JPS586939B2 - color - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a multilayer color photographic material with excellent color reproducibility and sharpness.

A silver halide color photographic material based on the subtractive color principle consists of an emulsion layer that develops a yellow color when exposed to blue light, an emulsion layer that develops a magenta color when exposed to green light, and an emulsion layer that develops a cyan color when exposed to red light. It consists of

As a coloring agent for such photographic materials, compounds that form dyes such as indophenol, indoaniline, indamine, azomethine, phenoxazine, and phenazine through a fogging reaction with an oxidized aromatic primary amino developing agent, so-called couplers, are used. is well known.

Couplers used in color photographic materials such as those mentioned above include:
Usually, acylacetamide or dibenzoylmethane derivatives are used as the yellow coupler, 5-pyrazolone, cyanoacetyl, indazolone or pyrazolobenzimidazole derivatives are used as the magenta coupler, and phenol or α-naphthol derivatives are used as the cyan coupler.

In a color photographic material based on the subtractive color principle, it is ideal that a yellow colored image selectively absorbs only blue light, a magenta colored image selectively absorbs only green light, and a cyan colored image selectively absorbs only red light.

However, in silver halide color photography using the above-mentioned couplers, the color images obtained are not necessarily ideal, and the color images often have secondary absorption and even absorb light in wavelength regions of unnecessary colors.

In order to correct the unnecessary absorption portion of this colored image, it is possible to use a masking method using a so-called colored coupler, for example.
It is well known as described in SA Journal, Volume 13, Page 94 (1947).

The color image obtained from phenol or naphthol derivatives used as cyan color-forming couplers has a wavelength of approximately 600 nm.
In addition to having main absorption in the red light region of 800 nm from
It also has sub-absorption in the green light region around 50 nm and the blue light region around 440 nm.

It is also well known that in order to correct this side absorption, a colored coupler in which an azo group is substituted at the para position to the hydroxyl group of phenol or α-naphthol is used.

However, p-azo-substituted phenol or α-naphthol type colored couplers have many unsatisfactory hues, especially
A material having a hue sufficient to correct sub-absorption in the green light region has not yet been obtained.

Further, the color image obtained from the 5-pyrazolone derivative used as the Mazenk coloring coupler has main absorption in the green light region with a wavelength of about 450 nm to 550 nm, and also has secondary absorption in the red light region and the blue light region.

It is also known that in order to correct this side absorption, a colored coupler in which the 4-position of 5-pyrazolone is substituted with an azo group is used.

However, the 4-azo-substituted 5-pyrazolone type colored couplers are often unsatisfactory in their hue, and in particular, one having a hue sufficient to correct sub-absorption in the red light region has not yet been obtained.

Further, the conventionally known colored couplers substituted with azo groups as described above have a slow reaction rate with an oxidized aromatic primary amine developer, and therefore do not have a sufficient masking effect.

Furthermore, the conventionally known colored couplers substituted with an azo group as described above have the defect that the hue changes depending on the pH of the processing solution, making it difficult to obtain a stable hue.

U.S. Pat. No. 3,476,563 describes a naphthol coupler having the following structure as a coupler for masking the blue light absorption region of a cyan image.

This type of coupler has a great masking effect and little change in hue due to pH, and is considered to be an improvement over the above-mentioned drawbacks of the diazo-type colored coupler. However, it has the disadvantage of causing fog in the photographic layer and worsening graininess. be.

A first object of the present invention is to provide a color light-sensitive material containing a diffusion-resistant colored coupling compound free from the above-mentioned defects.

Another object of the present invention is to provide a multilayer color photosensitive material in which one color-sensitive photosensitive layer is not exposed to light from a photosensitive area of another color-sensitive photosensitive layer, in other words, the color separation is good. There is a particular thing.

Another object of the present invention is to provide a color photosensitive material with excellent sharpness.

Another object of the present invention is to provide a color photosensitive material with excellent graininess.

Other objects of the invention will be understood from the description herein.

A feature of the present invention is that the diffusion-resistant colored coupling compound used in the light-sensitive material of the present invention has absorption in an unnecessary absorption region in the visible range of the color image-forming dye, and the coupling compound does not diffuse. The additive is fixed in the photographic layer and, during color development, couples with the oxidized product of the aromatic primary amine developer to release the diffusible dye in an imagewise manner, and the released diffusible dye flows out of the photographic layer or becomes colorless. It is to act in such a way that it becomes

The color light-sensitive material of the present invention has extremely improved color separation and at the same time can achieve the various objects mentioned above.

The objects of the present invention are achieved in a color photographic light-sensitive material containing a diffusion-resistant colored cyan coupler of the following general formula (I), specifically a blue-sensitive silver halide emulsion layer containing a yellow coupler, a green light-sensitive silver halide emulsion layer containing a Mazenk coupler, and a blue-sensitive silver halide emulsion layer containing a yellow coupler. In a multilayer color photographic material having at least on a support a sensitive silver halide emulsion layer and a red sensitive silver halide emulsion layer containing a cyan coupler, in the red sensitive silver halide emulsion layer or the gelatin intermediate layer adjacent thereto. This was achieved by a multilayer color photographic material characterized by containing a diffusion-resistant colored cyan coupler of the following general formula (I).

General formula (I) A-O-(L)n+1-X A represents the residue of a naphthol cyan coupler bonded to the -0-(L)n+1-X group at the coupling position.

L is -CH2CH2-O-, -CH2--CH2CHO
HCH20-, -(CH2)a-O- or -(CH2
) represents 4-O-.

n represents 0 or 1.

-O-(L)n+1-X is represented by the general formula (1
) is a residue that is released as a diffusible dye and flows out of the photographic layer when the coupler undergoes oxidative coupling with an aromatic primary amine developer to form a cyan dye.

The colored cyan coupler represented by the general formula (1) desirably contains at least one diffusion-resistant group having 8 to 32 carbon atoms in the molecule.

X is -[Ar1]-N=N-[Ph1], [-Art]
-N=N-[Ar2], -[Ar1]-N=N-[He
t], etc. (in the formula, -[Ar1]-
represents an arylene group (eg, phenylene group, naphthylene group, etc.).

Here, -[Ph1] is a phenyl group having a water-soluble group or a hydrophilic group (as a water-soluble group, for example, -SO3M,
-COOM, hydrophilic groups such as amide group, etc.)
shows.

[Ar2] is a hydroxynaphthyl group having a water-soluble group or a hydrophilic group (as a water-soluble group, for example, -SO3
Examples of hydrophilic groups such as M, -COOM include amide groups, etc.).

-[Het] represents an aromatic heterocyclic group, preferably an aromatic heterocyclic group having a water-soluble group such as -SO3M or -CO2M.

For example, (here, Z represents a group of nonmetallic atoms constituting a condensed allure ring.

),etc. In addition, M represents a cation such as an alkali metal ion or ammonium ion, and a hydrogen atom, and R1 is
It represents an alkyl group having 1 to 7 carbon atoms, a hydrogen atom, a phenyl group, a naphthyl group, etc., and R2 represents an amino acid, an alkyl group having 1 to 5 carbon atoms, an acylamino group, a sulfoamide group, a ureido group, an alkoxycarbonyl group, and the like. Indicates a substituted product, a carboxyl group, etc.

The colored cyan coupler represented by general E(I) fogs with the oxidized aromatic primary amine developer, and the separated -〇-(L)n+1-X group flows out from the photographic light-sensitive material into the processing solution. Therefore, it is desirable that X contains an acid group, that is, a water-soluble group (for example, a sulfone group, a carboxyl group, etc.) or a hydrophilic group (for example, a sulfoamide group) that promotes diffusivity.

The colored coupler of general formula (1) used in the photosensitive material of the present invention has the following features.

First, in p-azo-substituted phenol or naphthol, which is a commonly used colored coupler,
Due to the structural limitation that the chromophore is an azo group directly connected to the coupling position of phenol or naphthol, there is little freedom in selecting the hue, and it is difficult to obtain a color that has sufficient green light absorption. In the colored coupler of formula (1), the chromophore residue is located away from the coupling position, and the hue can be freely selected by devising the bond type.

Secondly, the colored coupler of general formula (I) has sufficient coupling activity and sufficient masking efficiency can be obtained.

Thirdly, the colored coupler of general formula (I) exhibits very little hue change due to pH change, and has few processing limitations.

In addition, colored couplers of the general formula (I), like naphthol type couplers having an aryloxy group at the p-position, may produce capri in the photographic layer or deteriorate graininess. There is nothing to do.

A particularly preferred diffusion-resistant colored cyan coupler of the present invention that satisfies the above characteristics can be represented by the following general formula.

Next, specific examples of the colored cyan coupler represented by the general formula (I) will be shown, but the invention is not limited thereto.

(1) 1-hydroxy-4-{β-(4=(1-hydroxy-3,6-disulfo-8-acetyla, minnow 2-
naphthylazo)phenoxy]ethoxy}-2-N-[γ
-(2,4-di-t-amylphenoxy)probyl]naphthamide, disodium salt (2) 1-hydroxy-4-{β-(4-(1-hydroxy-3,6-disulfo-8-acetylamino-2 -naphthynoreaso)phenoxy]ethoxy]-2-N-
(2'-chloro-5'-hexadecyloxycarbonyl)naphthanilide, disodium salt (3) 1-hydroxy-4-{β-(4-(1-hydroxy-3,6-disulfo-8-acetylamino- 2-naphthylazo)phenoxy]ethoxy}-2-N-(2'
-tetradecyloxy)-naphthanilide, disodium salt (4) 1-hydroxy-4-[4-(1-hydroxy-3,6-disulfo-8-acetylamino-2-naphthylazo)benzyloxy]-2-N −[γ−(2,4−
di-t-amylphenoxy)probyl]naphthamide,
Disodium salt (5) 1-hydroxy-4-{2-hydroxy-3-[4-(1-hydroxy-3,6-disulfo-8-acetylamino-2-naphthylazo)phenoxy]propyloxy}-2- N-hexadecylnaphthamide, disodium salt (6) 1-hydroxy-4-{γ-(4-(1-hydroxy-3,6-disulfo-8-acetylamino-2-naphthylazo)phenoxy)propyruoxy }-2-[
2-chloro-5-(2,4-di-tert-amylphenoxy)acetylamine] naphthanilide, disodium salt (7) 1-hydroxy-4-{δ-(4-(1-hydroxy-3,6-disulfonyl) -8-acetylamino-2-naphthylazo)phenoxy]butyl:oxy}-2-(N
-(γ-decyloxy)propyl]naphthamide, disodium salt (8) 1-hydroxy-4-{β-(4-(1-hydroxy-3,6-disulfo-8-acetylamino-2-naphthylazo)phenoxy) diethyloxy}-2-(4
-tetradecyloxy)naphthanilide, disodium salt (9) 1-hydroxy-4-{β-(4-(1-hydroxy-3,6-disulfo-8-acetylamino-2-naphthylazo)-1-naphthoxy) lagoon ethoxy}-N-(
γ-(2,4-di-tert-amylphenoxy)propyl]-2-naphthamide disodium salt (10) 1-hydroxy-4-{γ-[4-(1-hydroxy-5-sulfo-8-acetylamino) 2-naphthylazo)phenoxy]propylene-N-n-hexadecyl-2-naphthamide sodium salt (11) 1-hydroxy-4-{β-[4-(1-hydroxy-5-sulfo-8-methanesulfone) Amide-2-
naphthylazo)phenoxy]ethoxy}-N-(γ-(
2,4-di-tert-amylphenoxy)probyl]
-2-naphthamide sodium salt (12) 1-hydroxy-4-{β-(4-(1-hydroxy-3,6-disulfo-8-propionylamino-
2-naphthylazo)phenoxy]-N-n-
Dodecyl-2-naphthamide disodium salt (13) 1-hydroxy-4-{β-[4-(2-hydroxy-3,6-disulfo-1-naphthylazo)phenoxy]ethoxy}-N-(γ-(2 ,4-di-tert
-amylphenoxy)probyl]-2-naphthamide
Disodium Salt Next, a general synthesis method for the coupler used in the present invention will be shown with specific examples.

Synthesis Example 1 1-Hydroxy-4-{β-[4-(1-hydroxy-3,6-disulfo-8-acetylamino-2-naphthylazo)phenoxy]ethoxy}-2-N-(γ-2,4
-di-tert-amylphenoxy)propyl] naphthamide, disodium salt (coupler (1)) synthesis intermediate 1, 1-hydroxy-4-ethoxy-2-naphthoic acid: 1,4-dihydroxy-2-naphthoic acid The ethanol solution was heated to reflux and hydrogen chloride gas was passed through it for 5 hours to obtain 1-hydroxy-ethoxy-2-naphthoic acid (melting point: 190-5°C).

Intermediate 2 N-(γ-(2.4-di-tert-amylphenoxy)propyl}-2-naphthamide: A mixture of 23.2 g of Intermediate 1, 18 g of thionyl chloride, and 100 ml of benzene was stirred at 40 to 45°C for 3 hours. After that, γ-(2,4-
Di-tert-amylphenoxy: probylamine 60
g, DABCO(1,4-diazabicyclo(2,2,2
] A solution consisting of 23 g of octane and 100 ml of benzene was added and stirred for 2 hours to obtain the desired product.

Recrystallization solvent: methanol, melting point 130-1°C Intermediate 3, 1-hydroxy-4-[β-(4nitrophenoxy)ethoxy)-N-(γ-(2,4-di-ter
t-amylphenoxy)propyl]-2-naphthamide: A mixture of 5g of intermediate 2, 12g of β-(4-nitrophenoxy)ethanol, and 0.3g of methanesulfonic acid was heated to 140-150°C under reduced pressure for 3 hours. Obtained the object.

Recrystallization solvent: acetonitrile, melting point 166-8°C.

Intermediate 4, 1-hydroxy-4-[β-(4-aminophenoxy)ethoxy)-N-{γ-(2,4-di-t
ert-amylphenoxy)propyl}-2-naphthamide: 6.4 g of Intermediate 3 was dispersed in 64 ml of ethanol and hydrogenated using a palladium-carbon catalyst in an autoclave to obtain the desired product.

Recrystallization solvent: ethanol, melting point: 147-9°C.

Coupler (1): 6.1 g of intermediate 4 to methanol,
A diazonium salt was prepared with sodium nitrite according to a conventional method in a mixed solution of hydrochloric acid, and 3.6 g of 1-hydroxy-3,6-
Disulfo-8-acetylaminonaphthalene was coupled with a mixed aqueous solution of disodium salt in methanol and caustic soda, acidified with hydrochloric acid, and the resulting precipitate was collected, washed with water, dried, and washed with 300 mg of acetonitrile to obtain the desired product. Ta.

Melting point 300℃ or higher.

Coupler (2), (3), (4), (6), (7), (
8) was synthesized in the same manner as coupler (1).

Synthesis example 2 1-hydroxy-4-{2-hydroxy-3-[4-(
1-Hydroxy-3,6-disulfo-8-acetylamino-2-naphthylazo)phenoxy]propyloxy}
Synthesis of -2-(N-hexadecyl)naphthamide, disodium salt (coupler 5) 4.3 g of 1,4-dihydroxy-2-(N-hexadecyl)naphthamide, 2.2 g of p-nitrophenyl glycidyl ether and 1-Hydroxy-4-[2-hydroxy-3-(4-nitrophenoxy)propyloxy] was prepared by heating 0.85 g of penzyltrimethylammonium hydroxide (40% methanol solution) in 50 mg of methyl isobutyl ketone to reflux for 5 hours. )
-2-(N-hexadecyl)naphthamide was synthesized in the same manner as the synthesis of coupler 1.

In addition to the light-sensitive emulsion layer, the multilayer color photographic material of the present invention includes various auxiliary layers, such as an antihalation layer,
An optical filter layer, an anti-mixing layer, an anti-color irradiation layer, a protective layer, etc. can be provided.

In the multilayer color light-sensitive material of the invention, the colored coupling compound of the invention may be used in the emulsion layer or in the auxiliary layer.

In particular, when a colored coupler of general formula (I) is used in an emulsion layer, it is usually used in combination with a colorless cyan color-forming coupler in a red-sensitive emulsion layer. A combination in which the fogging rate is higher is particularly advantageous because the mask concentration can be lowered to exhibit an effective masking effect.

In particular, colored couplers of general formula (I) can be used in emulsion-free auxiliary layers adjacent to the red-sensitive emulsion layer.

In this case, a part of the oxidized developer generated in response to the development of the red-sensitive emulsion layer diffuses into the auxiliary layer and overlaps with the coupler of general formula (I), thereby exhibiting a masking effect. It is also possible to prevent color mixing due to diffusion of the oxidized developer to other photosensitive layers.

This effect is particularly remarkable because the colored coupler of general formula (I) has a high fogging rate.

In this case, a hydroquinone derivative can also be used in combination to further enhance the effect of preventing color mixture.

The layers constituting the multilayer color photosensitive material of the present invention can be arranged in various ways depending on the purpose.

For example, the red-sensitive layer, green-sensitive layer, and blue-sensitive layer may be arranged in this order from the support side, or the order may be interchanged.

Furthermore, one or more of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer can each be divided into two or more layers, and in this case, two or more layers in the same photosensitive area are adjacent to each other. It's good too,
It may be separated by emulsion layers of other light sensitive areas or other auxiliary layers.

When the red-sensitive layer of the multilayer color light-sensitive material of the present invention is arranged in the order of red-sensitive layer and green-sensitive layer from the support side, especially the formula (I)
If a colored coupler that absorbs in the green light region is used in the auxiliary layer between the red-sensitive layer and the green-sensitive layer, in addition to the above-mentioned masking effect and color mixing prevention effect, it will also improve the diffusion of oxidized developer. Improvement in sharpness is seen due to the so-called "bokeh mask" based on the spread of time, and when the light-sensitive material is exposed, green light that was not absorbed by the green-sensitive layer is absorbed by the auxiliary layer, and the green color is increased due to re-reflection. It is possible to prevent image blurring, and also to prevent color mixture due to unnecessary light-sensitive areas of the green part of the red-sensitive emulsion layer.

At this time, if a color mixture prevention layer (for example, a layer containing a hydroquinone derivative) is provided between the auxiliary layer and the green-sensitive layer, the cyan coloring of the colored coupler layer is caused by the diffusion of the oxidized developing agent generated by the development of the green-sensitive layer. This is particularly advantageous because it can prevent this.

When the photosensitive layers of the multilayer color photosensitive material of the present invention are arranged in the order of a red-sensitive layer and a blue-sensitive layer from the support side, the general formula (■
) among the colored couplers having absorption in the blue light region was included in the auxiliary layer between the red-sensitive layer and the blue-sensitive layer, the same effect as above was obtained.

The amount of the colored coupling compound of the present invention used in the multilayer color photographic material of the present invention varies depending on the purpose of use and the specific structure of the coupling compound, but may be 10-6
~10-3 mol/m2 is preferable, especially 10-5
A value between ˜5×10 −4 mol/m 2 is convenient.

There are various methods for adding the colored coupling compound of general formula (1) of the present invention to the coating layer constituting the photosensitive material, and typical examples thereof are as follows.

(a) Dissolved in an alkaline aqueous solution (aqueous solution of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, ammonia, trimethylamine, etc.) and added to the coating solution. If necessary, add an acid (acetic acid, citric acid, tartaric acid, hydrochloric acid, sulfuric acid, etc.) to adjust the pH.

(b) Water-miscible organic solvents (methanol, ethanol,
acetone, dimethylformamide, dimethyl sulfoxide, etc.), a mixed solvent thereof, or a mixed solvent of these and water, and added to the coating solution.

At this time, the alkali mentioned in (a) may be used in combination.

(c) An organic solvent that is difficult to dissolve in water (ethyl acetate, cyclohexanone, β-butylethoxyethyl acetate, dibutyl phthalate, tricresyl phosphate, etc.) and a mixed solvent thereof and emulsified and dispersed in an aqueous medium to form a coating solution. Add inside.

Dispersion aids include commonly used anionic surfactants (e.g. sodium alkylbenzene sulfonate, sodium dioctyl sulfosuccinate, sodium dodecyl sulfate, sodium alkylnaphthalene sulfonate,
Fischer type couplers, etc.), amphoteric surfactants (eg, N-tetradodecyl-N,N-dipolyethylene-α-petaine, etc.), and nonionic surfactants (eg, sorbitan hinolaurate, etc.) are used.

The coupler of the present invention may be added alone to the emulsion layer, or may be added in combination with couplers commonly known in the field of color photography.

At this time, the coupler of the present invention and the coupler to be used together may be added as separate dispersions, or may be mixed and dissolved and added as the same dispersion.

The colored coupling compound of the present invention (for example, a diffusion-resistant colored cyan coupler, etc.) is preferably added as an alkaline aqueous solution, and the phenol or naphthol type alcohol-diffusive cyan coupler is preferably added as oil droplets of a high-boiling organic solvent.

Next, examples of the present invention will be specifically shown, but the present invention is not limited thereto.

Example 1 A multilayer color photosensitive material A was prepared by coating layers 1 to 8 as shown in FIG. 1 on a transparent cellulose triacetate support.

1st Layer: Halation Layer 1 g of hardener (1) (described below) was added to 1 kg of a 5% gelatin aqueous solution containing black colloidal silver, and the mixture was coated to a dry film thickness of 1 μm.

2nd layer: Intermediate layer 50 g of 2,5-di-t-ocquelhydroquinone, 100 cc of tricresyl phosphate and 200 cc of ethyl succinate are dissolved, and 1 kg of 10% gelatin aqueous solution is added.
5g of Aerosol OT (manufactured by American Cyanamid)
250g of emulsion (I) obtained by adding and emulsifying and dispersing with a high-speed stirrer was mixed with 1kg of 10% gelatin aqueous solution, and 1g of hardener (1) was added to give a film thickness of 1μ when dry. I applied it to make it look like this.

Third layer; red-sensitive emulsion layer Ikg (silver amount;
0.6 mol, iodine content: 7 mol%, average particle size: 0.6μ
), 4 x 10-5 mol of sensitizing dye I and 1 mol of sensitizing dye ■
70 g of coupler I, 5 g of coupler ■ and 6 g of coupler
450 g of emulsion (2) prepared in the same manner as emulsion (1) by dissolving in 0 cc of emulsion (1) was added to 1 kg of the above spectrally sensitized emulsion, and a 5% alkaline aqueous solution (0.1 N Na
Contains OH: Add 90 cc of citric acid 2% aqueous solution 3
Add 0cc and further add 0.7g of hardener (1),
The coating was applied to a dry film thickness of 45 μm.

4th layer; same as the 2nd intermediate layer; 5th layer; green-sensitive emulsion layer; same as the 3rd layer; 2×
Spectral sensitization was carried out using 10-4 moles of sensitizing dye (1) and 6 x 10-5 moles of sensitizing dye (2). Add 600 g of emulsion (2) obtained in the same manner as emulsion (1) to 1 kg of the above spectrally sensitized emulsion, and add 0.99 of a hardening agent so that the dry film thickness is 4 μm. It was applied to.

6th layer: 1 kg of a 5% aqueous gelatin solution containing yellow colloidal silver was added to 200 g of yellow filter single-layer emulsion (2), and 1 g of cured film (1) was added to coat the layer to a thickness of 1 μm.

7th layer; blue-sensitive emulsion layer The same silver iodobromide emulsion as the 3rd layer (not spectrally sensitized)
kg, add 100 g of coupler ■ to 1 kg of dibutyl phthalate.
00 cc and 200 cc of ethyl succinate, add 500 g of emulsion ■ obtained in the same manner as emulsion ■, and further add 1 g of hardening agent (1) so that the film thickness when dry is 3 μm. It was applied to.

8th Layer: Protective Layer 1 g of hardener (1) was added to 1 kg of a 10% gelatin aqueous solution and coated to a dry film thickness of 1 μm.

The material used to prepare sample A is as follows:
1): 2,6-di-chloro-4-hydroxy-S-triazine sodium salt 2% aqueous solution coupler I; 1-hydroxy-N-[γ-(2,4-di-1-amylphenoxy)probyl]-2 -Naphthamide coupler ■; 1-hydroxy-4-(4-ethoxycarbonylphenylazo)-N-dodecyl-2-naphthamide coupler ■; α-(4-stearyloxybenzoyl)
-α-(2-, or 4-(N-methylbenzocareazolyl-2-amine)-1-benzotriazolyl]-2-methoxyacetanilide coupler IV; 1-(2,4,6-
trichlorophenyl)-3-(3{α-(2,4-di-
t-amylphenoxy)butylamido}-benzoylamino]-5-pyrazolone coupler V; 1-(2,4,6-trichlorophenyl)
-3-(2-chloro-5-tetradecanoylaminoanilino)-4-(3-methyl-5-hydroxyphenylazo)-5-pyrazolone coupler-■; 1-benzyl-3-
(2,chloro-5-tetradecylaminoanilino)-4
-(2- or 4-octanamido-1-penzotriazolyl)-5-pyrazolone coupler ■; α-pivaloyl-α-(N-benzylhydantoinyl)-2-chloro-5-[γ-( 2,4-di-
t-amylphenoxino)butyramide]acetanilide Coupler (4) was substituted for coupler (1) in the third layer of sample A.
), Coupler (12) Coupler ■, Same as sample A except that a 5% alkaline aqueous solution of Coupler Strain sample B
, D, E, and F were created.

Coupler ■; 1-hydroxy-4-{4-(1-hydroxy-3,6-disulfo-8-acetylamino-2-naphthylazo)phenoxy-N-[γ-(2,4-di-t
-amylphenoxypropyl)]-α-naphthamide Coupler I, ■, ■ instead of emulsion ■ in the third layer of sample A
Add 5g of V to 50cc of tricresyl phosphate.
and 100 cc of ethyl succinate to prepare emulsion V, which was obtained in the same manner as emulsion I. Sample C was prepared in the same manner as sample A except that coupler X was prepared.

Coupler ■; 1-hydroxy-4-(2-ethoxycarponylphenylazono-N-(2-ethylhexyl)-
2-naphthamide sensitizing dye I; anhydro-5,5'-dichloro 3,3
'-Disulfopropyl-9-ethylthiacarbocyanine hydroxide pyridinium salt sensitizing dye ■; Anhydro-9-ethyl-3,3'-di-(3-sulfopropyl)
-4,5,4',5'-dibenzothiacarbocyanine hydroxide triethylamine salt sensitizing dye ■: Anhydroguethyl-5, go-dichloro-3,3'-disulfopropyloxacarbocyanine sodium salt increase Sensitive dye ■: anhydro-5,6,5',6'-tetrachloro-1,1'-diethyl-3,3'-disulfopropoxyethylimidazolocarbocyanine hydroxide sodium salt samples A, B, C, D, E, and F were processed into color negative light-sensitive materials, photographed with a still camera, and developed at 38° C. in the following processing steps.

Development processing was performed at 38° C. in the following processing steps.

1. Color development 3 minutes 15 seconds 2. Bleach 6 minutes 30 seconds 3. Wash with water 3 minutes 15 seconds 4. Fixation 6 minutes 30 seconds 5. Wash with water 3 minutes 15 seconds 6. Stable 3 minutes 15 seconds The treatment liquid composition used in each step was as follows.

Color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate
30.0g potassium bromide 1.
4g hydroxylamine sulfate 2.4g 4-(N
-Ethyl-N-β-hydroxyethylamino)-2-methyl-anilinosulfate 4.5g with water 1l Bleach solution Ammonium bromide 160.0g Aqueous ammonia (28%) 25.0ml Ethylenediamine-tetraacetic acid 130g Sodium iron salt Glacial acetic acid 14ml Water 1l Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0ml Sodium bisulfite
With 4.6g water 1l Stabilized formalin (40%) With 8.0ml water
1l As a result, samples A, D, and E contained in the photosensitive material of the present invention
It was found that the color negative obtained from Sample C was significantly superior in sharpness and color purity to that obtained from Sample C.

In addition, the color negatives obtained from Samples B and F had larger fog in the red-sensitive layer than Sample A according to the present invention, and were inferior to Samples A, C, D, and E in terms of graininess. It turned out that.

Therefore, it was found that the color negatives obtained from Samples A, D, and E had excellent sharpness, graininess, and color purity.

The fog values are shown below.

Sample A (present invention) 0.06 B (comparative example) 0.15 D (present invention) 0.07 E (〃 ) 0.06 F (comparative example) 0.22 Example 2 A multilayer color sensitive material G having a layer structure as shown in FIG. 2 was prepared.

The composition of each coating layer is as follows.

First layer: Antihalation layer Same as the first layer of sample A Second layer: Intermediate layer 250 g of emulsion A of the second layer of sample A was mixed with 1 kg of 10% gelatin aqueous solution, and the coupler of the present invention was mixed with 1 kg of 10% gelatin aqueous solution. 30% of 5% alkaline aqueous solution (containing 0.1N NaOH) of (1)
cc, 10 cc of a 2% citric acid aqueous solution, and 1 g of a hardening agent were added, and the coating was applied to a dry film thickness of 1 μm.

3rd layer: 1st red-sensitive emulsion layer (film thickness 2 μm when dry) Silver iodobromide emulsion...Silver coating amount: 1.4 g/m2 (silver amount: 0.05 mol%, iodine in silver halide grains) Polymer content: 7 mol%, average grain size of silver halide grains: 0.4 μ, gelatin 6.2%
) Sensitizing dye I... 5 x 10-5 mol sensitizing dye ■... 〃〃 1.2 x 10-5 mol coupler ■... 〃〃 0.09 mol coupler ■... 〃〃 0.02 molar coupler ■... 〃〃 0.01 molar hardener (1)
...20mg/m2 4th layer; 2nd red-sensitive emulsion layer (film thickness 1.5μ when dry) Silver iodobromide emulsion ...Silver coating amount 1.0g/m2 (4th layer silver amount; 0 .05 mol%, iodine content of silver halide grains; 8
Mol%, average grain size of half a silver halide grain; 0.7μ, gelatin 6%) Sensitizing dye I...3x per mole of silver
10-5 mole sensitizing dye■ 1.
2×10-5 molar coupler I
0.05 molar coupler■
0.03 molar coupler■
0.01 mol hardener (1)...15mg
/m2 5th layer; magenta colored coupler single layer coupler (1) 30cc of 5% alkaline aqueous solution to 70c
The procedure was the same as for the second layer except that the amount of the 2% citric acid aqueous solution was changed from 10 cc to 27 cc.

(Film thickness 1.2μ) 6th layer; Intermediate layer Example 1 Same as the 2nd layer of sample A 7th layer; 1st green-sensitive emulsion layer (film thickness 2.4μ when dry) Silver iodobromide emulsion...・Silver coating amount: 1.4 g/m2 (same as third layer) Sensitizing dye ■... 3 x 10-5 mol sensitizing dye IV 〃 1 x 10-5 mol coupler IV 〃 0.05 per mol of silver Molar coupler V 〃 0.01 mol coupler ■ 〃 0.005 mol DIR Hydroquinone I 〃 0.004
Molar hardener (1)...25mg/m2 8th layer; second green-sensitive emulsion layer (dry thickness 1.8μ) Silver iodobromide emulsion...Silver coating amount 2.5g/m2 (thickness 1.8μ) Same as 4th layer) Sensitizing dye ■...2.4 x 10-5 mol sensitizing dye ■ for 1 mol of silver 〃 0.8 x 10-5 mol coupler IV 〃 0.005 mol coupler V 〃 0.015 mol coupler VI
〃 0.0006 mol hardener (1)
...20mg/m2 9th layer; Yellow filter single layer Sample A 10th layer same as 6th layer; 1st blue-sensitive emulsion layer (dry thickness: 2μ) Silver iodobromide emulsion Silver coating amount 1.3g/ m2 (silver content; 0.048
mol%, iodine content of silver halide grains: 7 mol%, average grain size of silver halide grains: 0.5 μ, gelatin: 6%) Coupler ■: 0.25 mol hardener per 1 mol of silver ( 1)...20mg 11th layer: 2nd blue-sensitive emulsion layer (dry thickness 1.3μ) Silver iodobromide emulsion...Silver coating amount 1.2g/m2 (silver amount: 0
．． 052 mol%, iodine content of silver halide grains: 6 mol%, average grain size of silver halide grains: 0.7μ, gelatin: 6%) Coupler■...0.06 mol hardness per mol of silver Film agent (1)...8 mg/m2 12th layer; 1st layer protective layer (dry film thickness 1μ) Silver bromide emulsion...Silver coating amount 0.4 g/m2 (silver amount; 0.06 mol) %, average grain size of silver halide grains: 0.05μ, gelatin: 6%) Hardener (1)...7 mg/m2 13th layer: 2nd protective layer Sample A Same as 8th layer Sample G Among the materials used to make the sample, the coupler, sensitizing dye, and hardener are the same as sample A, and the others are as follows: DIR hydroquinone: 2-o-hexadecylthio-5
-(1'-phenyltitrazol-5'-ylthio)-
6-Phenylthiohydroquinone Sample G was processed, photographed, and processed in the same manner as Samples A to C, resulting in a color negative that was even better than Sample A in terms of sharpness, granularity, and color purity. .

In samples A and G, coupler (1) was replaced by coupler (2),
Similar results were obtained even when (3) was used instead or when these were used in combination.

[Brief explanation of drawings]

FIGS. 1 and 2 schematically show the layer structure of the sensitive materials of Examples 1 and 2, respectively.

Claims (1)

[Scope of Claims] 1. A silver halide color photosensitive material containing a cyan coupler represented by the following general formula. A-O-(L)n+1-X A represents the residue of a naphthol cyan coupler bonded to the -0-(L)n+1-X group at the coupling position. L is -CH2CH2-O-, -CH2-, -CH2C
HOHCH2O-, -(CH2)3-O- or -(
CH2) represents 4-O-. n represents O or 1. X is -[Ar1]-N=N-[Ph1], [Ar1]-
N=N-[Ar2],-[Arl]N=N-(Het)
-[Ar1]- represents an arylene group, -(ph1) represents a phenyl group having a water-soluble group or a hydrophilic group, and -[Ar2] represents a hydroxy group having a water-soluble group or a hydrophilic group. -(Het) represents a naphthyl group and an aromatic heterocyclic group. X has at least one acidic group.