JPS62220954A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide interimage effect and to improve sharpness by constituting a photographic sensitive material to contain at least one kind of specified compds. CONSTITUTION:The photographic sensitive material is constituted so as to contain at least one compd. expressed by the formula, wherein R is a linear or branched alkylene group, linear or branched alkenylene group, linear or branched aralkylene group or arylene group; Z is a polar substituting group; X is H atom, alkali metal atom, ammonium group, or a group cleaved under alkaline condition. By this method, a multilayered color photographic sensitive material having high interimage effect and high sharpness is obtd. without impairing other photographic characteristics. Also a black and white silver halide photographic sensitive material having high sharpness as well as high graininess is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a silver halogenide photographic light-sensitive material having an improved interimage effect and improved sharpness and graininess.

(Prior art) By color-developing a silver halide color photographic material, an oxidized aromatic-amine color developing agent and a coupler react to form indophenol, indoaniline,
It is known that indamine, azomethine, phenoxazine, 7enazine and similar dyes are produced and color images are formed. In this method, a subtractive color method is usually used for color reproduction, with silver halide emulsions selectively sensitive to blue, green, and red, and yellow, which has a relationship with the remaining colors, respectively.
Magenta and cyan color imaging agents are used. To form a yellow image, for example, acylacetanilide or dibenzoylmethane couplers are used, and to form a magenta image, pyrazolone, pyrazolobenzimidazole, pyrazolopyrazole, pyrazolotriazole, cyano Acetophenone or indacylon couplers are used, and phenols or naphthols are primarily used to form cyan images.

By the way, each dye produced from these couplers does not have an ideal spectral absorption spectrum, and magenta and cyan dyes in particular have broad absorption spectra or have sub-absorption in the short wavelength region, resulting in poor color photographic sensitivity. Unfavorable for color reproduction of the material.

In particular, sub-absorption in the short wavelength region tends to cause a decrease in chroma. As a means of improving this, it is possible to improve it to some extent by creating an interimage effect.

Regarding the interimage effect, see, for example, Hanson (
Hanson et al., 'Journal on the Optical Science on America
of the 0ptical 5ociet
yof America), Vol. 4t2, pp. AAj-6, and A. Thel.
Zeitschrift fur Wissenschaftliche Photography
aphie.

Photophysiqueund, Photo-ch
emie), Volume 4t7, page 1θ ~ page //♂ and page 24tt ~ Ko! ! It is written on the page.

US Patent 3! 34, 4tL! , et al., by introducing diffusible gootiazolines into exposed color reversal photographic elements, and U.S. Pat.
．． ! 3g, 4t♂ No. 2 contains diffusible gootiazoline.
Introducing corchion into an unexposed color reversal photographic element,
A method for obtaining a favorable interimage effect is described.

In addition, in Tokuko Sho 4t♂-3ri/J9, when developing a color photographic light-sensitive material and reducing silver halide to silver, N-
It has been described that the presence of substituted goutiazoline-2-thione compounds produces a significant interimage effect.

Research Disclosure (
Research Disclosure), A/J
/, No. 13//O section (/977) K is mentioned.

Additionally, U.S. Patent No. 41. Q♂ko! ! No. 3 describes a color reversal photosensitive material with a layer arrangement that allows the movement of iodide ions during development, in which one layer contains latent image-forming silver haloiodide grains, and the other layer contains latent image-forming silver haloiodide particles. A method is described in which a good interimage effect is obtained by including silver halide grains and silver halide grains whose surfaces are caplaced so that they can be developed independently of imagewise exposure.

However, in the above method, the interimage effect is insufficient, the use of a colloidal silver-containing layer, the introduction of capacitated silver halide grains, etc. cause a decrease in color density in color reversal light-sensitive materials. It has its drawbacks.

In addition to the above, for example, in the color development process, a coupler (DIR coupler) that can release a development-inhibiting substance such as a benzotriazole derivative or a mercapto compound during a coupling reaction with an oxidized form of a color developing agent is used. It is also known that interimage effects can be produced by using hydroquinone compounds that can release development-inhibiting substances such as iodide ions and mercapto compounds during development. Their use was limited because they were accompanied by significant desensitization and decreased color density.

By the way, JP-A-60-69<10 discloses a compound similar to the compound of the present invention as a method for preventing the deterioration of image quality that occurs with the increase in sensitivity and/or rapid processing of silver halide photographic materials. /, 3,4 in combination with a thiadiazole compound and a benzenediol or its ether derivative has been disclosed. However, the 3,4t-thiadiazole compounds specifically described in the publication have a smaller interimage effect, which is the object of the present invention, than the compounds of the present invention.

OBJECTS OF THE INVENTION The first object of the present invention is to provide a multilayer color photographic material that has a large interimage effect without impairing other photographic properties.

A second object of the present invention is to provide a silver halogenide photographic material with excellent sharpness.

A third object of the present invention is to provide a black-and-white silver halide photosensitive material with high sharpness and good graininess.

(Structure of the Invention) The object of the present invention has been achieved by a silver halide photographic light-sensitive material, which is characterized by containing at least one compound represented by the following general formula CI).

General formula [I] In the formula, R represents a linear or branched alkylene group, alkenylene group, aralkylene group, or arylene group,
Z represents a polar substituent. Y-hashi, R1, R2, R3,
R4 and R5 represent a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, alkenyl group or aralkyl group. X represents a hydrogen atom, an alkali metal atom, an ammoniamyl group, or a group that cleaves under alkaline conditions.

More specifically, R is a linear or branched alkylene group (
For example, methylene group, ethylene group, propylene group, butylene group, hexylene group, /-methylethylene group),
Straight-chain or branched alkenylene groups (e.g., vinylene, /-methylvinylene, etc.), straight-chain or branched aralkylene groups (e.g., benzylidene, etc.), arylene groups (e.g., phenylene, naphthylene, etc.) represent.

Examples of the polar substituent represented by Z include substituted or unsubstituted amino groups (including salt forms, such as amine groups, hydrochloride of amine groups, methylamine groups, dimethylamino groups, hydrochloric acid of dimethylamine groups) salt, dibutylamino group,
Dipropylamino group, N-dimethylaminoethyl-N-
methylamine group, etc.), quaternary ammoniamyl group (e.g., trimethylammonylamyl chloride group, dimethylpenzylammonylamyl chloride group, etc.), alkoxy group (
For example, methoxy group, ethoxy group, -monohydroxyethoxy group, etc.), aryloxy group (e.g., phenoxy group, etc.), alkylthio group (e.g., methylthio group, butylthio group, etc.), arylthio group (e.g., phenylthio group, etc.) , etc.), heterocyclic oxy groups (e.g., copyridyloxy group, λ-imidazolyloxy group, etc.), peterocyclic thio group (e.g., cobenzthiazolylthio group, couvirazolylthio group, etc.), carbamoyl group (e.g., unsubstituted carbamoyl group, methylcarbamoyl group, etc.), sulfamoyl group (e.g., unsubstituted sulfamoyl group, methylsulfamoyl group, etc.), acyloxy group (e.g., acetyloxy group, benzoyloxy group, etc.), Ureido groups (e.g., unsubstituted ureido groups, methylureido groups, ethylureido groups, etc.), thioureido groups (e.g., unsubstituted thioureido groups, methylthioureido groups, etc.), sulfonyloxy groups (e.g., methanesulfonyloxy groups) , p-toluenesulfonyloxy group, etc.), heterocyclic group (e.g. /-morpholino group, /-piperidino group, copyridyl group, goupyridyl group, -1-thenyl group,
/-pyrazolyl group, /-imidazolyl group, 2-imidazolyl group, co- or di-imidazolyl group, cochtrahydrofuryl group, λ-tetrahydrochenyl group, etc.), cyano group, hydroxy group, sulfo group or salt thereof, A carboxyl group or a salt thereof can be mentioned.

, R,, R2, R3, R4, R5 are hydrogen atoms,
Substituted or unsubstituted alkyl groups (for example, methyl group, ethyl group, isopropyl group, dimethylaminoethyl group, hydroxyethyl group, etc.), fit-substituted or unsubstituted aryl groups (for example, phenyl group, goomethylphenyl group,
etc.), substituted or unsubstituted alkenyl groups (e.g. propenyl group, etc.), substituted or unsubstituted aralkyl groups (
For example, it represents a benzyl group, a phenethyl group, etc.).

and , X=H or an alkali metal group, such as an acetyl group, a cyanoethyl group, a methanesulfonylethyl group, etc.).

In general formula [I], preferably R is an alkylene group, Z
is a substituted or unsubstituted amino group or a salt thereof, a heterocyclic group, and R1, R2, R3, R4゜R5 is a hydrogen atom or a substituted or unsubstituted alkyl group.

In general formula (1), Z is more preferably a substituted or unsubstituted amine group or a salt thereof, R1゜R2, R3, R4
, R5 is a hydrogen atom.

Even in a black-and-white photographic material in which silver halide emulsion layers are composed of co-layers or more, an effect similar to the interimage effect in a color photographic material is observed between the silver halide emulsion layers.

For example, in a black-and-white photographic light-sensitive material, the silver halide emulsion layer has a two-layer structure: a high-sensitivity layer in which the grain size of the silver halide emulsion is generally large, and a low-sensitivity layer in which the grain size of the silver halide emulsion is generally small. , the high sensitivity layer is also developed in the high exposure dose range where the low sensitivity layer is developed. In this case, by containing the compound represented by the general formula [I] of the present invention in the high-sensitivity silver halide emulsion layer, the low-sensitivity silver halide emulsion layer, or both, the exposure amount can be increased. From low-speed silver halide emulsions,
Works to inhibit development of high-sensitivity silver halide emulsions.

As a result, the amount of developed silver in a high-sensitivity silver halide emulsion with a large grain size is generally reduced, thereby improving graininess in a high exposure range.

According to the present invention, an improvement in sharpness can be seen in a color photographic material and a black and white photographic material comprising at least seven or more silver halide emulsion layers.

At the same time as the interimage effect that occurs between different silver halide emulsion layers, an intralayer development inhibition effect occurs.

This development suppressing effect is expressed at the edges of the highly exposed areas and low exposed areas of each silver halide emulsion layer (edge effect).

By containing at least one compound represented by the general formula [l) of the present invention in the silver halide emulsion layer, development is inhibited from the high exposure area to the low exposure area at the edges of the high exposure area and the low exposure area. .

By suppressing the development of the edge portion, the edge becomes clearer and the sharpness is improved.

Specific examples of the compound represented by the general formula [I] are shown below, but the compounds of the present invention are not limited thereto.

(K) (4t) (Ri import) (Ri (/4t) (/ri U3Na (/♂) (2θ) (,23) (itsu・Hcl (2yo) (Carp) (Kori, HCl ・HCl (3g) (3-Hcl) The compound represented by the general formula [I] used in the present invention is
Easily available Koamino! -Mercapto-/, 3
．． It can be easily synthesized by reacting 4t-thiadiazole with incyanates, inthiocyanates, and chloroformates.

Also, if you want to generate a ureido bond, use co-amino instead of incyanate! -Mercapto-7,,?
, '1--F-7 Komer's force produced by the reaction of cyazole and phenylchloroformate! -Phenoxycarbonylamino-/j, 4t-thiadiazole may be reacted with an amine.

Typical synthesis examples are shown below.

Synthesis example/method for synthesizing compound (co) two amino-mercapto-7,! , 4t-thiadiazole/3J, 2g, pyridine rr, tmJ with dimethylacetamide! 00 ml, and 72.2 g of phenyl chloroformate was added dropwise while cooling with water. After the dropwise addition, the mixture was stirred in the room for 3 hours and poured into ice water 21 to cause crystallization. When the precipitated crystals are recrystallized from acetonitrile, zumercapto-j
-phenoxycarbonylamino-/, j, <4-thiadiazole/7♂, tg was obtained.

Cormelcapto thus obtained! -phenoxycarbonylamino-/, 3.41-thiadiazole/
Add 200ml of acetonitrile to 2.7g and add J- at room temperature.
0.2 g was added dropwise to N,N-dimethylaminopropylamine. After dripping! The mixture was heated and stirred at 0°C for 7.1 hours, and the precipitated crystals were collected by filtration and recrystallized from a mixed solvent of methanol and concentrated hydrochloric acid to obtain compound (4tr). Yield 10.7g
Melting point 2t-23o0c Synthesis example 2 Synthesis method of compound (4t) 2-amino-j-mercapto-/, 3. Dissolve 3.3 g of t-thiadiazole in 100 ml of acetonitrile and 4 tOml of dimethylacetamide, and dissolve at room temperature. -(N
, N-dimethylamino)probylthiocyanate)/
j, 9 g was added dropwise. After the dropwise addition, the mixture was heated and stirred at RO0C for 2 hours, and the precipitated crystals were collected by filtration and recrystallized from a mixed solvent of methanol and concentrated hydrochloric acid to obtain a compound (<=).

Yield/2. nig Melting point /4t6~/4t10C Synthesis Example 3
Synthesis method of compound (?) Komeriki Futo! -phenoxycarbonylamino-/
, 3. 10 ml of ethyl alcohol was added to 2.7 g of Goothiadiazole, and 7 g of 3-morpholinopropylamine♂ was added dropwise at room temperature. After the addition, the mixture was stirred at room temperature for 1 hour, and the precipitated crystals were collected by filtration and recrystallized from a mixed solvent of methanol and concentrated hydrochloric acid to obtain compound (♂). Yield/θ, 9g
Melting point 2J'! ~2!2°C Synthesis Example G Synthesis method of compound (9) Komel Kafto! -phenoxycarbonylamino-/
, J, II-Thiadiazole, 4tg, ethyl alcohol JOml was added, and histamine dihydrochloride was obtained at room temperature! ,
! A solution of 4 tg of sodium hydroxide U and 4 tg of sodium hydroxide U dissolved in θml of water was added dropwise. After the dropwise addition, the mixture was stirred at <tooC for 3 hours, and the precipitated crystals were collected by filtration and recrystallized from a mixed solvent of methanol and concentrated hydrochloric acid to obtain compound (wa). Collection kr-r
g Melting point 211t♂~ko! 0°C synthesis example! Synthesis method of compound (/6) Komelkabuto-yo-phenoxycarbonylamino/
, 3. 200 ml of acetonitrile was added to 2.7 g of Goothiadiazole, and 4 tg of /-(3-aminopropyl)-2-methylimidazole♂ was added dropwise at 0°C.

After stirring at θ0C for 3 hours after the addition, the precipitated crystals were collected by filtration and recrystallized from a mixed solvent of methanol and concentrated hydrochloric acid to obtain compound (/6).

Yield //, /g Melting point C3♂ to Cog θ0C When the compound represented by the general formula CI) of the present invention is used in a multilayer color photographic light-sensitive material, a silver halide emulsion layer or a yellow filter adjacent to the emulsion layer is used. It is contained in at least one layer such as an antihalation layer, an intermediate layer, or a protective layer, but it is most preferably contained in a silver halide emulsion layer.

Furthermore, when applying the present invention to black and white photographic materials,
A compound represented by general formula [I] is contained in a silver halide emulsion layer and/or a protective layer.

The compound of the present invention represented by the general formula CI) differs depending on the nature, purpose, or development method of the silver halide photographic material to which it is applied, but generally the compound of the present invention is a silver halide compound present in the same layer or an adjacent layer. lo-1 to 10 per mole
-5 mol, preferably 3 x 10-2 to 3 x 10
-4 moles.

In order to introduce the compound represented by the general formula [I] of the present invention into a light-sensitive material, it is dissolved in a solvent commonly used in photographic light-sensitive materials such as water, methanol, ethanol, propatool, or fluorinated alcohol, and then Add to hydrophilic colloids. When it is contained in a silver halogenide emulsion layer, it can be contained during grain formation of a silver halogenide emulsion, during physical ripening, immediately before chemical sensitization, during chemical sensitization, after chemical sensitization, or during preparation of a coating solution. Either one may be used and is selected depending on the purpose.

The photosensitive materials to which the present invention is applied include, for example, color negative films, color reversal films (inner and outer molds), color positive films, color reversal films, e-
, color diffusion transfer process, die transfer process, etc., and black-and-white photographic materials such as black-and-white negative film, black-and-white photographic paper, X-ray film, and lithographic film.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, any silver halide such as silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used. The silver halide is silver iodobromide or silver iodochlorobromide containing up to about 30 mole percent silver iodide. Particularly preferred is silver iodobromide containing from about 0.5 mole percent to about 10 mole percent silver iodide.

Silver halide grains in photographic emulsions may be so-called regular grains with regular crystal shapes such as cubes, octahedrons, and tetradecahedrons (and also grains with irregular crystal shapes such as spherical shapes). , particles with crystal defects such as twin planes, or a composite form thereof, or a mixture of particles of various crystal forms may be used.

The grain size of the silver halide may be fine grains of about 0.1 micron or less, large grains with a projected area diameter of up to about 10 microns, monodispersed emulsions with a narrow distribution, or polydisperse emulsions with a wide distribution. A dispersed emulsion may also be used.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method, such as Research Disclosure,
Volume 176, No. 17643 (December 1978), 2
2-23 pages %"I+ Emulsion P
187, No. 18716 (November 1979)
, 648i.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Kide Gura, published by Beaumontel (P.

C1afkides, Chilaie et PI+
ysique PbotographiquePaul
Honjel, 1967), Guffin's ``Photographic Emulsion Chemistry'', 7th Edition, published by Cal Press (Duffi, F., 1967).
n, Photo-Hraphic Emulsion
Chea+1stry (Focal Press
1966), Zelikman et al. [Manufacture and Coating of Photographic Emulsions], published by Vol.
n etal+ Making and Coating
g Photographic Emul-sion,
Focal Press, 1964). That is, any of the acid method, neutral method, ammonia method, etc. may be used.
In addition, as a method for reacting soluble silver salt and soluble halide salt, any one of the one-sided mixing method, simultaneous mixing method, seven-sided combination, etc. may be used. A mixed method) can also be used. As one form of the simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Funtrold tuple jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

In addition, known silver halide solvents (for example, ammonia, rhodankali, or Showa 54-100717
Physical ripening can also be carried out in the presence of thioethers and thione compounds described in No. 54-155828 or the like. This method also yields a silver halide emulsion with a regular crystal shape and a nearly uniform grain size distribution.

The silver halide emulsion consisting of the regular grains described above can be obtained by controlling lmAg and 9H during grain formation. For more information, see 7 Otographic Science.
and engineering (PI+otography
c5science and engineering
) Volume 6, pp. 159-165 (1962); Journal of 7 Otographic Science (Jour
nal ofPhotographic 5cienc
e), Vol. 12, pp. 242-251 (1964), U.S. Patent No. 3,655,394 and British Patent No. 1,4
No. 13,748.

Furthermore, as a monodisperse emulsion, silver halide grains having an average grain diameter of more than about 0.1 micron, at least 9
Typical emulsions are those in which 1% by weight is within ±40% of the average grain diameter. The average grain diameter is between 0.25 and 2 microns, and the average grain diameter is ±2.
Emulsions such as those within the 1lli range of 0% can be used in the present invention. A method for producing such an emulsion is described in U.S. Patent No. 1.574.
．． No. 628, No. 3,655,394 and British Patent No. ml, No. 413.748. Also, JP-A No. 48-8600, No. 51-39027, No. 51-8
No. 3097, No. 53-137133, No. 54-485
Monodisperse emulsions such as those described in No. 21, No. 54-99419, No. 58-37635, and No. 58-49938 can also be preferably used in the present invention.

Further, tabular grains having an aspect ratio of 5 or more can also be used in the present invention. Tabular grains are manufactured by Door Arrival, 7 Otographic Science and Engineering (
Cutoff+ Photographic 5ci-
ence and Engineering) + 14th
9, pp. 248-257 (1970); U.S. Patent No. 4,
No. 434,226, No. 4,414,310, No. 4,4
No. 33,048, No. 4,439,520 and British Patent No. 2.112.157. When tabular grains are used, there are advantages and disadvantages such as increased covering power and increased color sensitization efficiency by sensitizing dyes.
No. 434,226 describes this in detail.

The crystal structure may be uniform, the inside and outside may have different halogen compositions, or it may have a layered structure. These emulsion grains are described in British Patent No. 1,027,1
No. 46, U.S. Patent No. 3,505.0138, U.S. Patent No. 4,4
No. 44,877 and Japanese Patent Application No. 58-2248469. Furthermore, silver halides of different compositions may be bonded by epitaxial bonding, or may be bonded with compounds other than silver halide, such as silver oxide and lead oxide.These emulsion grains are disclosed in the US Pat. No. 4,094,684, No. 4,142.900, No. 4,459,353, British Patent No. 2゜038.7
No. 92, U.S. Patent No. 4,349,622, U.S. Patent No. 4,39
No. 5,478, No. 4,433,501, No. 4,463
, No. 087, No. 3,656,962, No. 3,852,
No. 067, JP-A-59-162540, etc.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the grains.

In order to remove soluble silver salts from the emulsion before and after physical ripening, Nudel water washing, 70-curation sedimentation method, 1-ultra-emission method, etc. are used.

The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization.

The additives used in such processes are based on the research and research mentioned above.
Disclosure + -No. 17643 (1978 1
February) and same No. 18716 (November 1979)
The relevant sections are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the above two research φ disclosures, and the locations listed are shown in the table below.

Additives 8i RD17643 RD1871
61 Chemical sensitizer Page 23 Page 648 Right column 2F
jA degree increasing agent Same as above 3 Spectral sensitizer, pages 23-24 Page 648 right column ~ Constant color sensitizer
Page 649 Right Column 4 Brightener Page 24 5 Antifoam Agent Page 24-25 Page 649 Right Column and Stabilizer 6 Light Absorber, 7 Page 25-26 649 Right Column - Ilter Dyes 650 Left Column Ultraviolet Absorber 7 Stin Inhibitor Page 25 Right column Page 650 Left to right column 8
Dye image stabilizer page 25 9 Hardener page 26 Page 651 Left column 10 Bingu Page 26 Same as above 11 Plasticizer, lubricant Page 27 650 Right column 12 Coating aid, Table 26~
Page 27 Same as above Surface activator 13 Static prevention Page 27 Same as above Stop agent Various color couplers can be used in the present invention.
o, 17643, ■-C-G in the patent f2. As dye-forming couplers, couplers that give the three primary colors (i.e., yellow magenta and cyan) in subtractive color development are important.Specific examples of diffusion-resistant, hydrophobic, 4-equivalent or 2-equivalent couplers are mentioned above. Research Disclosure No. 17643,
In addition to the couplers described in the patents described in Sections 1-C and D, the following can be preferably used in the present invention.

A representative example of the yellow coupler that can be used in the present invention is a hydrophobic acylacetamide coupler having a ballast group. A specific example is U.S. Pat.
No. 407,210, No. 52.875.057, and No. 3,265,506. The use of two-equivalent yellow couplers is preferred in the present invention, and US Pat. No. 3,408.194 No. 3,447,92
No. 8, No. 3.933.501 and No. 4.022
, 620, etc., or Japanese Patent Publication No. Sho 58-10739, U.S. Pat. No. 4,401,752, U.S. Pat.
No., RD18053 (April 1979), British Patent No. 1
, No. 425,020, West German Application No. 2,219.91
No. 7, No. 2,261,361, No. 2.329,5
Typical examples include the nitrogen atom separation type yellow couplers described in No. 87 and No. 2,433,812. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include ballast group-containing, hydrophobic ingzolone-based or Schiff/acetyl-based couplers, preferably 5-pyrazolone-based and pyrazoloazole-based couplers. A 5-pyrazolone coupler in which the 1±3-position is substituted with a 7-lyl, 7-mi, 7-group, or 7-syl, 7-mino group is preferable from the viewpoint of the hue and coloring density of the coloring dye. Second
, No. 311.082, No. 2,343.703, No. 2,600,788, No. 2,908,573, No. 3,062,653, No. 3,152,896 and No. 3,936,015, etc.

As the leaving group for the two-equivalent 5-pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or the arylthio group described in U.S. Pat. No. 4,351.897 is most preferred. , and European Patent No. 73
, No. 636, the 5-pyrazolone coupler having a ballast group can provide high color density. As a pyrazoloazole coupler, U.S. Patent No. 3,061,432
The birazolobenzimiguzole group described in US Pat. No. 3,725,067, preferably pyrazolo[
5,1-e][1,2,4]) Liazoles, Research Disclosure No. 24220 (June 1984)
) and pyrazolotetrazoles described in JP-A No. 60-33552 and Research Disclosure 1
No. 24230 (June 1984) and Japanese Unexamined Patent Publication No. 1983
Examples include pyrazolopyrazoles described in No.-43659. Imidazo[1,2-b]pyrazoles described in U.S. Pat. No. 4,500,630 are preferred from the viewpoint of low yellow side absorption and light fastness of the coloring dye, and imidazo[1,2-b]pyrazoles described in European Patent No. 119,860A are preferred Pyrazolo [1,5-bl
[1,2,4]) Riazole is most preferred.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant 7-toll and 7-enol couplers, and are described in U.S. Patent No. 2.474,293.
Tall couplers, preferably U.S. Pat. No. 4,052,
No. 212, No. 4,146.39f3, No. 4,22
Typical examples include two-equivalent 7-toll couplers of the oxygen atom elimination type described in No. 8,233 and No. 4,296,200. Further, specific examples of 7-el couplers are given in U.S. Pat.
No. 01.171, No. 2,772.162, No. 2.
895.826, etc.

Cyankabu 2-, which is robust against humidity and temperature, is preferably used in the present invention, and a typical example thereof is a furyl group having a niethyl group or more at the meta position of the 7 enol nucleus described in U.S. Pat. No. 13,772,002. Phenolic cyan couplers having groups, U.S. Patent Nos. 2,772,162, 3,758,308, 4,126,396
No. 4,334゜0.11, No. 41327,1
No. 73, West German Patent Publication Source No. 3,329,729, and European Patent No. i121゜365, etc. 2,5-
Noacylamino-substituted phenolic couplers and U.S. Pat.
Examples include phenolic couplers having a phenylureido group at the 2-position and a 7-sylami/group at the 5-position, as described in No. 67.

In order to correct unnecessary absorption of color pigments, it is preferable to perform masking by using a colored coupler in combination with the photosensitive material for photographic coloration, as disclosed in U.S. Pat. No. 4,004,92 or U.S. Patent No. 4,004,92.
No. 9, No. 4,138.258 and British Patent No. 1,
146,36.

Typical examples include the magenta-colored cyan coupler described in No. 8. The colored coupler in the pond is the aforementioned Research Disclosure.

No. 17643, described in sections ① to G.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such a coupler is
U.S. Patent No. 4.36 G, 237 and British Patent No.
A specific example of a magenta coupler is given in No. 2,125,570.
Also, European Patent No. 96,570 and West German Application Publication No. 3
, 234,533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and specialty couplers described above may form dimers or more polymers; typical examples of polymerized dye-forming couplers are described in U.S. Pat. No. 3,451.82.
No. 0 and No. 4,080.211. Specific examples of polymerized magenta couplers are described in British Patent No. 2.102,173 and US Pat. No. 4.36'7,
It is described in No. 282.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. As the DIR coupler that releases the development inhibiting layer, the patent couplers described in the aforementioned Research Disclosure, No. 17643, Items ① to F are useful.

The preferred combination of the present invention is Vf
Developer deactivated type represented by No. 7-151944; U.S. Patent No. 4.248.962 and JP-A-57-1542
Timing type represented by No. 34; patent application 1986-396
Particularly preferred are JP-A-57-151944 and JP-A-58-217932.
Developer deactivated DIR Kabuchi described in Japanese Patent Application No. 59-75474, Japanese Patent Application No. 59-82214, Japanese Patent Application No. 59-82214, Japanese Patent Application No. 59-90438, etc., and Vf Application No. 59-39653, etc. It is a reactive DIR coupler.

The coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods, such as a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. be able to. In the oil-in-water dispersion method, after dissolving either a high-boiling organic solvent with a boiling point of 175°C or higher and a so-called auxiliary solvent with a low boiling point, either alone or in a mixture of both, book or gelatin is dissolved in the presence of a surfactant. Finely dispersed in aqueous media such as aqueous solutions. Examples of high boiling point organic solvents are U.S. Pat.
．． 6 Dispersion described in No. 027 may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, or ultrafurnace method before use for coating. Good too.

The process, effects, and specific examples of latex for impregnation are described in U.S. Pat. No. 4,199,363, West H.
*"f:j'f Described in M (OLS) No. 2.541.274 and OLS No. 2,541,230.

The photosensitive material produced using the present invention contains hydroquinone derivatives, aminophenol derivatives, amines, gallic R11i conductors,
It may contain catechol derivatives, ascorbic acid yi conductors, colorless couplers, sulfonamidophenol derivatives, and the like.

- Various anti-fading agents can be used in the photosensitive material of the present invention. Specific anti-fading agents include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochroman M, p-flucoxyl 7-mer,
Hindered phenols, mainly bisphenols, gallic r11 derivatives, methylenedioxybenzenes,
Typical examples include 7-minophenols, hindered amines, and ester derivatives of ethers obtained by silylating or furkylating the phenolic hydroxyl group of each of these compounds. Further, metal complexes represented by (bissalicylfludoximato)nickel lead and (bi-N,N-dialkyldinaorubamato)nickel lead can also be used.

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually consist of a red-sensitive emulsion on a support.
, 1, each having at least one kk-sensitive emulsion layer and one blue-sensitive emulsion layer. The arrangement of these layers can be arbitrarily selected as required. The preferred order of layer arrangement is red sensitivity, green sensitivity, and blue sensitivity from the support side, or blue sensitivity, red sensitivity, and green sensitivity from the support side. Furthermore, each emulsion layer has two different sensitivities.
A cyan-forming coupler is added to a red-sensitive emulsion layer, which may be made up of more than one emulsion layer, and a non-light-sensitive layer may be present between two or more emulsion layers of the same sensitivity. Usually, the emulsion layer contains a magenta-forming coupler and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

The light-sensitive material according to the present invention has a silver halide emulsion layer containing:
Protective layer, intermediate layer, filter layer, antihalation layer,
It is preferable to provide an auxiliary layer such as a back layer as appropriate.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are formed on a flexible support such as a plastic film, paper, or cloth, which is usually layered in a photographic light-sensitive material, or on a rigid support such as plastic, ceramic, or metal. applied. Useful flexible supports include cellulose i-conductors (nitrocellulose,
Cellulose acetate 1, cellulose acetate butyrate, etc.), films consisting of synthetic polymers (polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc.), baryta layers or α-olefin polymers (e.g. polyethylene, polypropylene, ethylene/butene copolymers) #, etc. coated or laminated. The support may be colored using a dye or pigment, or may be black for the purpose of blocking light.

The surface of these supports is generally treated with an undercoat to improve adhesion to photographic emulsion Wi and the like. The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.

For example, dip coating, roller coating, curtain coating,
Various known coating methods such as extrusion coating can be used. If necessary, multiple layers may be applied simultaneously by the coating methods described in US Pat. No. 2,681,294, US Pat. No. 2,761,791, US Pat.

The color photographic light-sensitive material according to the present invention is disclosed in the above-mentioned Research Disclosure, No. 1, No. 17643, 28-. 2
The color photographic material of the present invention can be developed by the usual method described in the left column to right column of page 651 of the same, No. 18716. Usually washed with water or stabilized.

In the washing process, it is common to use a 2W1 or larger tank for self-flow washing to save water. As a stabilizing treatment, use V? instead of the water washing process. A typical example is a multi-stage countercurrent stabilization treatment as described in Japanese Patent Publication No. 57-8543. In the case of this process, 2
~ 9 countercurrent columns are required. 0 stabilization columns include various compounds added for the purpose of stabilizing images. 1 For example, membrane 1.
] Various buffering agents (e.g., borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, ammonia water monocarboxylic acid) to adjust H (e.g. If pH 3-8) Typical examples include (using a combination of acids, nocarboxylic acids, polycarboxylic acids, etc.) and formalin. In addition, water softeners (undefeated phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, amine/polyphosphonic acid, phospho/carboxylic acid, etc.) as necessary,
Various additives such as bactericides (benzisothiazolinones, verithiazolones, 4-thiazolinebenzimidazoles, halogenated phenols, etc.), surfactants, optical brighteners, hardeners, etc. may be used. Two or more of the same or different target compounds may be used in combination.

Further, it is preferable to add various ammonium salts such as ammonium chloride, heptammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a membrane c+H regulator after treatment.

(Examples) Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not limited thereto.

Example: A multilayer color photosensitive material consisting of each layer having the composition shown below was prepared on a cellulose triacetate film support as a sample.
/ri was made.

1st layer; antihalation layer black colloidal silver ・・・・・・・・・・・・ 0. /r
Gelatin layer λth layer containing g/m2; middle layer λ,! -G-t-bentadecylhydroxone...
・・・・・・・・・ 0. /rg/m2 Casolar C-,
?・・・・・・・・・ 0. //g/m2 gelatin layer 3rd layer; 7th red-sensitive emulsion layer silver iodobromide emulsion (silver iodide 1 molti, average grain size 0.<1μ)...
...Silver coating amount (same below) 0.7λg/m2 Sensitizing dye A
・・・・・・・・・ 9.0×10 for 7 moles of silver
-5 moles of sensitizing dye B 3 moles per mole of silver
．． 0x10-5 mol sensitizing dye C... q per mol of silver,
Rice 10-4 moles Sensitizing dye D 3 moles per mole of silver
．． 0x10-5 molar coupler C-e・・・・・・・・・0.093
g/m2 coupler C-r...
・・ 0.3/g/m2 coupler C-t ・・・・
・・・・・・ Gelatin layer qth layer containing 0.0/g/m2; First red-sensitive emulsion layer Silver iodobromide emulsion ・・・・・・・・・・・・・・・・・・
/,,2 g/m2 (silver iodide/θ mole, average grain size/, Qμ) Sensitizing dye A 7, ♂X10-5 mole sensitizing dye per mole of silver B......Co, Co, xio-s moles per mole of silver Sensitizing dye C......3.
0 x 10-4 mol sensitizing dye D... 2 per mol of silver
．． 2×10-5 molar coupler C-a ・・・・・・・・・・・・・・・0
．． /g/m2 coupler C-t ・・・・・・・・・0
．． 061g7m2 coupler C-7...------
Gelatin layer 1st layer containing o, o 4tt, g/m 2; Third red-sensitive emulsion layer Silver iodobromide emulsion ・・・・・・・・・・・・・・・・・・
/, jg/y12 (silver iodide 10 molti, average grain size /,!μ) Sensitizing dye A・・・・・・・・・ Silver 7
Against mole? , O×/θ-5 mol Sensitizing dye B・・・・・・・・・・K, G￥, 10−5 mol Sensitizing dye C・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・...3.3 x 10-5 mol per 7 mol of silver Sensitizing dye D 2.4tX/θ-5 mol coupler C per 7 mol of silver -7・・・・・・・・・・・・ 0.32g
/m2 coupler C-/7-------・0.00/g/
Gelatin layer 2nd layer containing m2; Intermediate gelatin layer 2nd layer; 1st green-sensitive emulsion layer Silver iodobromide emulsion ・・・・・・・・・・・・・・・ 0.
! ! g/m2 (silver iodide! Morch, average grain size 0.!
μ) Sensitizing dye ■-7... 3 for 7 moles of silver,
♂X10-4 mol Sensitizing dye E・・・・・・・・・・・・・・・・For 1 mol of silver/jXlo Molar coupler C−/ ・・・・・・・・・・・・0.29
g/m2 coupler C-3・・・・・・・・・・・・o
, oag/m2 coupler C-7o-...-o, os
tg/m2 coupler C-/ / ・=・0, 0!
Gelatin layer ♂ layer containing J''g/m2; th green-sensitive emulsion layer Silver iodobromide emulsion ・・・・・・・・・・・・・・・・・・
/, Og/m2 (silver iodide 6 molt, average grain size 7
．． (2 μ spherical particles) Sensitizing dye 1-7 2.
7X10 mol sensitizing dye E・・・・・・・・・・per mole of silver / , /X/θ−4 mol coupler C-♂・・・・・・・・・θ, 26g
/m2 coupler C-3・・・・・・・・・ 0. θ/
3g/m2 coupler C-70---0,009
g/m2 coupler C-// 0.0//
9th gelatin layer containing g/m2; 3rd green-sensitive emulsion layer silver iodobromide emulsion 2. θg/m2 (Silver iodide r mole, average grain size/.♂μ spherical particles) Sensitizing dye 1-7 3.0 per 7 moles of silver
×/θ-4 mol Sensitizing dye E・・・・・・・・・・・・/, 2X/θ-4 mol coupler C-j---・-0,00/ per 1 mol of silver g/m
2 coupler C-12...0.0! g/
m2 coupler C-/♂・・・O8θθ/g/m
Gelatin layer 70th layer containing 2; yellow filter layer yellow colloidal silver 0.
0'1g/m22,! Eleventh layer of gelatin layer containing -d-t-pentadecylhydroquinone θ, 03/g/m2; First blue-sensitive emulsion layer Silver iodobromide emulsion・・・・・・・・・・・・ 0.
32 g/m2 (Silver iodide! Morch, average grain size Q,'
lμ) Coupler C-/,?・・・・・・・・・O3
Otsu? g/m2 coupler C-/<t...
...0.0! g/m2 coupler C-/9-・----
Gelatin layer 1st layer containing 0,oitg/m2; 2nd blue-sensitive emulsion layer silver iodobromide emulsion 0.29g/m2 (silver iodide 10 molt, average grain size/, θμ) sensitizing dye F...
・・・・・・・・・λ, co×/θ− for 1 mole of silver
4 mole coupler C-/3・・・・・・θ, 2.2g/
Gelatin layer 73rd layer containing m2; Fine grain emulsion layer Silver iodobromide emulsion ・・・・・・・・・・・・・・・・・・
0, 4! Gelatin layer 14 containing g/m2 (silver iodide λ morch, average grain size θ, /!μ): Third blue-sensitive emulsion layer Silver iodobromide emulsion ・・・・・・・・・・・・・・・・・・ 0.
79 g/m2 (silver iodide 1 liter morch, average grain size 2.3μ) Sensitizing dye F・・・・・・・・・2.3×10−4 mol coupler per 1 mol of silver Coupler C-/ ,y・・・・・・・・・0. /g/m2 coupler C-/r --------o, 0
Gelatin layer 1 containing 0/g/m2! Layer: 1st protective layer ultraviolet absorber C-/ 0. /4t
g/m24! Line absorber C-1・・・・・・・・・ 0.
Gelatin layer 1st layer containing 22 g/m2; 2nd protective layer polymethyl methacrylate particles (diameter i, rμ)...
・・・・・・・・・ 0. In addition to the above composition, a gelatin hardening agent C-/Niya surfactant was added to each gelatin layer containing θj g/m 2 . The sample prepared as described above was designated as sample //4t.

The compounds used to prepare the samples are shown below.

C-no x:y=7:3 (weight ratio) C-coC-<t □H -t C- to C-7 ■ O2H -r CH3 C-/ / C-i<t C-/yoO C-/bu(CH2=CH8O2CH2CONHC)I2suC-/
♂ Sensitizing Dye A Sensitizing Dye B Sensitizing Dye C Sensitizing Dye D 2H5 Sensitizing Dye E Sensitizing Dye F Preparation of Sample /Q/ Sample //4t G layer, No.! Sample //4 except that the amount of compound β-1 shown in Table 1 was added to the layer when preparing the coating solution.
Sample 10/ was prepared in exactly the same manner as t.

10 samples N//3, samples//! Preparation sample 1 of ~//r
Samples 102 to //3 and Sample //! were prepared in exactly the same manner as Sample 10/, except that the compounds shown in Table 7 were added in the amounts shown in Table 1 in place of compound 1-J of 0/. ~7/♂
was created.

For these samples 707 to //♂, a portion of each sample was subjected to red wedge exposure, and the other portion was subjected to white wedge exposure (red+green+blue light). Red exposure amount during white exposure,
The exposure amount during red exposure was the same.

These exposed samples were subjected to color development processing.

The development process in this case was carried out at 310C as described below.

Comparing cyan exposed to red light and cyan exposed to white light, it can be said that the greater the exposure amount difference Δflag E at the density θ, the greater the interimage effect.

Further, the sharpness was determined based on the MTF value.

l Color development...3 minutes/! Bleach for 2 seconds......30 seconds Wash with water for 3 minutes...3 minutes/! second threat
Arrival: 4 minutes and 30 seconds. Wash with water.
・・・・・・・・・・・・ 3 minutes! Second 6 stable...
...... 3 minutes/j seconds The composition of the treatment liquid used in each step is as follows.

Color developer Sodium nitrilotriacetate・・・・・・・・・／,0
gSodium sulfite・・・・・・・・・・・・・・・
・・・・・・・・・ 11. □g Sodium carbonate...
・・・・・・・・・・・・・・・・・・・・・ 30,
0g Potassium Bromide ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・ /, 4tg hydroxylamine sulfate...old...2. l1
g-gu (N-ethyl-N-β-hydroxyethylamino)-comethylaniline sulfate ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・ a. Add tg water・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・／、OL Bleach Solution Ammonium Bromide・・・・・・・・・・・・・・・・・・・
・7g0.0g ammonia water (2♂chi)・・・・・・
・・・・・・2j, Occ ethylenediamine-tetraacetic acid sodium salt・・・・・・・・・・・・・・・・・・・・・
・・・・・・ 130.0g glacial acetic acid・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・ Add θcc water・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・01 Fixer Sodium Tetrapolyphosphate・・・・・・・・・ 2.
0g Sodium sulfite・・・・・・・・・・・・・・・
・・・・・・・・・ <t, og ammonium thiosulfate (70%)・・・・・・・・・・・・・・・・・・・・・
・ /7j, Occ Sodium Bisulfite・・・・・・・
・・・・・・・・・・・・・・・ ＜z、、＜g Add water ・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・ /, O1 stabilizer formalin ・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・♂、Add Occ water・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
/, O1 Comparative compound A Comparative compound B The following compound described in JP-A-6O-494tO Comparative compound C Comparative compound From these results, the present invention has an interimage effect compared to the comparative example. It can be said that it is clearly large.

Furthermore, it can be said that the present invention is clearly superior to the comparative example in terms of sharpness.

Example 1 Sample 2/3 was prepared by coating the first to first co-layers on a triacetate film base in the following order.

First layer: antihalation layer (gelatin layer containing black colloidal silver).

First layer; gelatin middle layer! - D-t-octylhydroquinone was dissolved in 100 cc of diptylphthalate and 100 cc of ethyl acetate, and 2 kg of the emulsion obtained by stirring at high speed with a 10% gelatin aqueous solution/kg was mixed into a fine-grain emulsion that was not chemically sensitized (particle size It was mixed with 70% gelatin i, rkg together with 70% gelatin i, rkg and coated to give a dry film thickness of μ (silver amount O, gg/m2).

3rd layer; low-sensitivity red-sensitive emulsion layer 100 g of 2-(heptafluorobutyramide>-6-(-'-(2", 4t"-di-monoaminophenoxy)butyramide)-phenol, which is a cyan coupler, is Cresyl phosphate 100cc and ethyl acetate 10
The emulsion roog obtained by dissolving occ/C and stirring at high speed with a 10% gelatin aqueous solution/kg was converted into a red-sensitive silver iodobromide emulsion/kg (containing 70 g of silver and 60 g of gelatin, and the iodine content was gmol%). The mixture was mixed and coated to give a dry film thickness/μ. (Silver amount θ, tg/m2) Layer: Highly sensitive red-sensitive emulsion layer cyan coupler λ-(heptafluorobutyramide)-, ? -(2'-(2", googe-t-aminophenoxy)butyramide)-phenol/θQg, tricresyl phosphate 10θcc and ethyl acetate 100%
cc and stirred at high speed with IO% gelatin aqueous solution/kg, 100 θg of the emulsion obtained was mixed into a red-sensitive silver iodobromide emulsion/kg (containing 70 g of silver and 0 g of gelatin, with an iodine content of ! Morch) mixed and dried to a thick film,! It was applied so that it was μ. (Amount of silver: 0.7 g/m2) 1st layer; Intermediate layer: J-t-octylhydroquinone was dissolved in 100 CC of dibutyl phthalate and ethyl acetate/θOcc, and stirred at high speed with an aqueous solution/kg of gelatin. The resulting emulsion/kg was mixed with 10% gelatin/kg and applied to give a dry film thickness/μ.

Layer 2: Low-sensitivity green-sensitivity emulsion layer with magenta coupler instead of cyan coupler /-(
λ, 4t, trichlorophenyl)-3-(3-(2
,4t-di-t-amylphenoxyacetamide)benzamide)-! - An emulsion JOOg obtained in the same manner as the emulsion of the third layer except that pyrazolone was used was used as a green-sensitive silver iodobromide emulsion/kg (20 g of silver, containing tog of gelatin, iodine content of 3 mole) The mixture was mixed and applied to a dry film thickness of 3 μm. (Amount of silver 0.7g/m2) Second layer;
Highly sensitive green-sensitive emulsion layer 1-(
z, 4t, +-trichlorophenyl)-3-(,?-(
4t-di-t-amylphenoxyacetamide)benzamide)-! - An emulsion/θθog obtained in the same manner as the emulsion of the third layer except that pyrazolone was used was used as a green-sensitive silver iodobromide emulsion/kg (containing 20 g of silver and 0 g of gelatin, with an iodine content of ,! Morch) and dry film thickness 3.
! It was applied so that it was μ. (Silver amount: 0.7 g, 7 m2) Second layer: Yellow filter An emulsion containing yellow colloidal silver was coated to give a dry film thickness/μ.

9th layer: Low-sensitivity blue-sensitivity emulsion layer α-(
hivaloyl)-α-(/-benzyl-!-ethoxy 3
-hydantoinyl)-,2-chloro-! - 1000 g of an emulsion obtained in the same manner as the emulsion of the third layer except that dodecyloxycarbonylacetanilide was used was mixed into a blue-sensitive silver iodobromide emulsion/kg (70 g of silver, oz. in gelatin, iodine content was mixed with λ, !mol%) and coated to give a dry film thickness of /, tμ. (Amount of silver θ, jg/m2
) 10th layer; Highly sensitive blue-sensitive emulsion layer α-(
hivaloyl)-α-(/-benzyl-j-nitoxy-3
-hydantoinyl)-2-riroro! - Emulsion iooog obtained in the same manner as the emulsion of the third layer except that dodecyloxycarbonylacetanilide was used was mixed into a spherical silver iodobromide emulsion/kg (70 g of silver, gelatin contains Og, and the iodine content is λ , J Morch) and applied to a dry film thickness of 3 μm. (Silver*/, /g/m2) 1st/layer;
The emulsion/kg of the ultraviolet absorber C-/ used in the second protective layer example was mixed with 10% gelatin/kg and coated to give a dry film thickness of 2 μm.

Layer 1.2: First protective layer A 70% aqueous gelatin solution containing polymethyl methacrylate particles (diameter/,!μ) was coated to give a silver coating amount of 0.7 g 7 m 2 and a dry film thickness θ, /μ.

Gelatin hardener C-/l and surfactant were added to each layer, respectively.

Preparation of sample θ/ Sample 2 except that the amounts of compound 1-2 shown in Table 2 were added to the third layer, second layer, seventh layer, and ninth layer of sample-73 when preparing the coating solution. Sample 20/3 was prepared in exactly the same manner as in /3.
was created.

Preparation of sample θ2~2/2, sample -/4t~-/B Add the compounds shown in Table 2 in the amounts shown in Table 2 to replacements for compound 1-u of sample 20/B, respectively. Sample 20 except
Samples 0 to 21 and samples 27 to 274 were prepared in exactly the same manner as in /.

For these samples 20/~2/lK, each part was exposed to red wedge light, green wedge light, and blue wedge light at different locations, and the other part was exposed to white wedge light (red + green + blue light). gave. The exposure amounts of red light, green light, and blue light during white exposure were the same as those of red light, green light exposure, and blue light exposure, respectively.

These exposed samples were subjected to the following development treatment.

Processing process Process Time Temperature First development: 3r0c Water washing - minutes Reversal - minutes Color development 1 minute 3♂0C Adjustment 2 minutes Bleached white 6 minutes Fixed arrival time: 9 minutes Wash with water Stable for 1 minute at room temperature drying The composition of the treatment liquid used is as follows.

No.-Developer water 700
m1 nitrilo-N,N,N-)rimethylenephosphonic acid! Sodium salt 3g Sodium sulfite 20g Hydroquinone monosulfonate 30g Sodium carbonate (/hydrate) 3 layers g/-phenyl-9-methyl-g-hydroxymethyl-3-pyrazolidone 2g Potassium bromide λ,! g Potassium thiocyanate /, 2g Potassium iodide (0,
/chi solution) Add 2ml water
/θ00m1 Inverted liquid water 7
00ml nitrilo-N,N,N-)rimethylenephosphonic acid! Natrirum salt 3g stannous chloride (cohydrate salt) /gp-aminophenol 0.1g sodium hydroxide
2g glacial acetic acid
Add 13ml water to make 1000ml
Color developer water 700
m1l Nitrilo・N,N,N-trinotylenephosphonic acid・! Natrirum salt 3g Sodium sulfite 7g Sodium triphosphate (dihydrate) 3g Potassium bromide 7g Potassium iodide (
007% solution) 90ml sodium hydroxide
3g citradinic acid
/,! gN・Ethyl-N-(β-methanesulfonamidoethyl)-3・Methyl-aminoaniline・sulfate //g Ethylenediamine Add 3g water
10100O adjusted liquid water 700
m1 Sodium sulfite 72g Ethylenediamine Sodium tetraacetate (dihydrate) /g Thioglycerin 0.4tml Glacial acetic acid
Add 3 ml water
7000ml bleach solution water ro
og ethylenediaminetetraacetic acid (lambda hydrate) -g ethylenediaminetetraacetate iron(III) ammonium (, dihydrate) 72og potassium bromide 700g Add water 10100O fixer water ro
oml Sodium thiosulfate 20.0g Sodium sulfite 5.0g Sodium bisulfite 1.0g Add water
7000ml stable liquid water ♂0
0 ml formalin (37% by weight)! , θml Fuji Drywell (surfactant manufactured by Fuji Film ■)! , Oml water was added, and cyan when exposed to 10100O red light was compared with cyan when exposed to white light, and the exposure amount difference Δlog E at a density of 7.0 was measured.

Also, in the case of green light exposure and blue light exposure, Δlo
gE was measured.

These are shown in Table 1.

Comparative Compound A Comparative Compound B The following compound described in JP-A-60-9<tθ Comparative Compound B From these results, it can be seen that the present invention has a very large interimage effect compared to the comparative example. I can say that.

Example 3 Preparation of Emulsion A Potassium bromide, potassium iodide, and silver nitrate were added to an aqueous gelatin solution with vigorous stirring to prepare a silver iodobromide emulsion (A g I = 3 mol %) with an average grain size of 0.1 μm. After desalting, silver iodobromide emulsion A was prepared by optimally sensitizing gold and sulfur with chloroauric acid and sodium thiosulfate.

Emulsion B (average grain size/μAgI-=J mol %) was prepared in the same manner.

As a sample, a black and white photographic material having each layer having the composition shown below was prepared on a cellulose triacetate film support.

7th layer: Low-sensitivity silver halide emulsion layer Emulsion A (coated silver t/g/m2) 2nd layer: High-sensitivity silver halide emulsion layer Emulsion B (coated silver amount , tg/m2) 3rd layer: Protection Layered gelatin (/, jg/m2) Polymethyl methacrylate particles (diameter/, jμ) 0, O
jg/m2 In addition to the above composition, gelatin hardener C-/g1 surfactant and thickener sodium polystyrene sulfonate were added to each layer. The sample prepared as described above was designated as sample 3//.

Preparation of sample 3θ/ During the formation of silver halide grains of emulsion A in the seventh layer and emulsion B in the second layer of sample 3//, the compound ! Sample 30/ was prepared in exactly the same manner as Sample 3//, except that -2 was added in the amount shown in Table 3.

Preparation of samples 302-3101 samples 3/2-3/g Sample 3
Samples 302-3IO and 372-3 were prepared in exactly the same manner as Sample 30/, except that the compounds shown in Table 3 were added in the amounts shown in Table 3 in place of Compound I-1 of 0/.
/4t was produced.

These samples were exposed to light through a pattern for measuring graininess or a pattern for measuring sharpness, and then subjected to the development process described below.

Developer Metol 2g Sodium sulfite 100g Hydroquinone
! gpolax jH20
/, 13g Add water /l Fixer ammonium thiosulfate 200.0g Sodium sulfite (anhydrous) 2o, 0g boric acid
! , θg ethylenediaminetetraacetic acid tetraacetic acid disodium θ, ig aluminum sulfate /! , 0g sulfuric acid
og glacial acetic acid
Add 226θg water
1. θ1 (pHVi<<, zK adjusted) Black and white development was performed for 20,007 minutes using the above developer.

Granularity (RMS granularity) is the standard deviation of the density variation that occurs when scanning with a microdensitometer.
Displayed as double value.

Further, the sharpness was measured using the MTF value.

These results are shown in Table 3.

Comparative Compound A Zhan H3 Comparative Compound B Comparative Compound C Comparative Compound C As shown in Table 3, the following compounds described in JP-A No. 2003-120002 θ-tqt, to No. 3 Comparative Compound C Comparative Compound C It can be seen that the sharpness has been improved.

Patent applicant Fuji Photo Film Co., Ltd. Year 1986? Day

Claims (1)

[Scope of Claims] At least one compound represented by the following general formula [I]
A silver halide photographic material characterized by containing seeds. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R represents a linear or branched alkylene group, alkenylene group, aralkylene group, or arylene group,
Z represents a polar substituent. Y represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R_1, R_2, R_3, R_4, R_5 are hydrogen atoms, Substituted or unsubstituted alkyl group, aryl group,
Represents an alkenyl group or an aralkyl group. X represents a hydrogen atom, an alkali metal atom, an ammoniumyl group, or a group that cleaves under alkaline conditions.