JPS62173466A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a color photographic sensitive material which decreases the generation of stains after a color developing process by having a layer contg. a specific cyan dye image forming coupler and specific compd. CONSTITUTION:This material contains at least one kind of the cyan dye image forming coupler expressed by the formula I and at least one kind of the compd. expressed by the formula II. In the formula I, R1 denotes a substd. or unsubstd. aliphat. group, etc., R2 denotes a hydrogen atom, etc., Z denotes a hydrogen group or a group which can be desorbed in the stage of oxidation coupling with a developing agent. In the formula II, A denotes a substd. or unsubstd. alkyl group, etc., R21, R22 respectively independently denote a hydrogen atom, substd. or unsubstd. alkyl group, R23 denotes a hydrogen atom, etc., R24 denotes a substd. or unsubstd. aryl group, P denotes an oxygen atom or sulfur atom. The coupler expressed by the formula I is preferably of 2X10<-3>-3X10<-1> molar ratio per mol of silver halide existing in the same layer and the compd. expressed by the formula II is added preferably in a 2X30mol% range of the coupler expressed by the formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a color light-sensitive material containing a phenolic cyan image-forming coupler.

More specifically, the present invention relates to a method for preventing staining after developing a photosensitive material containing a cyan seven-color image forming coupler (hereinafter referred to as cyan coupler).

(Prior art) After exposing a silver halide photographic light-sensitive material to light, color development is performed, whereby the aromatic-grade amine developing agent oxidized by the silver halide reacts with the color-forming coupler, resulting in a color image. is formed.

Typical cyan image-forming couplers include phenol couplers and naphthol couplers, and phenol couplers are described, for example, in U.S. Pat.
Same co, 77λ, /62, same j, 7rF, 30tr
No. 9. / Coro No. 139, 4t, 334t,
No. 077, same g, No. 327.173, same 3,4t g,
No. 622, same number, 333, No. 999, same number, ll!
/,! Ta No. 9, same as Tako 7.7. <7, etc., and the naphthol type coupler is described in U.S. Patent No. 2, g.
7 & , , No. 293, Same Gu, 0! There are descriptions in λ, No. 2/2, No. 2/2, No. 39, No. 4t, No. 22F, No. 233, No. 29t, No. 0θ, etc.

(Problems to be Solved by the Invention) However, color images obtained in this manner may cause staining (increase in density in unexposed areas) after processing, and this drawback has not been significantly improved. Although there were some, it wasn't enough.

Stain in the unexposed areas of a silver halide color photographic material is undesirable because it not only determines the quality of white areas in the image but also worsens color staining of the color image and impairs visual sharpness. Particularly in the case of reflective materials (for example, color filters), the reflection density of the stain is theoretically emphasized several times the transmission density, and even a weak stain impairs image quality, so this is a very important factor. be.

The occurrence of staining in silver halide color photographic materials can be broadly classified into three types depending on the cause. 7. Problems caused by heat and humidity after the unprocessed photosensitive material is manufactured and before processing; 2. Problems caused by development fog of silver halide; and 3. Problems caused by color coupler development processing solution. (e.g. air fog), or the developing agent remaining in the emulsion film is oxidized by the subsequent bleaching bath or oxygen in the air, reacts with the coupler, and becomes a dye (e.g. bleaching One of the causes is the change over time of the sensitive material in the development layer due to light and moist heat. The stain caused by the development treatment of the phenolic cyan coupler according to the present invention means the stain of 3 and 3 above.

Therefore, an object of the present invention is to provide a color photographic material in which staining is less likely to occur after color development processing as described above.

An example of using a 3-pyrazolidone derivative to prevent staining is known from JP-A-37-2//, /&7, but this 3-pyrazolidone compound has a substituent on the nitrogen atom at the co-position. , which is completely different from the present invention.

By the way, patents are known that use 3-virasoliton derivatives, especially their heptacursors, in silver halide photographic light-sensitive materials. For example, U.S. Patent No. 3,214/
Co(substituted methyl)-3-pyrazolidone is known in No. 9g2, but this is completely different from the present invention.
It also does not have the effect of the present invention. Japanese Patent Publication No. 67-41024tt
issue and Tokukaisho! 9-1041t<11 A precursor compound in which the 3-enol of 3-pyrazolidone is protected with an acyl ester or a carbonate ester is known. However, the purpose of adding these compounds to silver halide photographic materials is to provide good photographic sensitivity, maximum density, and desired sensitometric properties;
The contents described in No. 024tj are adapted to black and white photographic materials. On the other hand, Tokukai Akira! The content described in No. 4t1 of 9-/θ is that high sensitivity was achieved without an increase in fog density, and it is applicable to color photographic materials, but this is different from the purpose of the present invention. It is something.

(Means for solving the problems) As a result of various studies to achieve the above object of the present invention,
The objects of the present invention can be achieved by a silver halide color photographic light-sensitive material containing at least seven types of cyan image-forming couplers represented by the following general formula (1) and at least seven types of compounds represented by the following general formula (It). We have found that this can be achieved effectively.

General formula (1) General formula (1) General formula (II) or sulfur atom.

The compound of the general formula (IF) is disclosed in Japanese Patent Application Publication No. 2003-100002. -4t02g!
It can be synthesized by the method described in No. and Japanese Patent Application Laid-open No. Shoj9-IO'l≦G/No., or a method analogous thereto.

The phenolic cyan coupler in general formula (I) will be explained.

R1 is preferably an aliphatic group having a carbon number of ~3g, preferably an aromatic group having a carbon number of ~3g (e.g., phenyl group, naphthyl group, etc.), a heterocyclic group (e.g., a 3-pyridyl group, or aromatic or heterocyclic amino groups (e.g., anilino group, naphthylamino group,
λ-benzothiazolylamino group, copyridylamino group, etc.), and these groups further include alkyl groups, aryl groups, heterocyclic groups, alkoxy groups (e.g., methoxy groups, λ-methoxyethoxy groups, etc.), aryl groups, etc. Oxy group (
For example, 2. Goosey tert-amylphenoxy group,
(cochlorophenoxy group, cucyanophenoxy group, etc.), alkenyloxy group (e.g., 2-pro is a nyloxy group, etc.), acyl group (e.g., acetyl group, benzoyl group, etc.), ester group (e.g., butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group), amide group (e.g. acetylamino group, ethylcarbamoyl group, dimethylcarbamoyl group,
methanesulfonamide group, butylsulfamoyl group, etc.), sulfamide group (e.g., dipropylsulfamoylamino group, etc.), imide group (e.g., succi/imide group, hydantoinyl group, etc.), ureido group (e.g., phenylureido group, dimethylureido group, etc.), aliphatic or aromatic sulfonyl group (e.g., methanesulfonyl group, phenylsulfonyl group), aliphatic or aromatic thio group (e.g., ethylthio group, phenylthio group, etc.), hydroxy group, , a carboxy group, a nitro group, a sulfo group, a halogen atom, and the like.

As used herein, the term "aliphatic group" may be linear, branched, or cyclic, and includes saturated and unsaturated groups such as alkyl, alkenyl, and alkynyl groups ( Representative examples include methyl group, ethyl group, butyl group, dodecyl group, octadecyl group, alkynyl group, 1SO-propyl group, tert-butyl group,
7 ert-octyl group, tert-dodecyl group, cyclohexyl group, cyclo is butyl group, allyl group, vinyl group,
(2-hexadecenyl group, propargyl group, etc.)

R2 is a hydrogen atom, preferably an acylamino group having up to 3 g of carbon atoms (e.g., acetylamino, butyrylamino, tetradecanoylamino, benzoylamino group, etc.), or an aliphatic group having at least 7 g of carbon atoms, preferably 7 to θ carbon atoms. Represents a family group. These groups may be substituted with a permissible substituent in R1, for example, R2 includes a methyl group and a methyl group having a substituent, and this substituent includes an alkyloxy group (e.g., methoxy group, butoxy group). group, hensyloxy group, etc.), aryloxy group (e.g., phenoxy group, q-chlorophenoxy group, cucyanophenoxy group, <t-ter t-7 milk enoxy group, etc.), alkylthio group (e.g., methylthio group, dodecylthio group, etc.) ), arylthio groups (e.g. phenylthio group, chlorophenylthio L & -dodecylphenylthio group), alkyl or arylsulfonyl groups (e.g. eva, methanesulfonyl group, phenylsulfonyl LQ-chlorophenylsulfonyl group), Preferred are acylamino groups (eg, acetylamino groups, benzoylamino groups, etc.), imide groups (eg, succinimide groups, phthalimide groups, hydantoinyl groups, etc.), ureido groups (eg, phenylureido groups, methylureido groups, etc.), and cyano groups.

and The group may be substituted with permissible substituents on R1.

Moreover, R2 and X are connected to each other and are saturated or unsaturated! or a two-membered ring (excluding a benzene ring), in which case R2 preferably forms a nitrogen-containing heterocycle together with an acylamino group.

Z represents a hydrogen atom or a coupling-off group, such as a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), an alkoxy group (e.g., ethoxy group, dodecyloxy group, methoxyethylcarbamoyl group, etc.). methoxy group, carboxypropyloxy group, methylsulfonylethoxy group, etc.), aryloxy group (e.g., goochlorophenoxy group, coumethoxyphenoxy group, goocarboxyphenoxy group, etc.), acyloxy group (e.g., acetoxy group, tetradecanoylamino group, etc.) basis,
benzoyloxy group, etc.), sulfonyloxy group (e.g., methanesulfonyloxy group, toluenesulfonyloxy group, etc.), amide group (e.g., dichloroacetylamino group, heptafluorobutyrylamino group, methanesulfonylamino group, toluenesulfonylamino group) Such),
Alkoxycarbonyloxy groups (e.g. ethoxycarbonyloxy, benzyloxycarbonyloxy), aryloxycarbonyloxy groups (e.g. phenoxycarbonyloxy), aliphatic, aromatic or heterocyclic thio groups (e.g. ethylthio), group, phenylthio group, tetrazolylthio group, etc.), imide group (e.g.
succinimide group, hydantoinyl group, etc.), aromatic azo groups (eg, phenylazo group, etc.), and the like. These leaving groups may include photographically useful groups.

General formula (I) is preferably a cyan coupler represented by general formula (I[[) and general formula (IV).

O General Formula (III) Z General Formula (■) In General Formula (11[) and General Formula (f'/), X and 2 are as defined in General Formula (1).

R3, R4 and R5 each represent a substituted or unsubstituted aliphatic group having a carbon number of /~3 or a substituted or unsubstituted aromatic group having a carbon number of z~3, and R6 is a hydrogen atom, a carbon number / ~-〇 aliphatic group or carbon number 7-20
represents a substituted aliphatic group, and X and R4 or X and R6 are mutually connected to be saturated or unsaturated! or a 7-membered ring (excluding a benzene ring).

Preferred substituents for these groups include the substituents allowed for R1.

Preferred R3 is a substituted alkyl group or a substituted or unsubstituted aryl group, and particularly preferred as a substituent for the alkyl group is an optionally substituted phenoxy group or a halogen atom, and the aryl group has at least 7 groups. - A phenyl group substituted with a rogene atom, an alkyl group, a sulfonamide group, or an acylamino group is particularly preferred.

Preferred R4 is a substituted alkyl group or a substituted aryl group, and a phenoxy group which may be substituted is particularly preferred as a substituent of the alkyl group.

In the general formula (I[[), preferred X is a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, or an acylamino group.

X, l! : It is also preferable to form a t to 7-membered ring with R4, and in that case, it is particularly preferable to form a membered ring at j or .

In the general formula (In), 2 is preferably a hydrogen atom or a chlorine atom, with a chlorine atom being particularly preferred.

Preferred R5 is an optionally substituted alkyl group or a substituted aryl group, and particularly preferred is a substituted or unsubstituted alkyl group.

Preferred examples of R6 include an alkyl group having 7 to 10 carbon atoms and a substituted methyl group, with an ethyl group being particularly preferred.

In the general formula (■), preferable X is a halogen atom.

In the general formula (It/), 2 is preferably a norogen atom.

When R6 is a hydrogen atom, X is preferably an acylamino group.

The cyan coupler represented by the general formula (I) can be used alone or in plurality, and can also be used in combination with other known couplers (not limited to cyan). Also, the general formula (I
It is also possible to combine couplers of the general formula (IV) and (single or plural).

These mixing ratios can be effectively used in a wide range from t to 9 t molar ratio.

(to') . □ α (Summer-zung) (Summer-λ/) (I-koko) (■-2ri (I-kot) (1-J7) (1-u9) (■-30) (I-3, ?) (I-3g) (■-35) (■-36) (1-,?7) (I-JJ') Di (l-39) (+-4t/) (I-41 ( ><'o) ([-<', <) OH α (l-97) (I-g9) (1-ro) (I-!g) (1-tt) ([-j7) (■- YO♂) P′ (I-!RI) Next, the compound represented by the general formula [11] will be explained in detail. A is a substituted or unsubstituted alkyl group (for example, a methyl group, an ethyl group, a benzyl group, Allyl group, /chlorohequinyl group, octyl group, hydroquinemethyl group, hexanoyloxymethyl group, coethylhexynol group, dodecyl group, hexanoyl group, octadecenyl group, etc.), aryl group (e.g. eva, phenyl) M, t cr t
-furfuryl group, 3-ntadecylphenyl'J, 1
6.3-(,2-ethylhexaneamido)phenyl group,
3-naphthyl group, etc.), hetero radicals (e.g. furfuryl group, pyridyl group, etc.), acyl groups (e.g. a7tyl group, heptanoyl group, nee-ethylhexanoyl group, benzyl group, dodecanoyl group, etc.), Alkoxy groups (e.g., methquine, hexfur, λ-ethylhex'/l, dodecyloxy, hexadecyloxy/, λ-dode/ruoxyethoyacyl, λ-(,2-octyloxy-
! -LerL-octylbenzenesulfonamide) engineering 1
1'-7 group, etc.), aryloxy group (e.g., phenyloxy group, 2, II-di-tcrt-amylphenoxy group, 3-entate/rufenoyan group, cholestane-3-oxy/group, etc.) , heterocyclic oxy group (e.g. 3
-7 pyridyloxy groups, λ-furfuryloxy groups, etc.),
Alkylthio groups (e.g., ethylthio group, hexylthio group, dodecylthio group, benzylthio group, cyclohexylthio group, octylthio M%, etc.), 71J-ruthio group (e.g., phenylthio group, Hiroshi-octylthio group, 'A-LerL -butylphenylthio group,
3--? tate/ruphenylthio group, etc.), amino group (
For example, aε) group.

N-methylamino group, N, N-diethylamino group, N,
N-diethylamino group, anilino group, l-chloroanilinoMl''-anisidinyl group, Hiro-shi7/anilino group, 2-(dodecyloxy)ethylamino group, ψ-(u,
tA-di [e "[-amylphenoxy/)butylamino group, λ-pyridylamino group, λ, -pyrimidylamino group, N-dodecylamino group, etc.]" General formula (
The compound of IL) may form a dimer via A.

The substituted or unsubstituted alkyl group or aryl group of R21, It, 2, It-13o6, and R14 has the same meaning as explained for the substituted or unsubstituted alkyl group or aryl group of A above. P represents an oxygen atom or a sulfur atom, with an oxygen atom being particularly preferred. 8 is preferably a 14-substituted or unsubstituted alkokyne group.

Also, the It7:I substituent defined in
Preferably, it does not contain acid groups such as sulfonic acid.

Next, we will show an example of a typical (golden metal) body represented by 11 throwing type [1] 2 = u item Miki Length #1 巳 according to the present invention, but this is not intended to be limiting. .

(n-/) O (n--2) ○ (N-3) (III-4') ○ (III-1 (1-&) (If-, 2t) C2H5 (II-2, <) (■ -22) H3 (■-λ♂) H3 (■-λri) (II, ?O) (■-37) (■-32) (U, 33) (■-3g) (II-36) General The coupler represented by formula (1) is preferably added to the emulsion layer at a ratio of from 10-3 mol to 7 mol, more preferably from 10-3 mol per mol of silver halide present in the same layer. The ratio is 3 x 10-1 moles.

The compound of general formula (n) may be added to the coupler represented by general formula (I) in an amount of 7 to 20 mol, particularly preferably in a range of 2 to 3 mol.

The compound of general formula (II) may be added to the silver halide emulsion layer containing the compound of general formula (1), or may be added to other hydrophilic colloid layers (silver halide emulsion layer, intermediate layer, protective layer, etc.). ) can be added to

In carrying out the present invention, it is preferable that the lipophilic coupler represented by the general formula (1) and the compound represented by the general formula (If) be dissolved or impregnated in the lipophilic fine particles. In addition to the above-mentioned compounds, substances constituting the lipophilic fine particles include, if desired, an oily solvent for additives such as couplers (including those that are solid at room temperature such as wax), latex polymers, couplers, etc.
Additives such as color mixing inhibitors and ultraviolet absorbers are substances that also serve as oily solvents.

Here, lipophilic fine particles mean that substantially B is present in the gelatin aqueous solution.
It means fine particles that are not understood and exist as separate particles in an aqueous gelatin solution.

The lipophilic fine particles according to the present invention usually have the general formula (1
) ''' coupler and the compound of general formula (II) at atmospheric pressure at astigmatism/700C.
Dissolved in the above high boiling point solvent (oil) alone, or in the low boiling point solvent alone (if no oil is required as mentioned above), or in the mixed solvent of the above oil and low boiling point solvent i1#L/%
This solution is prepared by emulsifying and dispersing it in an aqueous solution of a di-aqueous colloid such as gelatin. There is no particular restriction on the particle size of the lipophilic fine particles, but O,OSμ~O0μ is preferable, 'J', '
jV? :, 0, / μm 0 , J μ is preferable.

Further, the oil/coupler ratio in fifl is preferably o, oo-i, or o in multilayer structure.

Specific examples of the oil include phthalic acid alkyl esters (dibutyl phthalate, octyl phthalate, diindecyl phthalate, dimethoxyethyl phthalate, etc.), phosphoric esters (cyphenylphthalate, etc.),
1., triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate, monophenyl-'p-t-j' tylphenyl phosphate),
citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide, dibutyl laurylamide), fatty acid esters (e.g. dibutoquinoethyl sacnonate, diethyl azelate), l-
rifufic acid esters (911, tributyl trimenoate), compounds containing Epoyan G1 (for example, the compounds described in U.S. Pat.
1 (e.g. c5'1ll(f) (-
l 21125([)C5H4s (t) Ethers m (eg phenol ethanol, diethylene glycol monophenyl ether) can be mentioned.

In addition, latex polymers include acrylic acid methacrylic acid and its esters (for example, methyl acrylate, ethyl acrylate, butyl methacrylate, etc.),
Acrylamide, methacrylamide, vinyl esters (e.g. vinyl acetate, vinyl propionate, etc.), acrylonitrile, styrene, cyhinylbenzene,
Monomers such as vinyl alkyl ethers (t3'ltH: vinyl ethyl ether), maleic esters (e.g. maleic acid methyl ester), N-vinyl-λ-pyrrolidone, N-vinylpyridine, λ-od and Hiro-vinylpyridine. Latex polymers made alone or with a polymeric compound may be used.

In addition, the low υ11 point solvent that can be used to produce the lipophilic fine particles according to the present invention includes those having a IIIi point of about 300C to /jo0C at atmospheric pressure (good solvents, such as ethyl acetate, isopropyl acetate, butyl acetate). Lower alkyl acetates such as ethyl propionate, methanol, ethanol, λR-j methyl alcohol, 7-chlorohexyl alcohol, fluorinated alcohol, methylinobutyl ketone, β-
Ethoxyethyl acetate-1, methyl cellosolve acetate, acetone, methyl acetone, acetonitrile, dioquine, dimethylporamamideroloporum, and dichlorophequine 11T are produced.

In the present invention, magenta and yellow couplers can be used in addition to the cyan couplers.

Typical examples of these include pyrazolone or pyrazoloazole compounds and open-chain or heterocyclic ketomethylene compounds. These magentas that can be used in the present invention,
And specific examples of yellow couplers are Research Disclosure (RD)/7t<3 (/q7♂year/month)■-
D and the patent cited in 7/7/979.

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized. A two-equivalent color coupler substituted with a leaving group can reduce the amount of silver coated than a four-equivalent color coupler in which the coupling active position is a hydrogen atom. Couplers in which the color-forming dye has adequate diffusivity, non-color-forming couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is US Patent No. 2. '4
No. 07,210, same No. 2. ♂7j, No. 03-7 and No. 3 and 2 of the same! ,! It is written in θ Otsu issue etc. The use of a two-pixel yellow coupler is preferred for the present invention;
U.S. Patent No. 3,4t0♂, 799, U.S. Patent No. 3. Google 7,
No. 92♂, No. 3.933.301 and No. G, 0
22.

Oxygen atom separation type yellow couplers described in No. 320, etc., or Japanese Patent Publication No. Sho J'J'-70739, U.S. Patent No. 9,4tO/, 72 Yuko, No. 32g, 0
No. 2, RD/, rθ! 3 (/1979Q), British Patent No. 1, 4t23.020, West German Application No. 2, 2
/9, 9/7 issue, 2nd, 24th/, jt1 issue, 2nd issue,
Typical examples include the nitrogen atom separation type yellow couplers described in Japanese Patent No. 329,127 and No. 2'433,712. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

The magenta coupler that can be used in the present invention is preferably an oil-protected indacylon or cyanoacetyl coupler! - Pyrazoloazole couplers such as pyrazolone and pyrazolotriazoles are mentioned. ! - As for the pyrazolone couplers, couplers in which the 3-position is substituted with an arylamino group or an acylamino group are preferred from the viewpoint of the hue and coloring density of the coloring dye, and typical examples thereof are U.S. Pat. No. 2, No. 2゜3
4t3.703, same No. 2, too, 7.11
'? No. 2.90r, j73, No. 3. θgko,
No. 53, No. 3. /! Ko, No. 96 and No. 3゜9
3g, 0/O issue, etc. Two pixels! - As a leaving group for pyrazolone couplers, U.S. Pat.
Particularly preferred are the nitrogen atom leaving groups described in /θ, ti, or the arylthio groups described in US Pat.

Also, European Patent No. 73. A pyrazolone coupler having a ballast group as described in No. 3 can provide a high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3
+ot/, <t3. Pyrazolobenzimidazoles as described in No. z, preferably US Pat. No. 3.22, 047
Pyrazolo CJ”, /-(!]C/+, z
+4t] Triazoles, Research Disclosure
J'4 in year g) and JP-A-Sho gθ-'43. <! Examples include pyrazolopyrazoles described in No. U.S. Pat.

Preferred are the imidazo[/,J,-b]pyrazoles described in U.S. Pat. ≦! The pyrazolo [/, t-b] [/, 2°] triazole described in No. 3 is particularly preferred.

The silver halide emulsion used in the present invention is usually prepared by mixing a water-soluble silver salt (for example, silver nitrate) solution and a water-soluble halide salt (for example, potassium bromide, sodium chloride, potassium iodide alone or a mixture thereof) solution with gelatin. It is produced by mixing in the presence of a water-soluble polymer solution such as

Silver halide grains may have different layers inside and on the surface, may have a multiphase structure such as a bonded structure, or may consist of a uniform phase throughout the grain. Moreover, they may be mixed.

For example, silver chlorobromide grains having different phases may have a core or single or multiple layers within the grain that are richer in silver bromide than the average halogen composition.

It may also be a grain having a core or single or multiple layers rich in silver chloride than the average halogen composition.

The average grain size of silver halide grains (in the case of spherical or nearly spherical grains, the grain diameter is taken as the grain size, and in the case of cubic grains, the ridge length is used as the grain size and the projected area is also calculated on average) is 2 μ or less It is preferable that it is 0, /μ or more, but
Particularly preferable values are /μ or less and 0.7 μ or more. The particle size distribution may be narrow or wide.

So-called monodisperse silver halide emulsions can be used in the present invention. The degree of monodispersity is determined by the coefficient of variation obtained by dividing the standard deviation derived from the grain size distribution curve of silver halide by the average grain size. It is preferably 70% or less, particularly preferably 70% or less.

In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are mixed in the same layer or in separate layers in emulsion layers having substantially the same color sensitivity. Can be applied in multiple layers. 2 more
It is also possible to use more than one type of polydisperse silver halide emulsion or a combination of a monodisperse emulsion and a polydisperse emulsion by mixing or layering them.

The shape of the silver rodanide grains used in the present invention is regular (cubic, octahedral, dodecahedral, dodecahedral, etc.).
r), or may have an irregular crystal shape such as a spherical shape, or may have a composite shape of these crystal shapes. Tabular grains may also be used, especially those having a length/thickness ratio of 5 or more. The total projected area of the tabular grain is as follows! An emulsion occupying more than θ may also be used. An emulsion consisting of a mixture of these various crystal forms may also be used. These various emulsions may be either a surface latent image type in which a latent image is formed mainly on the surface or an internal latent image type in which a latent image is formed inside the grains.

The photographic emulsion used in the present invention is the photographic emulsion by P. Gerafkides [
Chemistry and Physics of Photography J (Chimie etPhys
ique Photographique) (Paul
Montell Publishing, 7942), by G. F. Duffin [Photographic Emulsion Chemistry J]
lsionChemistry) (7 orca/lz
・Press Publishing, 1979), V. L. Zelikman et al. [Making and Coating of Photographic Emulsions J]
CoatingPhotographic Emuls
ion) 7 Ocal.

It can be adjusted using the method described in Press Publishing Co., Ltd., 1969). That is, acidic method, neutral method,
Any method such as the ammonia method may be used, and methods for reacting soluble silver salts with soluble halogen salts include one-sided mixing method,
Either a simultaneous mixing method or a combination thereof may be used. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). It is also possible to use a conversion method in which a halogen salt is added to form a less soluble silver halide. As one of the simultaneous mixing methods, it is also possible to use a method in which the pAg in the liquid phase in which silver halide is produced is kept constant, that is, the so-called Chondrald double jet method. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

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.

After grain formation, silver halide emulsions are usually subjected to physical ripening, desalting and chemical ripening before being used for coating.

Known silver halide solvents (e.g. ammonia, rhodankali or U.S. Pat. No. 3,27/137, JP-A-6
No. 1-72340, Tokukai Sho! 3-♂2gθ? No., JP-A-3-799379, JP-A-KAI! Goo 1007/7 issue or Tokukai Sho! Na-/jj? 2r etc.) can be used in precipitation, physical ripening, and chemical ripening. In order to remove soluble silver salts from the emulsion after physical ripening, Nudel water washing, 70 Quray/Yon sedimentation method, ultrafiltration method, etc. are used.

The photographic emulsion used in the present invention can be spectrally sensitized with methine dyes or the like, if necessary.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance.

The light-sensitive materials produced using the present invention can be used as color-fogging inhibitors or color-mixing inhibitors such as hydroquinone derivatives, aminephenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, and sulfones. It may also contain amidophenol derivatives and the like.

In the photosensitive material of the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer (protective layer, intermediate layer, etc.).

The ultraviolet absorber can be either solid or liquid at room temperature.

Specific examples of liquid ultraviolet absorbers include JP-A-Shoyo 7-/
'7297j, Special Publication Shoj, f-3A9t4, US Patent No. 3,79g, 9t93, sameg, j/d, /s!
λ-(2'-hydroquinophenyl) described in No. 6 etc.
Examples include benzotriazole compounds.

, 2-(x'-hydroxyphenyl)benzotriazole compounds preferably have a melting point of /j0C or less.

Other examples of ultraviolet absorbers that can be used in the photosensitive material of the present invention include U.S. Patent No. 3. ! j3.79<7
Issue, same issue, 23t, 0/j issue, Tokko Akira! /-6j'I
Benzotriazoles substituted with aryl groups as described in U.S. Patent No. O and European Patent No. 52,730; ,9
Butadines described in US Pat. No. 99, U.S. Patent No. 3.70
! , 201 and 3.7o, 7.373, U.S. Pat. No. 3,2/! .

! No. 30 and British Patent No. 1. ! 2/,,? ! Benzophenones described in No. T, U.S. Patent No. 3.7g/,
27.2 and e, 4t3/? A polymer compound having an ultraviolet absorbing residue as described in No. 2 O can be used. Ultraviolet absorbing fluorescent brighteners as described in U.S. Pat. No. 3.4t99.7≦2 and U.S. Pat. Typical examples of ultraviolet absorbers are described in F, D24t23q (/qr<=g month), etc.

Various anti-fading agents can be used in the light-sensitive material of the present invention. As a specific example of the anti-fading agent, the following general formula (V
) or (■).

X.

■Here, RR or R45 may be the same or different43"
44 and each represents an aliphatic group, an aromatic group, an aliphatic oxy group, or an aromatic oxy group, and these groups are RL -
c R, RR, R which may have permissible substituents
and R38 are the same, 34 35' 36
37 may also be different, and R33 and R34 are bonded to each other to form a 5-membered or 6 negative rings may be formed. R, R, R and R42 may be the same or different and represent a hydrogen atom and an alkyl group, respectively. X is a hydrogen atom, an aliphatic group, an acyl group, an aliphatic group or aromatic sulfonyl group,
A represents an aliphatic or aromatic sulfinyl group, an oxy radical group, and a hydroxyl group, and represents a group of nonmetallic atoms necessary to form a 5-, 6-, or 7-membered ring.

shi411911no
し48gtll'C6H13(
tl Shi113 B-13 B-14 [3-19 H3CH3 The photosensitive material of the present invention can be used as a coating aid, antistatic, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (for example, development acceleration, high contrast, sensitization, etc.). ) may contain one or more surfactants for various purposes.

In addition to the above-mentioned additives, the photosensitive material of the present invention further contains various stabilizers, anti-staining agents, developers or their precursors,
Development accelerators or precursors thereof, lubricants, mordants, matting agents, antistatic agents, plasticizers, and other various additives useful for photographic materials may be added. A typical example of these additives is Research Disclosure/264t.
3 (792! 72) and the same /♂27 Otsu (/979
(Year/July) K is listed.

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

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as required. Each of the above emulsion layers may be made up of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may be present between two or more emulsion layers having the same photosensitivity. .

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

In the photographic material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal that is commonly used in photographic materials. be done.

Among the supports used in the present invention, baryta paper and paper supports laminated with polyethylene containing a white pigment (for example, titanium oxide) in polyethylene are preferred.

The present invention can be applied to various photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color wapar, color positive film, and color reversal porpar. The present invention can also be applied to black-and-white light-sensitive materials using a mixture of three color couplers as described in Research Disclosure/7ir, i (July 1997).

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, p-phinidine diamine compounds are preferably used, and a representative example thereof is 3-methyl-guamino-N,N
-diethylaniline, 3-methyl-guamino-N-ethyl-N-β-hydroxyletheraniline, 3-methyl-9-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-g- Amino-N
-Ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like.

Color developing solutions contain preservatives such as alkali metal sulfites and hydroxylamine, as well as alkali metal carbonates,
It is common to include pH buffering agents such as borates or phosphates; development inhibitors or antifoggants such as bromides, iodides, vanzimidazoles, benzothiazoles or mercapto compounds. In addition, organic solvents (such as benzyl alcohol and diethylene glycol), polyethylene glycol, quaternary ammonium salts, and development accelerators such as amines may also be included.

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

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents include iron (III)
), compounds of polyvalent metals such as cobalt (1), chromium (■), copper (II), peracids, quinones, nitroso compounds, etc. are used. Typical bleaching agents include ferri heptaanide; dichromate; iron ([[) or cobalt ([l)]
organic complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 3-diamino-2-propatoltetraacetic acid, or organic acids such as citric acid, tartaric acid, and malic acid; Sulfate; manganate; nitrosophenol, etc. can be used. Among these, ethylenediaminetetraacetic acid iron (III) salt and persulfate are preferred from the viewpoint of rapid processing and environmental pollution. Furthermore, the ethylenediaminetetraacetic acid iron(III) complex salt is particularly useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

If necessary, various accelerators may be used in combination with the bleaching solution and bleach-fixing solution.

After bleach-fixing or fixing, washing with water is usually performed. Various known compounds may be added to the water washing process for the purpose of preventing precipitation and saving water. For example, to prevent precipitation, use water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid; A hardening agent typified by an aluminum salt, a surfactant for preventing drying load and unevenness, etc. can be added as necessary. Orori.

E. West “Water Quality Judgment Criteria J”
ality Cr1teria), "Science and Engineering of Photography" (Photo, Sci, Eng,), Vol. 3'
It is also possible to add compounds described in pages 11 to 369 (/Riotsuri et al.).Addition of chelating agents and anti-spill agents is particularly effective.

In the washing process, it is common to use countercurrent washing in tanks larger than one to conserve water. Further pressure is applied in place of the water washing process.
- A multi-stage countercurrent stabilization treatment process as described in No. #j'lJ may be implemented. Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, adjusting membrane pH (
For example, pHJ'~? ) Various buffering agents (e.g., borates, metaborates, borax, phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, etc.) Typical examples include (used in combination) and formalin. In addition, water softeners (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), disinfectants (benzisothiazolinone, isothiazolone, goutiazoline benzimita, etc.), as needed. Various additives such as surfactants, fluorescent brighteners, hardeners, etc.), surfactants, fluorescent brighteners, hardeners, etc. may be used, and two or more compounds for the same or different purposes may be used in combination.

Ammonium chloride is still used as a membrane pH adjuster after treatment.
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate.

The silver halide photosensitive material of the present invention may contain various /-phenyl-3-pyrazolidones, if necessary, for the purpose of promoting color development.

Those typical compounds are published by Tokukai Sho! Ni-6 No. 339,
same! 7-/Guq! Gu No. 2, same! 7-ko///4t No.7,
same! /-30632 issue, same ♂-j0!3 Otsu issue, same ta ♂
-60! No. 33, same number? -! 0!3g issue, same jr-! 0
j3J- issue and the same! ♂-/ Described in No. 161137, etc.

Various processing solutions in the present invention are used at 10'C-too, but it is preferable to develop at a temperature of 33°C to 30°C. In addition, West German Patent No. 2.22A, 770 or U.S. Pat. A treatment using cobalt intensification or hydrogen peroxide intensification as described in 7G, No. 999 may be performed.

A heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a float, a squeegee, etc. may be provided in each of the processing baths as necessary.

EXAMPLES Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example / Double-sided laminated with polyethylene on a paper support
A multilayer color photographic paper having the layer structure shown in the table was prepared. The coating solution was prepared as follows.

Preparation of first layer coating solution: To 70 g of yellow coupler (a) and 3 g of color image stabilizer (b), z, 10 ml of ethyl acetate and z ml of solvent (c) were added and dissolved.
0% sodium dodecylbenzene sulfonate rml
The mixture was emulsified and dispersed in 90 ml of a 70% aqueous gelatin solution. On the other hand, silver chlorobromide emulsion (silver bromide 20 mol%, Ag7θg
2.0 x 10-4 mol per mol of silver chlorobromide was added to the following blue-sensitive dye (containing /kg) to make a blue-sensitive emulsion.
I made 0g.

The emulsified dispersion and the emulsion were mixed and dissolved, and the concentration was adjusted with gelatin to give the composition shown in Table 1 to prepare a coating solution for the first layer.

In addition, the couplers 1-g and I-3B of the present invention are included in the first layer.
:/(mOl/m0l) was used as a mixture.

The coating liquids for the second to seventh layers were also prepared in the same manner as the seventh layer coating liquid. As a gelatin hardening agent for each layer /-oxy-3
，! -dichloros-) riazine sodium salt was used.

The following spectral sensitizers were used in each emulsion.

Blue-sensitive emulsion layer: (2'1C10-4 mol added per 1 mol of silver halide.) Green-sensitive emulsion layer; (CH2)2SO3Na (2.tx/θ-4 mol added per 1 mol of silver halide.) Red Sensitive emulsion layer; (per mole of silver halide x, s×/θ-4 moJL/
Floor strength 1-) The structural formulas of the compounds used in this example, such as couplers, are as follows.

(a) Yellow coupler (b) Color image stabilizer (C) Solvent (iso CgHlgO)-P=0(d) (e) Magenta coupler α (f) Color image stabilizer (h) Ultraviolet absorber /, Oni 3 mixture (molar ratio) (i) Color mixing inhibitor (j) Solvent (iso Cg) (IgO amount p=Q The following dyes were used as the irradiation preventing dyes in each emulsion layer.

Green-sensitive emulsion layer; Red-sensitive emulsion layer; Next, comparative and inventive light-sensitive materials (B) to (I) were prepared.

Photosensitive material [B) In the fifth layer of the photosensitive material [A], general formula (I) of the present invention is used.
Exemplary compound [1-/:) of I) was added to the coupler at 30 m
Photosensitive material [same photosensitive material as Al except that it further contains 1% Al.

Photosensitive material [C] In the evening layer of the photosensitive material (A), the general formula (n
) Exemplary compound [ll-0 to coupler 30mol
The same photosensitive material as photosensitive material CA) except that it further contains %.

Photosensitive material [D] Same photosensitive material as photosensitive material (A) except that the fifth layer of the photosensitive material (A) further contains 30 mo1% of the exemplary compound (na) of the general formula (1) of the present invention based on the coupler. material.

Light-sensitive material (E) In the gr layer of light-sensitive material CA), the exemplified compound [[-/, 2) of the general formula (2) of the present invention is added to the coupler at 3omal
156 The same photosensitive material as CAI except that it further contains 156.

Photosensitive material CF] In the fifth layer of the photosensitive material [A], general formula (I
f) exemplified compound Cll-24t] to the coupler.
The same photosensitive material as photosensitive material [A] except that it further contains 0mo1%.

Photosensitive material [G] In the fifth layer of the photosensitive material [A], the general formula (I
Example compound CII, 20 of f) was added to the coupler at 30 m
The same photosensitive material as photosensitive material [A] except that it further contains o1%.

Photosensitive material (H) In the th layer of photosensitive material [A], Exemplary Compound 11-3
! The same photosensitive material as photosensitive material [A] except that it further contains 30m01% of the coupler.

Photosensitive material CI) In the fifth layer of the photosensitive material (A), the following compound R-7 described in U.S. Pat. Photosensitive material (same photosensitive material as Al.

Photosensitive material [J] Photosensitive material [A] No. In the layer, JP-A-Sho r7-. The following compound R described in No. 2///417
- The same photosensitive material as photosensitive material [A] except that it contains 3 Cmol % of J based on the coupler.

Photosensitive material INK) Photosensitive material [A) No.! In the layer, as a comparative compound,
The following structure R-3 described in JP-A No. 77-2///417
A photosensitive material that is the same as photosensitive material [A] except that it further contains JOmolfr for the coupler.

The photosensitive materials (A) to (K) obtained as described above were exposed to light through an optical wedge, and then color developed according to the processing method described below. However, in order to clearly demonstrate the effects of the present invention, the processing method described below is formulated so that the developing agent and other processing solution components tend to remain at least 1 to 10%, and staining is likely to occur.

Color development 336C 3 minutes 30 seconds Fixation 33°C 7 minutes 30 seconds Washing with water 20~2r 0C/min (no stirring) Drying! 00~tro0c 2 The components of the published treatment liquid are as follows.

Color developer bleach-fix solution The above composition solution was used after being aerated for 1 hour.

Note) The above bleach-fix solution is formulated to be used in cases where the color developer adheres to the photosensitive material during running and the composition of the solution changes due to a large amount being brought into the bleach-fix solution. be.

Next, for each of the above-mentioned photographic light-sensitive materials [A] to [K] that has been processed, the cyan reflection density of the non-image area is measured using a Fuji type self-recording densitometer under red light. ♂0°C704R
When left under H for 3 days! 0 °C dry (70
~/ta%RH) After being left for r days, the cyan reflection density of the non-image area was measured again in the same manner.

Table 2 shows the increase in cyan density from the density immediately after treatment.

As is clear from Table 1, when the cyan coupler of the general formula (1) according to the present invention is used, staining due to moist heat can be significantly prevented by using the additive of the general formula (I [) of the present invention. I understand.

On the other hand, in the comparative light-sensitive materials [I] to [K], no stain suppression effect was observed.

EXAMPLE The photographic materials (A) to (K) prepared in Example 2 were exposed to light through an optical wedge, and then color developed according to the following processing method.

After exposing the above photosensitive material through an optical window, it was processed in the following steps.

Treatment process (33°C) The components of each treatment liquid are as follows.

Color developer benzyl alcohol 12ml diethylene glycol 1ml potassium carbonate
-! g Sodium chloride
9θ,/g sodium bromide
0. ! g Anhydrous sodium sulfite
2g Hydroxylamine sulfate 2g Fluorescent brightener /g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-guamine aniline sulfate gg Add water to make /l and add NaOH to pH 10°2 do.

Bleach-fixing solution Ammonium thiosulfate / 241, jg Sodium metabisulfite / 3.3g Anhydrous sodium sulfite 2.7g EDT) lX2 Iron ammonium salt to Og color developer (above)
100ml pH 4.7-4. Add water to make /l treatment solution.
A conventional roller transport type developing processing machine was used in which development processing was carried out while performing normal replenishment, and the composition of the processing solution was almost at equilibrium.

Next, for each of the above-mentioned photosensitive materials that had been developed, the non-image area was measured for red light after the processing/hours had passed, and then the results were shown in the results when they were left at 20°C-70°RH for 3 days and at 20°C. C-dry (/θ~/!%RH) was left for a day, and the non-image areas were again measured for cyan reflection density.

Table 3 shows the increase in stain from post treatment/time.

Table 3 As is clear from Table 3, when the cyan coupler of the general formula (I) according to the present invention is used, staining due to heat and moist heat is significantly prevented by using the additive of the general formula (II) of the present invention. I know what I can do. On the other hand, in the comparative light-sensitive materials [I] to [K], no stain suppression effect was observed.

Example 3 Photographic materials (A) to (K) were prepared according to Example 1, exposed through an optical wedge, and then processed according to the following steps.

In this processing, the photographic materials (A) to (K) of Examples were processed using a rapid processing step and a processing solution assuming a running equilibrium state of rapid processing.

Processing process C Temperature Time Color development 37°C/min θ θ fixing White fixing 33°C/min θθ sec Washing / 3θ0C 2θ sec washing 30°C 20 sec washing 33θ' Crθ seconds drying ?θ 0C/min 00 sec Includes 70 seconds of travel time.

Washing with yellow water is a countercurrent washing from 3 to ko to /.

water ? θθ
ml diethylenetriaminepentaacetic acid 3.0g benzyl alcohol / ! ml diethylene glycol 10ml sodium sulfite 2.0g potassium bromide
0. ! g potassium carbonate
30,0gN-ethyl-N-(β-methanesulfamidoethyl)-3-methyl-teraminoaniline sulfate! ,! g Hydroxylamine sulfate 4t, 0g fluorescent brightener (stilbene type) /, add 0g water
10100O bleach-fix ammonium thiosulfate (20%) 200ml Sodium sulfite / Fg ethylenediaminetetraacetic acid iron acetate II) Ammonium tag ethylenediaminetetraacetic acid / 2Na 6g pH 7, 0θ Next, for each of the above-mentioned photosensitive materials that have been developed, The non-image area was measured with red light after a period of time, and then it was left under rO'c-70%RH for 3 days and the case where it was left in ro0c dry (10~/!%RH) for J-days. The non-image area was measured again using red light.

Table 9 shows the increase in stain from 7 hours after treatment.

Table 9 As is clear from Table 9, when the /uncoupler of the general formula (1) according to the present invention is used, the general formula (It) of the present invention
It can be seen that staining caused by moist heat can be significantly prevented by using this additive.

On the other hand, no stain suppression effect was observed in the comparative light-sensitive materials [■] to [K].

Example group A comparative photographic material was prepared as shown below.

A color photographic material was prepared by applying the following layers from the first layer to the first layer on a paper support laminated on both sides with polyethylene. The first layer coating side of the polyethylene contains titanium white as a white pigment and a trace amount of ultramarine as a bluish dye.

(Photosensitive layer composition) The components and coating amount in units of g/m2 are shown below. Regarding silver rodanide, the coating amount is shown in terms of silver.

1st fi (antihalation layer) Black colloidal silver ...0.07 gelatin ...0.2nd λ layer (low sensitivity red sensitive layer) Spectral sensitization with red sensitizing dyes (Kaoru! and 4T) Silver iodobromide emulsion (silver iodide 3.! molar ratio, average grain size 0.7μ)
...Silver θ, /! gelatin
...7.0 cyan coupler (+3)
...0.30 anti-fading agent (Kaoru 2) ...
...0.7! Coupler solvent (Kaoru/! and arrow/)...0.
θg 3rd layer (high sensitivity red-sensitive layer) Silver iodobromide emulsion spectrally sensitized with red sensitizing dye (Kaoruyoto-Akuna) (silver iodide er, o molar average grain size 0.7μ
)...Silver 0. IO gelatin
...0. ! .

Cyan coupler (-+3)... θ, 10 Anti-fading agent (Kaoru 2)...0.0! Coupler solvent (AX/O and -X-/)...0. θ-Qth layer (intermediate layer) Yellow colloidal silver 0.02 gelatin 7.0 θ Color mixing inhibitor (Kaoru/
4t) ... o, o, r Color mixing inhibitor solvent (-
+73) ...0.7t polymer latex (-
+, < )...o, 4t.

No.! Layer (Low sensitivity green sensitive layer) Silver iodobromide emulsion spectrally sensitized with green sensitizing dye (-X-/2) (silver iodide, !Molar average grain size 0.4tμ
)...Silver 0.20 gelatin
...0.70 magenta coupler (+//
) ... o, y.

Anti-fade agent A (-1+70) ...0.0 / Anti-fade agent B (yellow 9) ...0.0 / Anti-fade agent C (+ri) ...0.02 Coupler solvent (
+//) ...0. 0th G layer (high sensitivity green sensitive layer) Silver iodobromide emulsion spectrally sensitized with green sensitizing dye (+/2) (silver iodide 3.t molar ratio, average grain size 0.9μ)
...Silver 0.20 gelatin
...0.20 magenta coupler (-p/-//)
・・・0． ￥θ Anti-fading agent A (Kaoru 10)...
・0,0! Anti-fading agent B (bitter 9) ・=-o, or
Anti-fading agent C (bitter male)...0.02 Coupler solvent (-1+/J')...0. 0 7th layer (yellow filter single layer) Yellow o-Coloy) "Silver---o, , z.

Gelatin.../, θ0 color mixing inhibitor (yellow/g)...0.0g Color mixing inhibitor solvent (-+/j)...0.2', J' layer (low sensitivity Blue-sensitive layer) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye (-+7g) (silver iodide,!morch, average grain size 0.!μ)
...Silver 0. /j gelatin
...0. ! 0 Yellow coupler (Kaoru/Yo)...
・0,20 coupler solvent (+7r) ・・・O1
θ! 9th layer (high-sensitivity back layer) Silver iodobromide emulsion spectrally sensitized with a blue sensitizing dye (bitter/black) (iodide, ! morch, average grain size/, gμ)
...Silver 0. θ 1st O layer (ultraviolet absorption layer) Gelatin ・・・／,! O UV absorber (-%/9) ... /, 0 UV absorber solvent (%/J') ... 0.30 Color mixing prevention agent (+
/7) ... θ, 02 1st/layer (retention layer) Gelatin ... /, Q The compounds used here are as follows: bitter / dioctyl phthalate yellow 2 coffee (coffee droxy 3-see-boo-y-
(t-t-)f-ruphenyl)benzotriazole63-1[α-(2, goosey monoamylphenoxy)butanamide)-<1, 1-dichloro-! -Ethylphenol yellow! ,5'-dichloro-3,3'-di(3-sulfobutyl)-9-ethylthiacarbonylcyanine Na salt)ethylammonium-3-[,2-(co[3-(3-sulfopropyl)naphtho) (i, z-d)
Thiazolin-2-ylidenemethyl]-/-butenyl)-
3-naphtho (z, 5-d) thiazolino] prono sulfonate bitter polyethyl acrylate arrow 7 phosphate trioctyl ester + f♂ i, goosey - hexylhydroquinone -1 + 9 2- (no hydroxy-3-t- Butyl-
t-methylphenyl) methane bitter 10 3,3.3',3'-tetramethyl-! .

and t'1g'-tetrapropoxy-/.

/'-Bisspiroindan arrow/2! ,! '-diphenyl-9-ethyl-3゜3
'-Disulfopropyloxacarbocyanine Na salt Kaoru/3 Phosphoric acid-〇-cresyl ester%/g 2.
'l-G t-octylhydroquinone Kaoru/! α-pivaloyl-α-C(,2,terdioxo-/-benzyl-!-ethoxyhydantoin-3-yl)-2-chloro-! -(α-!, Gudioxo-t-amylphenoxy)butanamine]acetanilide-1+, #)IJIJ-ruammonium 3-C,2
-(3-Benzylrhodanin-r-iUf7)-3-benzoxazolinyl]propanesulfonate aromatic acid/7 2. (1-G5ee-Octylhydroquinone bitter/Ryo Phosphate trinonyl ester Kaoru/9 Ochroluco (Cohydroquinone 3-L-
Butyl-1-1-octyl)phenylbenztriazole Next, light-sensitive materials (B) to (J) for comparison and of the present invention were prepared as follows.

Photosensitive material (B) In the second and third layers of the photosensitive material (A), the general formula of the present invention [
■] The photosensitive material (A
) is the same photosensitive material.

Photosensitive material (C) In the third layer of the photosensitive material (A), an exemplary compound of the general formula [■] of the present invention ■-! The photosensitive material is the same as the photosensitive material (A) except that it contains 3 layers mo1% of the coupler and the same amount as the reprocessed coupler in the lipophilic fine particles.

Photosensitive material (D) In the λ-th, third layer of the photosensitive material (A), exemplified compound ■-♂ of the general formula [■] of the present invention is added to the coupler in an amount of 30 mo
The same photosensitive material as photosensitive material (A) except that 1% of the coupler was further contained in the lipophilic fine particles.

Photosensitive material (E) In the second and third layers of the photosensitive material (A), 30 mo of the exemplified compound ■-72 of the general formula [■] of the present invention is added to the coupler.
The same photosensitive material as photosensitive material (A) except that it further contains 1% of the coupler in the lipophilic fine particles.

Photosensitive material (F) In the third layer of the photosensitive material (A), exemplified compound 1l-24t of the general formula [■] of the present invention is added to the coupler in an amount of mo1% in the third layer, and the same amount as the coupler is contained in the lipophilic fine particles. The same photosensitive material as photosensitive material (A) except that it further contains.

Light-sensitive material (G) In the 2nd and 3rd layer of the light-sensitive material (A), exemplified compound ■-23 of the general formula [II] of the present invention is added to the coupler, and the 3-layer mo1% coupler is added to the same lipophilic fine particles. The same photosensitive material as photosensitive material (A) except that it further contains.

Photosensitive material f) 1) In the 2nd and 3rd layers of the photosensitive material (A), exemplified compound ■-
For the 3-t coupler, the photosensitive material (A) had the same mol % of the 3 layer as the coupler, except that it was contained in the lipophilic fine particles.
The same photographic material.

Photosensitive material (I) In the 2.3 layer of the photosensitive material (A), the following compound R-/ described in U.S. Pat. Same as - The same photosensitive material as photosensitive material (A) except that it is contained in the lipophilic fine particles.

Photosensitive material (J) In the third layer of the photosensitive material (A), 30 mol of the following compound R-1 described in JP-A-67-2///4t7 was added to the coupler as a comparative compound, and the coupler was further added to the coupler. Same as - The same photosensitive material as photosensitive material (A) except that it is contained in the lipophilic fine particles.

(R-, z) Photosensitive material (K) In the 2nd and 3rd layers of the photosensitive material (A), the following structure R-J described in JP-A-7-2///\7 was used as a comparative compound.
The same photosensitive material as photosensitive material (A) except that it further contains 30 mo1% of the coupler.

(R-3) The photosensitive materials (A) to (K) obtained as described above were exposed to light through an optical wedge, and then color developed according to the processing method described below.

[Processing process]

First development (black and white development) 3cr 'C/'/C' water
Washing 3/ 'CI' jθ〃Reverse exposure 10θLux or more / “Color development
3♂0C, 2'/! 〃Water washing
3tr 0c 4tr” bleach fixing
310C-2'oθ〃Water wash
3/ 'CJ' /l〃[Processing solution composition] First developer nitrilo-N,N,N-)rimethylenephosphonic acid, pentasodium salt O9, g diethylenetriaminepentaacetic acid, pentasodium salt 9.0g Potassium sulfite 3θ , 0g potassium thiocyanate 7.2g potassium carbonate
3! , Og hydroquinone monosulfonate potassium salt 2J-, 0g diethylene glycol / j, Oml/-phenyl-terhydroxymethyl-goomethyl-3 -pyrazolidone 2.0g potassium bromide 0.6g potassium iodide
! , add Omg water
/ 1 (pH 9,70) Color developer Benzyl alcohol /O, Oml diethylene glycol /2.0m13, t-dithia-/, f-octanediol 0.2g Nitrilo-
N,N,N-trimethylenephosphonic acid pentasodium salt 0. ! gDiethylenetriaminepentaacetic acid pentasodium salt 2.0g Sodium sulfite 2 layers θg Potassium carbonate
Ko! , 0g hydroxylamine sulfate
3.0gN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-teraminoaniline sulfate!・0g potassium bromide 0.5g potassium iodide
/ , add Omg water
/ 1 (pH 70, 4t0) Bleach-fix solution Komel Kabuto 7, 3. Gutriazole /, θg ethylenediaminetetraacetic acid disodium trihydrate! , θg ethylenediaminetetraacetic acid/Fe (III) ammonium hydrate, ro, og sodium sulfite /r, Og sodium thiosulfate (700g/di)/o, om
l glacial acetic acid r, o ml
Add water / 1 (pH 6
，! Q) Next, for each of the above-mentioned photosensitive materials that have been developed, measure the non-image area using red light from the time after processing, and then? When left under θ0-70SRH for 3 days and ♂
00 Dry (/θ~/!CHRH) was left to stand for a day, and the non-image areas were again measured using green light.

Table 1 shows the increase in stain from 7 hours after treatment.

table! As is clear from Table 1, when the cyan coupler of the general formula N) according to the present invention is used, staining due to moist heat can be significantly prevented by using the additive of the general formula (II) of the present invention.

On the other hand, no stain suppression effect was observed in the comparative light-sensitive materials [■] to [K].

Note that similar effects were obtained when the compound of general formula (II) of the present invention was used alone in the 2nd and 3rd layers.

Claims (1)

[Scope of Claims] It is characterized by having a layer containing at least one cyan image-forming coupler represented by the following general formula (I) and at least one compound represented by the following general formula (II). Silver halide color photographic material. General formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼General formula [I] [In the formula, R_ is a substituted or unsubstituted aliphatic group, aromatic group, heterocyclic group, aromatic amino group, or hetero represents a cyclic amino group, R_2 represents a hydrogen atom, a substituted or unsubstituted aliphatic group having 1 or more carbon atoms, or an acylamino group, X represents a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic group, It represents an aromatic group or an acylamino group, and Z represents a hydrogen atom or a group that can be separated upon oxidative coupling with a developing agent. Here, R_2 and X may be connected to each other to form a 5- to 7-membered ring (excluding a benzene ring), and R_1
One group among R_2, X, and Z may form a dimer or more multimeric coupler. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. Represents an alkylthio group, an arylthio group, or an amino group, R_2_1 and R_2_
2 each independently represents a hydrogen atom, an unsubstituted or substituted alkyl group, R_2_3 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group, and R
_2_4 represents a substituted or unsubstituted aryl group,
P represents an oxygen atom or a sulfur atom. ]