide followed by 4-hydroxy-6-methyl-1
, 3,3a,7 tetrazaindene (1.0 J) and 1-phenyl-5-mercaptotetrazole io, oq were added thereto and adjusted in a conventional manner to prepare a blue-sensitive, high-sensitivity silver halide emulsion. Furthermore, α-pivaloyl-α-(1-benzyl-2-
Phenyl-3,5-dioxo-1,2゜4-triacylidin-4-yl)-2'-chloro-5'-[:α-(dodecyloxycarbonyl)ethoxycarbonyl]acetanilide, goli was added and dibutyl phthalate was added. )80I
i, heating and dissolving a mixture of ethyl acetate 2401117;
A blue-sensitive, high-sensitivity silver halide emulsion was prepared by adding the dispersion (6) emulsified and dispersed in a colloid mill to an aqueous gelatin solution containing sodium triisopropylnaphthalene sulfonate so that the dry film thickness was 2.0μ. Km clothed. (Contains 240 p of gelatin per mole of silver halide) 12th layer: Intermediate layer di-2-ethylhexyl 7 tale) 2,9.2-[3-
Mix 2 g of cyano-3-(n-dodecylami7carbonyl)allylidene-1-ethylpyrrolidine and 2-ethyl acetate, add a dispersion in an aqueous seratin solution containing 0.6Ii of sodium triisopropylnaphthalenesulfonate, and add this. was applied at a ratio of 1.0117 t of gelatin to a dry film thickness of 1.0 μm.

13th layer: A gelatin aqueous solution containing 0.2.9 gelatin 4,9.1.2-bisvinylsulfonylethane per 100 id of protective layer was prepared at a ratio of 1.311 gelatin/d to a dry film thickness of 1.2 μm (
Note) The upper row of numbers in the table represents the content% of washed coal, and the lower row represents the DIR compound contained in the washed coal and its addition amount. However, D
The amount of the IR compound added represents the number of moles per 100 moles of silver halide, and the DIR compound is the number of moles per 100 moles of silver halide. 210 was processed into a 35rrna color negative photosensitive material, photographed with a still camera, and subjected to in-situ processing at 38° C. in the same processing steps as in Example-1.

As a result, it was found that the color negatives obtained from samples 205 to 210 had extremely superior performance in color reproduction color purity compared to the color negatives obtained from samples 201 to 204 for comparison. Ta.

Furthermore, the granularity (RMS) was measured as graininess.

The measurement was carried out by comparing 1000 times the standard deviation of the variation in density value that occurs when scanning with a microdensitometer having a circular scanning aperture of 25 μm. The results are shown in Table 2-2.

Table 2-2 As is clear from the 12R measurement value table, the effect of improving the line granularity of the present invention was confirmed, and the effect of improving the granularity of the photosensitive layer (red-sensitive layer) close to the support was particularly remarkable. .

Agent Yoshi Kuwahara Beautiful Procedural Amendment (Method) 1. Indication of the case Patent Application No. 18673 filed in 1988 2. Name of the invention Silver halide color photographic light-sensitive material 3. Person making the amendment Relationship to the case Patent applicant residence Address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name:
Name (127) Konishiroku Photo Industry Co., Ltd. 6, Subject of amendment Specification 7, Contents of amendment; engraving of specification (no change in content) Procedural amendment ↑ IJ 19857 Patent Application No. 28673 2 Name of the invention Silver halide color photographic light-sensitive material 3 Capturing it Relationship with "I (I"l) Patent Application No. 28673 Patent Application No. 28673 Nishi-Shinjuku 1'J'l + 26 Sho 2, Shinjuku-ku, Tokyo
Name Author (127) Roku Konishi Photography Co., Ltd. 4 Agent 6 Column L of "Detailed Description of the Invention" of the Specification Subject to Amendment Contents of the Amendment The detailed description of the invention is amended as follows.

Claims (1)

[Scope of Claims] 1) A plurality of light-sensitive silver halide emulsion layers having different color sensitivities are provided on a support, and the light-sensitive silver halide emulsion layers having the same color sensitivity have different sensitivity. In a silver halide color photographic light-sensitive material composed of one or more layers, the normal content of silver halide contained in each of the light-sensitive silver halide emulsion layers having different color sensitivities is different from that of the support. A silver halide color photographic light-sensitive material characterized in that the light-sensitive silver halide emulsion layer on the side closest to the support is the largest, and the light-sensitive silver halide emulsion layers on the side further away from the support become smaller. . 2) Claim 1, characterized in that the photosensitive silver halide emulsion layer closest to the support side contains at least one non-diffusible DIR compound represented by the following general formulas (1) to (4). Silver halide color photographic light-sensitive material 5 (1) (here A, [yellow coupler residue, magenta coupler residue, cyan coupler residue, malondiimide coupler residue, malondiimide coupler residue or indanone] Represents a coupling compound residue. jaBx represents a bromine atom, an amylamino group, a penzothiazolidenamino group, or an aralkyloxy group. iRl represents an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group, an alkenyl group, or Represents a 5- to 6-membered ring HeteollI residue.