JPS6143745A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sharpness and graininess by forming a silver halide emulsion layer contg. a diffusive DIR coupler forming a color substantially same as a coupler forming one of three primary colors and a nonphotosensitive layer on a support. CONSTITUTION:One or more silver halide emulsion layers each contg. a coupler forming one color of the three primary colors of the subtractive process and a diffusive DIR compd. forming a hue substantially same as said coupler are formed on the support. Further, one or more nonphotosensitive layers contg. the diffusive DIR compd. are formed at the pistion adjacent to these emulsion layers to obtain the silver halide color photographic sensitive material. This diffusive DIR compd. is a compd. capable of coupling with the oxidation product of a developing agent and releasing a diffusive developmemt inhibitor or its precursor.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to silver halide color photographic materials, particularly sharp I
This invention relates to a nine-silver halide color photographic light-sensitive material with excellent graininess.

(Prior art) In recent years, with the spread of small cameras, there has been a demand for image quality enlarged from a small size screen to be equivalent to image quality enlarged from a larger normal size screen.
became. In order to satisfy these needs, it is necessary for K to develop a color photographic material that has enough graininess and sharpness that the printed image quality is not impaired even when the enlargement magnification is increased.

Previously, 1liII@! Various methods are known for increasing the sharpness of photographic materials, but it is widely known that great effects can be obtained by increasing the edge effect and decreasing light scattering in photographic materials. Among these, the edge effect utilizes the electrical gradient of the development inhibiting substance present during development. In this case, known development inhibiting substances include, for example, iodide ions released when silver halide is developed in a developer solution, and oxidation products of the developing agent. Effects similar to those provided by these development inhibitors are described in US Patent SG3゜2.
core,! Yohiro issue, same number J, l, /j, jO6 number, same number 3
．． t/7. Compounds described in λri No. 1, No. 3,70/, 7r3, etc., or Tokuko Shojyoichi 3μ? As stated in No. 33,
It is also known that it can be actively enhanced by using further improved WFIDIR compounds and DIR couplers (including DIR couplers with so-called timing groups as described in U.S. Pat. There is.

However, even when using the above-mentioned DIR couplers, a large amount of DIR couplers must be used when it is necessary to produce a strong edge effect, and this inevitably greatly suppresses the edge effect. , this will inevitably lead to a decrease in the maximum density of the image obtained and a decrease in the risk of electric shock.
There is naturally a limit to the amount of DIR Cub 2- that can be used,
The edge effect of the above-mentioned DIR coupler and the like has a drawback in that it has to be acknowledged that there is a limit. Increasing the amount of silver applied to solve this problem would not only result in an increase in product cost! - Light scattering due to silver halide increases, resulting in deterioration of the sharpness of the DIR-added layer and the underlying layer, especially in a high spatial frequency region.

DIR that improves the conventional drawbacks and can particularly enhance the edge effect while ensuring a constant sharpness at the highest # of images.
A coupler was filed. (Ivf1! Iakiyo I-7/j
No. O). This invention is directed to a diffusible development inhibitor-releasing coupler (hereinafter referred to as a diffusible DIR coupler) that reacts with the oxidation product of a developing agent during development and releases a development inhibitor having a diffusivity of O0 or more. ) The present invention relates to a silver halide color photographic light-sensitive material characterized by containing the following.

Furthermore, in order to further improve the above invention and obtain a silver halide color photographic light-sensitive material with excellent sharpness and color reproduction, a cyan color-forming diffusive DIR additive layer was added to the red-sensitive layer, and a magenta color-forming DIR additive layer was added to the green-sensitive layer. An application has been filed for a method of using a yellow coloring DIR additive layer in each of the yellow-coloring layer and the blue-sensitive layer (Japanese Patent Application No. Sho!r-λ3706).

In order to improve sharpness, same color coloring diffusivity DI is added to the emulsion layer.
In order to increase the interlayer effect and improve sharpness using R compounds, the diffusible DIR compound needs to be more active than the main coupler. However, when a large amount of such highly active couplers is used, a large dye cloud forms, especially in low concentration areas, which causes a major drawback in that graininess becomes sensitive.

In this way, it has not been possible to simultaneously achieve excellent color reproduction, extremely high sharpness, and fine graininess using conventional techniques.

(Object of the Invention) Therefore, the first object of the present invention is to reduce graininess, lll1I(8
) To provide a silver halide color photographic material with extremely excellent sharpness.

The λth object of the present invention is to provide a silver halide color photographic material with extremely excellent color reproducibility.

(Structure of the Invention) The object of the present invention is to coat a support with a coupler that develops one of the three subtractive primary colors (hereinafter referred to as the main coupler) and a diffusible DIR coupler that develops substantially the same hue as this color. at least one silver halide emulsion layer containing;
This is achieved by a silver halide color photographic light-sensitive material characterized by having at least seven non-photosensitive layers adjacent to the emulsion layer and containing a diffusive DIR compound.

Having a diffusive DIR compound that develops the same hue as the main coupler not only improves color reproduction, but also has the effect of greatly improving sharpness by reducing film thickness and increasing the edge effect. are doing.

Furthermore, by including a DIR compound in the adjacent non-photosensitive layer, it was discovered that not only the graininess was greatly improved, but also the sharpness was actually improved, a surprising effect that was previously thought to be difficult to achieve. This makes it possible to simultaneously improve sharpness, graininess, and color reproducibility.

Furthermore, in order to increase the effect of improving color reproducibility, it is preferable that the diffusive DIR compound used in the non-photosensitive layer also develops a color having substantially the same hue as the coupler in the adjacent emulsion layer.

The term "diffusible DIR compound" as used in the present invention refers to a compound that can cause a chibling reaction with the oxidized product of fresh chestnuts during tasting to release a diffusible present chestnut inhibiting compound or a savory taste inhibiting precursor. A diffusible DIR coupler refers to one that releases a υ diffusible development-inhibiting compound or its precursor through a coupling reaction and simultaneously forms a dye.

In the present invention, the diffusion distance is O9a or more (the measurement method and the diffusible DIR compound are described in European Patent Nos. 10/ and 62/).
R compounds are preferred, and DIR couplers are preferred among DIR compounds. This twisted IR coupler is represented by the following general formula [I].

General formula [l] A-4-Y l m In the formula, human represents a coupler component, m represents l or λ,
Y is a group that binds to the coupling position of the turn 2 component and leaves by reaction with the oxidant of the main color developer, and is a compound capable of releasing a highly diffusible phenomenon inhibitor or phenomenon 5 inhibitor. represents.

In the general formula [[], Y is the following general formula [■a] ~ (V
) represents.

General formula Cna) General formula (nb) General formula [Rho] In general formulas CI[a], (llb] and (III), R1ti alkyl group, alkoxy group, acylamino group, halogen atom, alkoxycarbonyl group, thiazolilidene Amino group, aryloxycarbonyl group, acyloxy group, carbamoyl group, N-alkylcarbamoyl L
N, N-dialkylcarbamoyl group, nitro group, amino group, N-dialkylcarbamoyloxy group, sulfamoyl L N-alkylcarbamoyloxy group, hydroxy group, alkoxycarbonylamino group, alkylthio group,
Arylthio group, aryl group, heterocyclic group, cyano group,
Represents an alkylsulfonyl group or an aryloxycarbonylamino group. In general formulas (Ila), [11b] and [■], n represents l or ko, and when n is ko,
R□ may be the same or different, and n R1
The total number of charcoal purples contained in is 0 to 10.

In the general formula CIV), R2 represents an alkyl group, an aryl group or a heterocyclic group.

In the general formula [■], R3 is a hydrogen atom, an alkyl group,
Aryl group or tetracyclic group, R4 is hydrogen atom, alkyl group, aryl group, norogen atom, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkanesulfonamide group, cyano group, heterocyclic group , represents an alkylthio group or an L-amino group.

When R1, R2, R3 or R4 represents an alkyl group,
It may be either direct or unsubstituted, chain or cyclic. The substituents include a nitrogen atom, a nitro group, a cyan group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group,
Examples include sulfamoyl group, carbamoyl M, e-droxy group, plucansulfonyl group, arylsulfonyl group, alkylthio group, and aryluna7r group.

R, R2, R3 or R47): When representing an aryl group, the aryl group may be substituted with t. As a substituent, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, a nitro group, an amino group, a sulfamoyl group, a hydroxy group, a carbamoyl group,
Examples include an aryloxycarbonylamino group, an alkoxycarbonylamino group, an acylamino group, a cyano group, and a ureido group.

When R1, R2, R3 or R4 represents all heterocyclic groups,
Contains nitrogen atoms, oxygen atoms, and sulfur atoms as heteroatoms! Represents a single-membered or 6-membered ring or fused ring, such as a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group, an oxasilyl group, an imidazolyl group, a thiazolyl group, a triazolyl group, a benzotriazolyl group, an imide group, an oxazine group, etc. These selected from may be further substituted with the substituents listed for the above ary-y group.

In the general formula CIV), the number of carbon atoms present in R2 is /
, / j.

In general formula (V), the total number of carbons contained in R3 and R4 is /~/! It is.

In the general formula (1), Y can also be represented by the following general formula [■].

General formula [■] -TIME-INHIBIT In the formula, the TIME group is a group that is bonded to the coupling position of the coupler and can be cleaved by reaction with a color developing agent,
After cleavage from the coupler, the INHIBIT group can be released in a suitably controlled manner.

The INHIBIT group is a tailing inhibitor.

In the above formula, the -TIME-INHIBIT group is preferably the general formula [■] described in European Patent No. 10/, 1,2/
~ General formula CXII [).

Among the above diffusible DIR compounds, general formulas [■a), c
Particularly preferred are those having leaving groups represented by nb) to [■].

The yellow color 1III design coupler residue represented by A includes pivaloylacetanilide type, benzoylacetanilide type, malon diester type, malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type, and malon ester monoamide. type, benzothiazolylacetate type, benzoxacylylacetamide type,
Coupler residues of benzoxacylylacetate type, malondiester type, benzimidazolylacetamide type or benzimidazolylacetate type, U.S. Patent No. J
, Iμ/, 110, or coupler residues derived from heterocycle-substituted acetamides or heterocycle-substituted acetates contained in US Pat. No. 3,770, II Ko 6, British Patent No. 1. ljri, No. 771, West German Patent (OLS) No. 2. Coupler residues derived from acylacetamides described in JOJ, OP No., JP-A-60-/3-731 or Research Tis-Froger/No. 737,
or the heterocyclic coupler residues described in US Patent No. U, OVT, 7≠.

The busenta colored microforming coupler residues represented by A include j-oxoco pyrazoli/nucleus, pyrano o-[/,!
-a] A coupler residue having a benzimidazole core or a cyanoacetophenone type coupler residue is preferred.

The cyan colorant-forming coupler residue represented by A is:
Coupler residues with a phenolic or alpha-naphthol core are preferred.

In the general formula [lj, A is the general formula CIA described in European Patent No. 10/427], [■A], [■A], (IVA
), (VA), (MA), [■A], [■A), (IX
Those represented by A and l are preferred.

Specific examples of diffusible DIR couplers are shown below.

])-/ to D-lV- is the cyan coloring diffusivity D
IR coupler, 1)-/yokara D-, 2r Haase/recolor-forming diffusive DIR coupler, D-λ rikara D-≠6 is a specific example of a yellow-color-forming diffusive DIR coupler.

])-/D-20H D-j (tCsHl 1
])-1 ])-4 -N -r H H D' 0C19H29 ])-10 (tC5H11 ])-// ])-12 H2 D" 0C14H29 H2 D-/j α ])-/A COOC1, H2゜NHL(Juti3 ])-/7 α D/r 1)-/riα D-λQ CHa D-2yoα D-33 1)-J Hiro1)-Jj (tC5H11 D-37(t)CsHu- 3t oz ])-JriD-μO CO2C14H29 p-G'/ D-Hiroshi2 D-←← D-≠6 The above-mentioned diffusive DIR compound according to the present invention is disclosed in U.S. Pat.
3,227. jj'7 No. J, A/7゜λri No. 1,
3.2 JJ, No. 500, 3゜Yjl, 99
No. 3, Hiroshi No. 3, /GC Ri, RTT No. F, JJF,
A7f, JP-A No. 77-j1.
tJ7, British Patent No. 2゜070.264, British Patent No. 2.
No. 072,363, Research Disclosure J/
The bottom can be easily reached by the method described in λ No./RIJ'/Year 1 Month February 2/221.

In the present invention, the effect of the present invention itself is not affected whether the non-photosensitive layer contains silver halide or does not contain silver halide at all. When photosensitive silver halide is incorporated, it accounts for at least 10%, preferably 70% of the total molar amount of the compound that can cause a coupling reaction with the oxidation product of the active ingredient contained in the non-photosensitive layer. more than 10%, more preferably 100% or more
If it is 0%, it is extremely advantageous. ) is coated with a DIR compound, development of photosensitive silver halide in the layer is significantly inhibited, and the layer can be said to be substantially non-photosensitive.

The amount of diffusive DIR compound added is 0 for both the non-photosensitive layer and the photosensitive layer.
,0000/~0.002mol/m, more preferably 0.00002~0°00/mo
t/m2.

The thickness of the non-photosensitive layer is 0. /~jμ is desirable, 0, J~
3μ is more preferable.

In the present invention, a known method such as the method described in US Pat. No. 2,322,027 can be used to introduce the diffusible DIR compound and other couplers described below into the silver halide emulsion layer or the non-photosensitive layer. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl buty7X/7 osphate), Que/! 2 esters (e.g. tribudel acetyl citrate), benzoic acid ester A/ (e.g. octyl benzoate A-)
, ano-kylamides (e.g. diethyl laurylamide)
, fatty acid esters (e.g. diduthoxyethylsuccinate, diethyl/L/azelate), trimedi/acid esters (e.g. trimedi:/@)butyl), or organic solvents with a boiling point of about 300C to /joOC, e.g. After being dissolved in a lower argyl acetate such as ethyl acetate or butyl acetate, ethyl propionate, secondary butyl alcohol, methyl in butyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

Also, JP Shoj/-39113, JP Shoj/-JFPj
The dispersion method using polymers described in No. tJ can also be used.

When the coupler calfone has an acid group such as sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

The emulsion layer and non-photosensitive layer of the light-sensitive material of the present invention (as the binder or protective colloid that can be used, gelatin 7 (+
- Although it is advantageous to use other hydrophilic colloids, other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein;
Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc., sugar derivatives such as sodium alginate, starch derivatives;
Abbreviation for polyvinyl alcohol, polyvinyl alcohol partial acetal, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic/I/acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc.
Alternatively, a variety of synthetic hydrophilic polymeric materials such as copolymers can be used.

Gelatin includes lime-processed gelatin, acid-processed gelatin, Bull, Soc, Sci, and Phot.

Japan, A/A, PJ O (/ri66) 1
(Enzyme-treated gelatin, such as gelatin, may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. Gelatin derivatives include gelatin 7, acid), acid anhydrides, Those obtained by reacting various compounds such as incyanates, bromoacetic acids, alkanesartinos, vinylsulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds can be used.

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. Preferred silver halide is silver iodobromide containing less than lj morti of silver iodide. Particularly preferred is silver iodobromide containing from λmolti to 12 mofiV% silver iodide.

The average grain size of silver halide grains in a photographic emulsion (the grain diameter is used for spherical or approximately spherical grains, and the principal grain size is used for cubic grains, and expressed as an average based on the projected area) is Although not particularly limited, it is preferably 3μ or less.

The particle size may be narrow or wide.

The silver halide grains in the photographic emulsion may have a regular crystalline structure such as a cube or a hexagonal, or may have a spherical or hexagonal shape.
It may be an irregular crystal such as a plate shape, or a composite of these crystal forms. It may also consist of a mixture of particles in an offshore crystalline form.

Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of five times or more the grain thickness occupy 10% or more of the total projected area.

The silver halide grains may have a layered structure in which the interior and surface layers have different phases, a bonded structure, or a uniform phase. Further, the particles may be particles in which the latent iron is mainly formed on the surface, or may be particles in which the latent iron is mainly formed inside the particle.

The photographic emulsion used in the present invention is p, Q1afkid
Written by 6s Chimie et physiqu6 Pho
tographiqu6 (published by Paul Mote1, / 1967), G, F.

Photographic lli:m by puffin
ulsionChemistry (The )'o
Cal Press, 1966), V, L, Ze
Making an by likman 6t al
d Coaling photography Em
ulsion ('l'he Focal Pr
It can be adjusted using the method described in ess, published by / 6 Koji). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of 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 controlled double 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.

Two or more types of separately formed No. Rogge/Silver Fide emulsions may be mixed and used.

During the formation of silver halide grains or the progress of physical ripening, cadmium, zinc salt, lead salt, thallium salt, iridium salt or a complex salt thereof, rhodium salt or a complex salt thereof, iron salt or iron complex salt, etc. may be allowed to coexist.

After the emulsion is precipitated or after physical ripening, the soluble salts are removed.As a means for this purpose, the long-known tardel water washing method, which involves gelatinization of seranan, may be used; billions of salts consisting of polyvalent anions, such as sodium sulfate, anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or gelatin spindles (such as aliphatic acylated gelatin, aromatic acylated gelatin, aromatic It may also be used in a sedimentation method (Flocule-7 Yo/) using carbamoylated gelatin, etc.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example, t-1, Fr16s6r @l') i6 Qrundlag6n d6r
photography1prOZe3s6 mit
3i1berhalog6niden” (Akad6
mische V6rlagsges6Hschaft
The method described in 61) pages 673-73μ can be used.

i.e. sulfur that can react with active gelatin and silver? : Sulfur sensitization method using chemical compounds (e.g. thiosulfate, thiourine compounds, mercapto compounds, rhodanines); Reducing substances (e.g. tin salts, amines, hydrazine derivatives, formamidine sulfur) 7tL silane compound) reduction sensitization method: Pt
S Ir, Pd, etc., all complex salts of group ■ of the periodic table)? The Noble Kanemaki sensitization method used can be used independently or in combination.

The photographic emulsion used in the present invention may contain various compounds such as t-gold for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing the overall photographic performance. . i.e. azoles such as benzothiazolium salts, diCh6n troimidazoles,
Nitrobenzimidazoles, chlorobenzimidazoles, bromobenz imidazoles, mercaptothiazofushi, mercaptobenzothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially l-phenyl-j-mercabutodetrazole); mercaptopyrimidines; mercaptotriazine; thioketo compounds such as oxadolinthione; azaindenes, such as triazaindenes, tetraazaindenes, etc. V-hydroxy substitution (/,!,
3a, 7) tetraazaindenes), interazaindenes; many compounds known as antifoggants or stabilizers, such as henchiosulfonic acid, benzenesulfine modified, benzenesulfone amide, etc. You can add money.

The photographic emulsion layer or other hydrophilic colloid layer of the external light material prepared using the present invention may include coating aids, antistatic properties, slip property improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
For various purposes such as development acceleration, contrast enhancement, sensitization, etc., specific surfactants may be included.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates,
Polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol rubitan ester M, poly(alkylene/glycol alkyl amines or amides, polyethylene oxide adducts of silicone), glycidol visiting conductors ( For example, alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols,
Nonionic surfactants such as alkyl esters of sugars;
Alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkyl naphthalene/sulfonates, alkyl phosphates, alkyl phosphates, N-acyl-N-alkyl taurines,
Acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. Anionic surfactants containing; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or halogen acid esters, alkyl betaines, amine oxides; alkylamine salts, aliphatic or aromatic surfactants; Surfactants such as secondary ammonium salts, heterocyclic primary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives,
Urine accumulative conductors, imidazole derivatives, 3-pyrazolidones, etc. may also be used.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or difficult-to-rock synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters (for example, vinyl tetraacetate), acrylonitrile, olefins, styrene, etc. alone or in combination, or these. Poly2 can be used as a combination titanium component of acrylic acid, methacrylic acid, α,β-unsaturated dicarboxylic acid, hydroxy/alkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc.

Photographic processing of layers comprising photographic emulsions made using the present invention includes, for example, Research Disclosure No. 76 No. 2
Any of the known methods and known treatment liquids as described on pages t to 30 can be applied. This photographic processing may be any photographic processing that forms a color chart (color photographic processing) depending on the purpose. Processing i1
[is usually /I 0CkaG)10'C(7)fZl
ca hare, if, / , m degree lower than r'C or JO
The temperature may exceed 0C.

As a special form of development processing, herbal medicines are added to the light-sensitive material.
For example, a method may be used in which the photosensitive material is included in the emulsion layer and developed by processing the photosensitive material in an alkaline aqueous solution. Among the current main drugs, hydrophobic ones are Research Disclosure 1
6ri No. 16ri 21゜U.S. Patent 2.73ri, tri No. 0,
British patent l:/J.

It can be incorporated into the emulsion layer by the glazing method described in No. 233 or West German Patent No. i, z≠7.763. Such dilution treatment may be combined with silver salt stabilization treatment with thioanate.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-bathable aluminum salt as a hardening agent.

Conventional methods can be applied when forming a pigment squad.

For example, negative-positive method (for example, “Journal of
th6 3ociety of Motion pi
clur6and'l'e16vision Eng
in6erS' 6/vol. (1953), 667-7
0/page) etc.

Color developers generally consist of alkaline aqueous solutions of color-producing herbal medicines. The color developing agent is a known primary aromatic amine developer, such as phenylenediamines (for example -
monoamino-N,N-diethylaniline, 3-methyl-hiro-amino-N,N-dief A/7niline, ≠-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-l-amino- N-ethyl-N-β-hydroxyethylaniline, 3-methyl-≠-amino-N-
ethyl-N-β-methanesulfamide ethylaniline,
Hiro-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition, Photograph by F. A. Mason
icprocessing Ch6mistry(Fo
P226-2 of cal pr6ss (1964)
2, U.S. Patent λ, 13. No. III, same λ, j octopus,
The material described in Hiroyoshi No. 36, JP-A No. 2003-121000, Akihiro R-+μ233, etc., may be used.

Other color toy liquids include sub-Vic salts to alkali gold,
pH buffering agents such as carbonates, borates, and phosphates, development inhibitors such as bromides, iodides, and anti-capri agents, and antifoggants may be included. In addition, if necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyfluoricol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, zero-forming couplers, and competitors may be added. Coupler, fogging agent such as sodium boron hydride, auxiliary developer such as l-phenyl-3-pyrazolidone, viscosity imparting agent, polycarboxylic acid chelating agent, antioxidant, etc. may contain gold.

The photographic emulsion layer after color development is usually bleached.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As a bleaching agent, for example, iron (III
), Kobanosite (I [[), Chromium (■), Copper (II)
Polyvalent all-pole compounds such as, peracids, quinones, nitroso compounds, etc. are used.

For example, ferriheptadide, dichromate, iron (Tit)
) or Kobal) (In), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, /3-diamino-
Amitibolic AI acids such as coprobanoltetraacetic acid, or complex salts of π-organic acids such as citric acid, tartaric acid, and malic acid; persulfates, pernonganic salts; nitrosophenols, and the like can be used. Of these, potassium ferricyanide, sodium iron(III) ethylenediaminetetraacetate, and ammonium ethylenediaminetetraacetate+1it) are particularly useful. Ethylenediami/four vinegar 1j2 (
1) Complex salts are suitable for M both in stand-alone bleach solutions and in -bath bleach constant solutions.

Bleaching or bleach-fixing solution has 8 national patents 3.0≠λ,!
No. 20, 3.2≠l, No. 266, Tokuko Sho pyo-tro
In addition to the bleaching accelerators described in Japanese Patent Application Publication No. 4136/1983 and the thiol compounds described in Japanese Patent Application Laid-Open No. 3-41732, various additives can also be added.

The photographic emulsion used in the present invention may be spectrally sensitized by methine color chips or the like. The dyes used include
cyanine dye, merocyania dye, mosquito amine dye,
Included are complex merocyania dyes, holocyania dyes, hemi-7anine dyes, steryl dyes and hemioxonol dyes. Particularly useful dyes are cyanine dyes,
It is a derivative of merocyania pigments and composite merocyania pigments. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. Namely, pyridine nucleus, oxazoline nucleus, thiazoline nucleus, virole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon tight ring is fused to the nucleus, sokuchi, indolenine nucleus, benzindolenine nucleus,
Indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazoline-yone nucleus, a theohydantoy/nucleus, and a λ-thioxazolidine-2 nucleus as a ketomethylene structure tW.
J to 6-membered heterocyclic nuclei such as a 1 μm dione nucleus, a 20 μm thiazolecy dione nucleus, a rhodanine nucleus, and a thiobarbic acid nucleus can be applied.

These sensitizing dyes may be used singly or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light.
A substance exhibiting supersensitization may also be included in the emulsion.

The present invention provides at least λ different spectral paths y on a support.
It is also applicable to multilayer, multicolor photographic materials having t-. A multilayer natural color photographic material usually has at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. Cyan-forming coupler in red-sensitive emulsion layer and green-sensitive emulsion layer!
It is customary to include a zenta-forming coupler and a yellow-forming coupler in the blue-sensitive emulsion layer, but different combinations may be used in some cases.

The photographic emulsion layer and non-light-sensitive layer of the photographic light-sensitive material prepared using the present invention contain a main coupler and other 8-element forming couplers, that is, aromatic 7th-class amine developer@
! A compound that can develop color by oxidative coupling with a drug (eg, phenylenediamine derivative, aminephenol derivative, etc.) may also be used. For example, as a Tsuzenta coupler! - Pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, cyano-heptylcoupler/couplers, open-chain acylacetonitrile couplers, etc. Yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, pivaloylacetanilides), etc. This includes oxidation, cyankabu 2-, naphtho-y coupler, phenol coupler, etc. These couplers are preferably non-diffusible and have a hydrophobic group called a pallast group in their molecules, or are polymerized.

The coupler may be either ψ-component or 4-component to silver ions. Alternatively, it may be a colored turnip 2-1 which has a color correction effect or a normal DIR coupler which releases a development inhibitor with low diffusivity during development.

In addition to DIR couplers, there are also colorless DIR couplers in which the coupling reaction product is colorless and releases a development inhibitor.
The photosensitive material may contain a coupling compound or a compound that releases a development inhibitor during development.

Specific examples of magenta coloring couplers are given in U.S. Patent No.
o, 'yrr, same no. λ, yr3. toe issue, same No. 3.
Q6λ, No. 6/3, No. 3. /λ7゜ko6ri No. J
, 311. Hiro 7. ≦ No. 3゜μl, 3ri No. 7, same No. J, j/7. Hiroλri issue, same issue J, J! rr, J/R No. J, 612. J Co. λ No. 3.6/yo, 306
No. J, r3'f, No. 901, No. 3.85P1
, FF7, West German Patent No. 1.110. μ66, West German Patent Application (OLS) No. 2. μor, ttz issue, same No. 2. Hiro 17, Rihiro! No. 2. Hiroit, Rijri No. 2.
Hiro 244. tIl, No. 7, Tokuko Sho μ0-603/No., Tokusho Sho same Turf μO core No., same μ Turf 4co, No. 2r, same py-ixyszr No., same! No. 0-602JJ, No. 10-/j No. 1336, No. r/-, No. 1Or26, No. j
/-26j%/issue, same! Ko ≠ 2/2/ issue, same j Ko j
r Octopus No. 2, same! 3-! J/22, etc.

Specific examples of yellow coloring couplers are given in U.S. Patent No. λ,t7j,0
! No. 7, same No. J, 21. j,! No. 06, No. 3. ←or
, Iri Hirosaki, same No. J, Nij/, No. 1211, same No. 3. z
rco, No. 3-2, No. J, 7λj, No. 072, No. 3.
tyi, ≠←! No. 1, West German Patent No. 1. Yoμ'i, RTR issue, West German application publication number λ.

λ/2. No. 17, No. 2.2t/, No. 361, No. 2
．． ≠ia, oot issue, British patent no. 1. μko, 020'
pj, JP Sho J/-107rJ, JP Sho Guar 247
No. 33, No. 1-1-73/μ7, No. jO-1. JGcI
No. 1O-47jO, No. 0-/233μλ, JiO-/J (No. 7 Hiroko, No. jl-λ/127, No. J/-102636, No. 12-42'it2 Hiro) No. j2-//j2/Y, etc.

A specific example of a cyan coloring coupler is given in U.S. Patent No. λ.

J4F, FJP No. λ, Me J Hiro, No. 27, No. 2
．． Gc7'1l-0221, No. 2, 12/, For
No. 2. In2.124, same No.3. OJP, 19
No. 4, No. J, Jl/, Gc No. 74, 1 Tsukasa No. 3, Hirohiro t
, No. 422, No. 3. Hiroyo r, No. 311, same No. 3. ≠7
4. ! No. 63, same No. 3. Yor3゜ri No. 71, same No. 3. t
ri, 3t3, same No. 3゜711.301, same No. J,
7t7, 4t// No. 3. rro, tti issue, 3.2ri 6.2jJ, ooGc, riλri issue,
West German Patent Application A (OLS) No. J, F/u, 1
304j, same 1gx.

Hiroyo μ, 3λri issue, Tokkai Sho μr-joyo 5, same ttr
-zyrJr issue, ji-x6o3tt issue, same j/-/
l/-6121, same! 2-tYls21fi issue, same j
2-TaOri No. 32 and No. 16-6113≠.

Colored Turnip 2-, for example, U.S. Patent No. 2,!
λ/, ri0, No. J, 0JiL, r Octopus, No. 3
．． Hiroshi 74.160, special public show 3r-22J3j, same%
2-//301A No., same GcGc-20/&, same Hiro-32←61, JP-A Shoj/-2603μ, same j2-
Ko 212/No., West German Patent M (OLS) No. 2,4/lr
, 91ter WHCEJK can be used.

In order to satisfy the characteristics required of a photosensitive material, two or more types of the above-mentioned Kabu 2- etc. can be used in the same layer, or the same compound can be added to two or more different layers.
Of course it doesn't matter.

The photographic color developer used is a medium scale image t-
The maximum absorption band of the cyan dye formed from the cyan coloring agent is from about 6oo to 720
The maximum absorption band of the magenta dye formed from the magenta color former is between about 100 and 10 nm, and the maximum absorption band of the yellow dye formed from the yellow color former is between about ≠00 and 100 nm. Preferably, it is between LILtOnm.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example, chromium salts (chromium alum, chromium acetate, etc.)
, aldehydes, (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (λ, 3-dihydroxydioxane, etc.), activated vinyl compounds (/, J, j -) lyacryloyl-hexahydro-3-) riazine, /, 3-
vinylsulfonyl-2-brono
IF sheets, IJ azines, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloric acid, etc.), etc. can be used alone or in combination.

In the photosensitive material produced using the present invention, when dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an amine phenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifogging agent, and specific examples thereof include US Pat. No. 1.360. 220
No., same, 33bu.

3Jj, same, ≠03, 7λ1, same, ←lr, t
i3 issue, same co, 671. J/Hirogo, same.

70/, /ri 7, same λ, 70 Hiro, 7/J, same! ,7
,2f,! No. 77, same, No. 732.300, same 2.7
3! , M issue, Tokukai Shojo-ycoytrJP! , also 0-
No. 42119, same! 0-FJ Octopus, same jO-//1
No. 7337, Jλ-7 Hiroshi No. 6231, Special Public Shoj-0-
d described in No. 23113 etc. The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with an aryl group (e.g., those described in U.S. Pat.
Same 3.3j.

tri), be/siphenon compounds (e.g., those described in JP-A-Sho←J-27rV-), cinnamon powder ester compounds (e.g., U.S. Pat. No. 3.7oz, ROR, J, 707.J7J) ), butadiene compounds (e.g., those described in US Pat.

O Hiromu, No. 222) or benzoxidol compounds (eg, U.S. Pat. No. 3.700, ←j!
) can be used. Additionally, U.S. Patent 3. Hiro W? , No. 762, and those described in Japanese Patent Application Laid-open No. Shojp-≠ryoJj can also be used. UV-absorbing couplers (e.g. α-naphthol-based cyan dye-forming couplers) and UV-absorbing poly! - etc. may also be used. These ultraviolet absorbers may be mordanted in specific layers. .

The light-sensitive material produced using the present invention may contain a water-soluble dye as a hydrophilic colloid layer filter dye or for various purposes such as preventing irradiation. Such dyes include oxynol dyes, hemioquinnol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes. Of these, oquinol dyes; hemioquinnol dyes and merocyanine dyes are useful.

In carrying out the present invention, the following known deterioration inhibitors may be used in combination, and the color iron stabilizers used in the present invention may also be used in combination. Known anti-fading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenol L p-oxyphenol derivatives, and bisphenols.

Specific examples of hydroquinone derivatives are described in US Patent λ.

31.0, 2ri 0, Dou, Hiroshi/1, 1. LJ No., same λ
, 7j, J/gu issue, same, 70/, /ri 7, same 2
．． 70μ, 713 issue, same λ, 7λr, + issue, same co,
73, No. 300, 2.73, 7t! No., same λ,'
yio, toi issue, same 2. lrl&.

oxr issue, British patent/,! 63. Y2/, etc., and gallic acid derivatives are described in US Pat. No. 3, Koj7,
No. 07P, No. 3.04, No. 242, etc., and p-alkoxyphenos are described in U.S. Patent No. 2.7.
Jj, Vt6, same 3°6ri1. It is described in the rioi issue, the special public show μter issue 20?77, and the same issue 62-A4Jj9.
, p-ox7phenol derivatives are disclosed in U.S. Patent 3. μ
3 pieces.

300, same J, Jr73, 0yo0, same 3. ! 7 Hiroshi,
t27, same J, 71. Lfi, J, No. 37, JP-A-Shoj.
2-4! No. 433, same! λ-／≠7≠3LtL, ゛Same! Call! λ2ko! Bisphenols are described in U.S. Pat. No. J, 700, No. μj.

Example-1 Photographic light-sensitive element sample 10/10 was prepared on a polyethylene terephthalate support with a color consisting of each layer having the composition shown below.
was created.

1st layer, 8gt red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide: 6 molti, average grain Suise o,
tμ) ・・・・・・Amount of silver coating 0,71723 mol/□2 Sensitizing dye ■・・・・・・・・・・・・A for 1 mol of tM
×10 molar sensitizing dye■・・・・・・・・・・・・i for 1 mol of silver, zxio Molar coupler A・・・・・・・・・・・・o, for 1 mol of silver or Molar coupler B・・・・・・・・・＠0.002 moles per mole of coupler/Hiroshi…0.003 moles of tricresyl phosphate per mole of silver… ...0.7 g for 7 g of coupler Second layer: Second red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; t molch, average grain size/,
2μ) ......Silver coating amount o, oii mol/m 2 Sensitized color accumulation■......Tx per 1 mole of silver
io Molar sensitizing dye■・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・･･･････････････｡ B......0.00 λ mol for 1 mole of silver Coupler D-/G'...0.002 for 1 mole of silver
Moltricresyl phosphate...0.7 grams per coupler/gram Third layer; protective layer polymethyl methacrylate particles (diameter approx. l).

! gelatin layer containing μ).

The couplers in each layer were prepared by heating a solution of the above-described high-boiling solvent and ethyl acetate (dissolved by heating, mixing with an io% aqueous gelatin solution to which sodium p-dodecylbenzenesulfonic acid was added as an emulsifier, and emulsifying it in a colloid mill. I used something.

In addition to the above composition, a gelatin hardener H-/ and a surfactant were added to each layer.

Compound sensitizing dye used to prepare the sample ■: Anhydro j, j'-dichloro-3,3
7-di(γ-sulfopropyl)-terethyl-thiacarbocyanine hydroxide pyridinium salt sensitizing dye ■: Anhydroterethyl-3,31-di(γ-sulfopropyl AI)-Hiro, J, Hiro'.

! '-Sibenzothiaka/L/medianine hydroxide triethylamine salt coupler B H coupler C H-/CH2-cH8O□CH2C0NHCH2CH2N) (
COCH2SO2C Sample H2 Sample 102 Prototype 2 An intermediate layer having the following composition was provided between the 7th layer and the 2nd layer of the sample 102, and a coupler 1) between the 1st and 2nd layers was added.
In place of the above coupler C, the amount is each coupler 1)-/μ
It was produced in the same manner as sample 101 except that it was set to //J.

Intermediate layer: Cobra-C...i x 10 mol/rr
L2 tricresyl phosphate...For coupler 11 / gelatin layer sample containing 6 grams of emulsified dispersion / (first layer, middle layer, and second layer of 10 preparation samples of 113) Coupler (4-
Coupler])-j/ was replaced by an equimolar amount, and the amount of silver applied in the first layer was increased by 10 tchi, and the amount of silver applied in the second layer was increased from sample 102 to 102. did.

Preparation of sample iohiro Coupler c4- of the 7th layer, intermediate layer, and 2nd layer of sample 102
Coupler 1) -/4! It was produced in the same manner as sample 102 except that - was replaced by an equimolar amount.

When these samples /0/, IO← were given a red moat-like exposure and the color development shown below was carried out, almost the same sensitivity and gradation were obtained.

In this case, the development process is carried out using jr'C as shown below.

1. Color development・・・・・・・・・・・・・・・・・・
・・・・・・・・・3 minutes/j seconds 2, bleaching・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
...6 minutes 30 seconds 3, wash with water...
・・・・・・・・・・・・・・・・・・・・・・・・3
Minutes/j seconds 4, fixed...
・・・・・・・・・・・・・・・・・・Hirobu Q seconds 5
, Washing, Seal, Group, 1 River, Old...
Old...3 minutes/1 second 6, stable...
1 minute 30 seconds The composition of the treatment liquid used in each step is as follows.

Color liquid sodium nitrilotriacetate・・・・・・・・・・・・
・・・／Sodium sulfite・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・1. Q Sodium carbonate・・・・・・・・・・・・・・・Mark・old・・
30.0? Potassium bromide・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・1.
≠1 Hydroxylamine sulfate, old, old, old...λ, ≠2
Hiro-(N-ethyl-β-hydroxyethylamino)-λ-methylaniline@acid acid・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・μ、! ? Add water...
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・／、OL bleaching solution ammonium bromide・・・・・・・・・・・・・・・・・・・
... ito, aya/Sonia Mizu (Jr Chi)...
・・・・・・・・・・・・λ, OCX:.

Ethylenediamine-sodium iron tetraacetate・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・／30.0? Glacial acetic acid...
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・L←、Q■ Add water・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・／、01 Fixer Sodium Tetrapolyphosphate・・・・・・・・・・・・
λ, Q2 Sodium sulfite・・・・・・・・・・・・
・・・・・・・・・・・・・・・Hiroshi, 0? Ammonium deoate (70%).../71. OCI:.

Sodium bisulfite・・・・・・・・・・・・・・・
・・・・・・・・・≠、Add 62 water・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・／、01 Stable liquid formalin・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・t, ocx:.

Add water・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・/, OL The cyan color graininess of these samples was determined by the conventional RMS method. Although the determination of graininess using the RMS method is well known among the parties involved,
the photography proc6ss
' % th Ed (by James, Nie P Cumilla/Company) Pbi (described in ~1.21. The measurement aperture is ≠
rμ.

Also, the measurement of MTF of cyan color is °'l'h6Theo.
r)' of the Photographic
It was carried out according to the method described in prOc6ss'G4th Ed (written by James: Macmillan) Pj Octopus ~6/I.

The measurement results of RMS value and MTF value are shown in Table-/.

Sample ioi is an example in which a cyan color-forming diffusive DIR compound is added only to the red-sensitive emulsion layer. In this case, the MTF shows a very high value, but the graininess expressed by the RMS value is noticeable. Sample 102: A DIR compound that develops cyan color and has a small diffusion I was added to the intermediate layer adjacent to the red-sensitive emulsion layer, but the effect of improving both graininess and MTF was insufficient. In sample 103, a yellow color-forming diffusive DIR compound was added to the intermediate layer adjacent to the red-sensitive emulsion layer, but it was necessary to increase the amount of cyan coupler silver to match the photographic performance, and as a result, the MTF significantly increased. decreased. In sample 10←, which is the present invention, by adding a cyan coloring diffusive DIR compound to the red-sensitive emulsion layer and the intermediate layer adjacent thereto,
It has become possible to obtain a can-photosensitive element with excellent graininess and sharpness (MTF).

Example 2 A multilayer color photographic material sample 20 was prepared on a cellulose triacetate film support, including each layer of the set shown below.

1st layer: antihalation layer black gelatin layer containing colloidal silver λ layer; intermediate layer gelatin layer 3rd layer; 1st red-sensitive emulsion layer silver iodobromide emulsion (silver iodide: bumolti, average grain size 0.
6μ) ...Amount of silver coated 0.023 mol/m2 Sensitizing dye■ ......Axlo per 1 mol of silver
Molar sensitizing dye ■・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・01 Molar coupler D-/μ... 0.003 moles per 1 mole of silver Coupler B... Flexible... 0.002 per 1 mole of silver
Moldi-n-butyl phthalate... Contains i and o grams for coupler/gram! ! ←Layer I λth red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide t molten, average grain size i, o
μ) ...Amount of silver coated o, oor-e, □2 sensitizing dye■ ......Group - LXlo per mole of silver
5 moles of sensitizing dye■...1 old...@i1 mole/,!
X10 ”Molar coupler K...mark...O2 per mole of silver
0 mole coupler B... old... 0.00 per mole of silver
2 mole di-n-butyl phthalate river... For coupler/gram 1. Contains o-grams.

jth layer; middle layer λ,! - Gelatin layer containing d-t-octylhydroquinone...2.2 x IO'mol/rn2.

6th layer; 1st green-sensitive emulsion I- Silver iodobromide emulsion (fk silver 4 lurti average grain size 0.
1μ) ・・・・・・Amount of silver coated o, oii mol/m2 Concentrating dye ■・・・・・・・・・JXlo per mol of silver
Molar sensitizing dye ■...Scream.../x10 per mole of scissors
Molar coupler D: 0.0 mol coupler E for 1 mole of silver (for 0.03 mole coupler D-λ7. ...0.01 mole of tricresyl phosphate per mole of silver, old... Contains 1.0 grams per coupler/gram.

7th layer: 1st blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide r morch, average grain size i, o
μ) ・・・・・・Silver coating @ 08oo mol/□2 sensitizing dye■・・・・・・・・・・・・3×1 for 1 mol of silver
0 mole sensitizing dye■......scream...@ixi for 7 moles
o Molar coupler F old... o per mole of silver,
oi, z mole coupler G... Old... 0.0 for 1 mole of silver.
001 mole coupler D: Contains 1.5 grams per 7 grams of o,oot mole tricresyl phosphate/former coupler per mole of silver.

2nd layer; Yellow filter layer; gelatin layer containing yellow colloidal silver and an emulsified dispersion of λ, J-1 octyl hydroquinone tricresyl phosphate in an aqueous gelatin solution; warming layer; 1st blue-sensitive emulsion layer iodobromide layer; Silver emulsion (iodide scissors; 6 mol, average grain size 0.7μ) ... Coated silver amount θ, oi + mole / m2 Coupler H ...... Silver / mole 0.2 against
j mole coupler]) -j/...0.00λ per 1 mole of silver
Moltricresyl phosphate: Contains 1j grams of O per 1 gram of coupler.

io layer; second blue-sensitive emulsion layer silver iodobromide (silver iodide; r morch, average grain size/, 2μ)...
・・・・Coating silver 1j; 0.010 mol/m2 coupler H・・・・・・・・・o, o per mol of silver
t mole coupler D-3/... 0.001 mole tricresyl phosphate per mole of silver... per gram of coupler O0! Eleventh layer containing duram; first protective layer silver iodobromide fine grain emulsion (silver iodide 1 molt, average grain size 0.0
7μ) with a coating silver amount of 0. 72nd layer of gelatin layer containing an emulsified dispersion of ultraviolet absorber UV-/ and tricresyl phosphate; @1 protective layer polymethyl methacrylate particles (diameter approx. l.

Apply a gelatin layer containing 5μ).

The coupler in each layer was emulsified in the same manner as in Example-1.

In addition to the above composition, a gelatin hardener H-/ and a surfactant were added to each layer.

Compound m used to prepare the sample Color-sensitivity t, 61.4/ -tetrachloro-/, l'-
Diethyl-3,3'-cy(β-[β-(r-sulfopropyl)ethoxy]ethylimidazolocarbo7-anine hydroxide sodium salt Kabucy D Coupler ■(Coupler I H3 sH11 Coupler K tcaHx? UV-/ Sample Co Between the 7th layer and the 10th layer of sample 20/, an intermediate gold film having the following composition was added;
Sample 201 was prepared in the same manner as Sample 201 except that the amount was changed to 1/H of coupler D-37 instead of 3/f coupler.

Middle layer; Kashi9-1・・・・・・・・・・・・／, jt
Preparation of gelatin layer sample 203 containing i, z grams of emulsion dispersion for coupler/2. 10th layer coupler [-
Changed to coupler D-27, and wetted each coupler I / 3
And so. Furthermore, the 10th layer @
Apply t/! Sample 202 was prepared in the same manner as sample 202 except that each of the sample sizes was increased.

Preparation of Sample 20≠Trial #+: Produced in the same manner as Sample #+202 except that coupler I of the second layer, intermediate layer, and first OWJ of 102 was replaced with coupler DJ/VC.

Preparation of sample 20 Sample 20 was prepared in the same manner as sample 20←, except that the coupler p-Ji6i of the first O layer of sample λO≠])-3/f was removed and the coupler p-Ji6i of the middle +=1 layer was doubled.

These multilayer samples 201-20jvC, blue image-like &!
When the original color was reproduced as shown in Example 1, almost the same electric shock and gradation were obtained.

The RMS and MTF of the yellow color family of these samples were measured in the same manner as in Example 1, and are shown in Table 1.

From this result, it was found that by adding a yellow coloring diffusive DIR compound to the intermediate layer adjacent to the blue-gold-blue emulsion layer,
A color photographic material with excellent graininess (RMS) and sharpness (MTF) was obtained.

Procedural amendment rare Showa era year io month date

Claims (1)

[Claims] on a support, at least one silver halide emulsion layer containing a coupler that develops one of the three subtractive primary colors and a diffusible DIR coupler that develops substantially the same hue as this color; 1. A silver halide color photographic material comprising at least one adjacent non-photosensitive layer containing a diffusive DIR compound.