JPS60237448A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve heat and light fastness of a color image by incorporating a specified cyan dye image forming coupler. CONSTITUTION:The cyan dye image having superior fastness to light, heat, wet heat, etc., can be formed by incorporating the cyan dye image forming color coupler represented by the formula in which R<1> is -CONR<3>R<4>, -NHCOR<3>, or -NHCONR<3>R<4>; R<3> is optionally substd. aliphatic, aryl, or heterocyclic group; R<4> is H or same as R<3>; R<2> is -COR<5>, -CONR<5>R<6>, -SO2R<5>, or -SO2NR<5>R<6>; R<5> is same as R<3>; R<6> is same as R<4>; X is H or a group releasable by the coupling reaction with the oxidation product of a developing agent; and each of (R<3> and R<4>) and (R<5> and R<6>) may form a hetero ring.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material containing a cyan dye-forming coupler.

(Background technology) After giving silver halide photography, a light-sensitive material is exposed to light.

By color development, the oxidized aromatic-grade amine developing agent and the dye-forming coupler react to form a color image. Generally, this method uses a subtractive color reproduction method to reproduce yellow, green, and red, each of which is a complementary color.

Magenta and cyan color images are formed. Phenols or naphthols are often used as cyan image forming couplers.

However, several problems remain in the storage stability of color images obtained from conventionally used phenols and naphthols. For example, U.S. Patent 2.31.7. f3/
The color images obtained from the 2-acylaminophenolic cyan couplers described in Kfta, Ko, No. 23.730, generally have poor heat fastness, and U.S. Pat. The color images obtained from the 2,5-diacylaminophenol cyan couplers described in the specification generally have poor light fastness, and the /-hydroxy-λ-naphthamide cyan couplers generally have insufficient light fastness and heat fastness. be.

(Purpose of the invention) The first object of the present invention is to remedy these drawbacks.

The second objective is to provide a cyan dye-forming coupler that has excellent heat and light fastness of color images, and the second purpose is to produce a color photographic material containing the cyan coupler as described above. It is to provide.

(Structure of the Invention) The object of the present invention is achieved by a coupler represented by the following general formula (1).

The ratio of 2 to general formula (1) is -C (JN).

-N)icUI: L' or 1NHcON, R represents a substituted or unsubstituted aliphatic, aryl, or heterocyclic group, and R is a hydrogen atom, a substituted or unsubstituted aliphatic, Representing an aryl or heterocyclic group, 几 is -CO, and -CONl is also 几.

-802R or -802Nl (represents 几, 几5
represents a substituted or unsubstituted aliphatic, aryl, or heterocyclic group; 几6 represents a hydrogen atom, a substituted or unsubstituted aliphatic, aryl, or heterocyclic group; Represents a group that can be eliminated in an oxidative coupling reaction with the main drug.

R3 and phosphor 4 may be combined to form a nitrogen-containing heterocycle, and lt5 and phosphor 6 may be combined to form a nitrogen-containing heterocycle.

The above R1, 几2, R3, 144゜R of general formula (1)
5,) R6 and X are detailed below.

In general formula (1), approximately 1 is -C(JN几3几4゜-N
HCOkL3 or -, NHCOf~几3 kL4
Ratio 3 represents a chain or cyclic aliphatic group having 7 to 30 carbon atoms [generic term for alkyl group, alkenyl group, and alkynyl group] (for example, methyl group, dodecyl group, cyclohexyl group, fluorinyl group, fluoropargyl group) etc.), aryl groups having t to 30 carbon atoms (e.g. phenyl group, naphthyl group, etc.), heterocyclic groups having -30 carbon atoms (e.g. imidazolyl group, 1 morpholyl group, 2-pyridyl group, 2-furanyl group, etc.) ), which are aliphatic groups (for example, methyl groups).

butyl group, bontadecyl group, cyclohexyl group),
Aryl group (e.g. phenyl group, naphthyl group, etc.),
Heterocyclic groups (e.g. λ-pyridyl group).

Hiro-pyridyl group, 2-furanyl group, 2-oxipzolyl group, 2-imidazolyl group, etc.), alkoxy group (e.g. methoxy group, dodecyloxy 7 group, co-methoxyethoxy 7 group, etc.), aryloxy group (e.g. Phenoxy group, 2. Hiro-G tert-amylphenoxy group, 3-
tert-butyl-ψ-hydroxyphenoxy group, naphthyloxy group, etc.), carboxyl group, carbonyl group (
For example, acetyl group, tetradecanoyl group, penzoyl group, etc.), ester group (for example, methoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc.), amide group (for example, acetylamino group, ethercarbamoyl group, methanesulfonylamino group, phtersulfamoyl group, etc.), imide group (e.g. succinimide group, hydantoinyl group), sulfonyl group (ritoevamethanesulfonyl group, toluenesulfonyl group), It may be substituted with a substituent (including substituent atoms; the same applies hereinafter) selected from a hydroxyl group, a cyan group, a nitro group, and a halogen atom.

R4 represents a hydrogen atom and a substituent group having the same meaning as R3.

In general formula (1), the ratio is -CIJ)L, -CON
几l also represents -SO2几5 or -802NR5R', and R5 represents a substituent group having the same meaning as R3. (2) represents a hydrogen atom 2 and a substituent group having the same meaning as I:R3.

In the general formula CI), in addition to a hydrogen atom, , dotesyloxy group, methoxyethercarbamoylmethoxy group, carbomethoxy group, etc.), aryloxy group (for example, phenoxy group, naphthyloxy group, Hiro-carboxyphenoxy group, etc.).

Acyloxy group (eg, acetoxy group, tetradecanoyloxy group, benzoyloxy group, etc.).

An amide group (e.g. dichloroacetylamino group).

(heptafluorobunalylamino group, methanesulfonylamino group, toluenesulfonylamino group, etc.)

Alkoxycarbonyloxy groups (such as ethoxycarbonyloxy groups and benzyloxycarbonyloxy groups), aryloxycarbonyloxy groups (such as phenoxycarbonyloxy groups and ψ-chlorophenoxycarbonyloxy groups).

Examples include imide groups (for example, succini, do group, hydantoinyl group, etc.).

In order to achieve the object of the present invention, Bl is preferably -CONi(,3B'). R2 is preferably -8(J2 or 100)L, and the most preferable is -CONi(,3B'). )2B. Preferred R5 is an aliphatic group or an aryl group, and the most preferred is carbon 6! l/~30 straight chain bend 1i7j
It is a group group or an aryl group having t to 30 carbon atoms, and these may be substituted with the substituents mentioned in this section above. Preferred R is a hydrogen atom. ratio
Preferred examples are chain or cyclic aliphatic groups with a size of k4<several l-λ, aryl groups or heterocyclic groups with a carbon number of z~30, and these are mentioned in the above section H. It may be substituted with a substituent. Preferably, R6 is a hydrogen atom or the same as R5. 11 is -C
When 0R5, I (preferably as 5) is substituted with an electron-withdrawing substituent (e.g., fluorine atom, chlorine atom, sulfonyl group, nitro group, cyano group, etc.). .

Next, specific examples of couplers that fall within the scope of the present invention will be illustrated, but the 2'L couplers used in the present invention are not limited to these. In the following structural formula (11C5H
l l represents -C(CHa)2C2H5, (t)C
s l (t 7 is 10 (C) i3) C) i2c (C1 (
3) Represents a.

1 (2) (3) 012H25 014 12H25 Next, the composite ν and τ bore.

(1) Tertrifluoroacetamide-/-hydroxynaphthoic acid teramino-l-hydroxynaphthoep,! o.

39 was dispersed in 100 rall of tetramethylene sulfone, and to this was added trifluorochloric anhydride TTSG.

The mixture was heated and stirred using GOOC for several hours. λOmL of water was added, and after stirring for 30 minutes, 1 full of acetonide, 200 m9, was added and cooled. The resulting precipitate was washed with 5-acetonitrile and dried to obtain 7 g of 5-trifluoroacetamide-/-hydroxynaphthoic acid.

L2) Synthesis of I)-nitrophenylj-1-lifluoroacetamide-/-hydroxynaphthoate tert-trifluoroacetamide/-hydroxynaphthoate (lit,
200'ij and 700 g of p-nitrophenol in 1. ! ; Disperse in 1 ml and heat and stir. Dimethylformamide/ml was added to this, and 10 mQ of thionyl chloride I was added thereto. After the completion of the dropwise addition, the mixture was heated and stirred for an hour and then cooled. The resulting precipitate was washed with source L7 acetonitrile and then dried.

p-nitrophenyl 3-1-lifluoroacetamide-/
-Hydroxynaphthoate, 23o 9 obtained.

(3) Synthesis of coupler (1) p-nitrophenyltertrifluoroacetamide-7-
Hydroxynaphtonite≠29 was dispersed in 00 ml of tetrahydrofuranco and stirred at very high temperature. To this J-(2
, Processing of tert-amylphenoxy)propylamine 2-9, /.

! The mixture was poured into 500 ml of drained water that had been stirred for hours. The supernatant liquid was discarded, the remaining oily substance was dissolved in methanol 2θθmQ by heating, insoluble matter was filtered off, and the filtrate was cooled.

The resulting crystals were collected by filtration to obtain the desired coupler (114/9). The melting point /j/, j-/octopus, and 26C0 elemental analysis results are shown below.

Calculated value (96) 4. f7 t7. // 11.1? (
5)! -Amino-7-hydroxy-N-[3-(2,Hiro-G-tert-amylphenoxy)propylcou 2-
Synthetic coupler of naphthamide (1) 31. 'j was dissolved in 200 ml of ethanol, an aqueous sodium hydroxide solution (Na hydroxide IJ Wham λ09, water s o mo.) was added to the solution, and the mixture was heated at 60 ml in a nitrogen stream.
Stirred at 0c for 2 hours. Glacial acetic acid ψOmQ was added and cooled. Filter and collect the resulting precipitate. Wash with ethanol water #
Temporarily dried, 5-amino-l-hydroxy-N (3('
+≠-tcrt-amylphenoxy)propyl]-
λ-naphthamide λP9 was used.

(2) Synthesis of coupler (3) j-amino-hydroxy-N-(J-(J, Hirojit
ert-amylphenoxy)propyl]-. 2-Nutamide 2119, acetonitrile/! OmQ, 20rnQ of pyridine, methanesulfonyl chloride/3. ! 19. A solution consisting of 30 mQ of acetonitrile was added dropwise. ! After stirring for an hour, add 20 ml of glacial acetic acid. was added, and further 0 m9 of water was added little by little. The resulting precipitate is washed with water, dried, and then recrystallized from ethanol. Kabuji (3)/79. Melting point/g2.0-/1
2. The results of the aC0 elemental analysis are as follows.

Calculated value (related) 7.1.3 t7. ia s, os The coupler represented by the above general formula (I) is usually present in the halogenated emulsion layer constituting the photosensitive layer in an amount of 0.1 to 7.0 mol, preferably 0.1 to 7.0 mol per mol of halogen. / ~ Contains 15 moles of O.

In the present invention, various publicly known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by the oil-in-water dispersion method known as the oil protection method. For example, dibutyl phthalate,
High boiling point organic solvents such as phthalic acid esters such as dioctyl phthalate, glue/acid esters such as tricresyl phosphate, trinonyl phosphate, or teric acid esters.

After dissolving in a low boiling point bathing medium such as alone or in a mixed solvent, it is emulsified and dispersed in an aqueous gelatin solution containing a surfactant.

Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surface active compound to form an oil-in-water droplet dispersion with phase inversion. Alkali-soluble couplers can also be dispersed by the so-called Fischer dispersion method. A coupler dispersion with a low boiling point of +9. After removing the solvent, it may be mixed with a photographic emulsion.

Various halogenated compounds can be used in the halogenated complex emulsion layer according to the present invention. for example.

These include silver chloride, silver bromide, @silver bromide, silver iodobromide, and silver chloroiodobromide. Silver iodobromide containing boron iodide in a molar proportion of 0 to 20, and silver chlorobromide containing silver bromide in a molar proportion of IO to SO are preferred. Crystal form and crystal structure 1 of 2-rogenated complex particles
There are no limitations on particle size, particle size distribution, etc. Silver halide crystals may be normal crystals or twin crystals, and may be hexahedral, octahedral, or μ-hedral. Length - Thickness is 0.0mm as described in Chidisklo Jerko 2534c. The grains may be tabular grains having a diameter of at least 0.014 micron or less and an average aspect ratio of 5 or more.

The crystal structure may be uniform (σ), but the inside and outside may have different compositions, even if they form a single layer structure, or silver halide with different compositions may be bonded by epitaxial bonding. It may also consist of a mixture of particles of various crystalline forms. Further, the latent image may be formed mainly on the surface of the particle or may be formed inside the particle.

The grain size of the halogenated image may be fine grains of 0.1 micron or less, large buoyant grains with a projected area diameter of up to 3 microns, a monodisperse emulsion with a sloped distribution, or a polydisperse emulsion with a wide distribution. But that's fine.

These noroge/ka@particles are commonly used in this world! It can be manufactured by a known method.

The silver halide emulsion can be sensitized by a conventional chemical sensitization method, such as a yellow sensitization method, a yellow sensitization method, or a combination thereof. Furthermore, the silver halide emulsion according to the present invention can be imparted with color sensitivity in a desired wavelength range by using a sensitizing dye. Examples of pigments usefully used in the present invention include cyanine, hemicyanine, rhodacyanine, and merocyanine.

There are methine dyes such as oxonol and hemioxonol, and sunaryl dyes, and seven types or a combination of two or more types can be used.

Furthermore, in the case of a fine-grain silver halide emulsion having substantially no photosensitivity (for example, silver chloride, silver bromide, with an average grain size of 0.20 μm or less) in the halogen ratio emulsion layer or other hydrophilic colloid layer. , chlorbrominated sauce 1L) may be added.

The cyan coupler of the present invention can be used in conjunction with macenta 2 and yellow couplers to produce natural color materials or, when these couplers are chosen to give a neutral gray color, to produce black and white materials based on dye images. Can be used for manufacturing. The cyan coupler of the present invention may be used in combination with a conventionally known cyan coupler in an equimolar amount or less.

These couplers that can be used in combination may be either ≠ equivalent or λ equivalent to the button ion.

A colored coupler which also has the effect of one-color correction, or a coupler which releases an image inhibitor upon development (so-called DIR coupler) may be used in combination.

In addition to DIR couplers, there are also colorless DIR couplers in which the product of the coupling reaction is colorless and releases a developing needle.
Coupling compounds may also be added.

A typical example of a yellow coupler is a US patent! .

lr7! , No. 057, 2,1AO7,2'10@, 3.261. jOt, 4λ, 22F, 'l'13.

Same 3. C#r, 1Fi1 No. 3, 4<≠7, 9.
It is described in No. 21 etc. Among these yellow couplers, acylacetamide derivatives such as benzoylacetanilide and pivaloylacetanilide are preferred.

A typical example of a magenta coupler is U.S. Patent-9A00
．． No. 711, the same 2 or 3 tons? , 4#9, 2.31A
No. 3,703, No. 2,3//, No. 012, No. 3. /riλ
, ♂ P6 No. 3,57, Hirokota No. 3,042.
It is described in No. 1, No. 53, No. 1, No. 53, No. 73, etc. Among these magenta couplers, typical examples of cyan couplers that can be used in combination with pyrazolones or pyrazoloazoles (virazoe pyrazole, pyrazoloimidazole, pyrazolotriazole, pyrazolotetrazo) are U.S. Pat. x, ryr, rs6, 3,002.Ir36, 3.03'A.

r Octopus, same 2. Hiro 7 Hiro, Kota 3, same, Hiro 2J,
No. 730, λ, 367.13/, and 3.0 Hiro/, 23.

The support used in the present invention may be either a transparent support such as polyethylene terephthalate or cellulose triacetate, or a reflective support described below. Examples of reflective supports include baryta paper, polyethylene-coated paper,
Polypropylene synthetic paper 1 Transparent support with a coating layer or a reflector 1 For example, glass plate, polyester film such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide film, polycarbonate film, polystyrene film, etc. These supports can be appropriately selected depending on the purpose of use.

In addition to the halogenated emulsion layer, the color photographic light-sensitive material of the present invention may be provided with auxiliary layers such as an undercoat layer, an intermediate layer, and a protective layer. Further, if necessary, an ultraviolet absorbing layer may be provided at a position farther from the support than the emulsion layer or between the red-sensitive silver halide emulsion layer and the green-sensitive silver halide hole layer.

As a binder or protective colloid in photographic emulsions.

Gelatin is advantageously used, but other hydrophilic colloids can also be used.

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

Enzyme-treated gelatin as described in Japan, A/A, p. 30 (196 O) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

In the photographic material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers may contain a brightening agent such as a stilbene type, a triazine thread, an oxidizole type, or a coumarin type. These brighteners may be water-soluble, or water-insoluble brighteners may be used in the form of a dispersion. Specific examples of fluorescent brighteners are US patented! .

t3.2, 70/issue, 3.2A? , ItfO issue, same 3
．． 352, 10.2, British Patent No. 152,079, 3/P, 743, 1 (esearch Discl.
osure/Volume 76/71.4L3 (Published December 7R), Bright on page 2, lines 2 to 36 in the left column.
It is described in the description of teners, etc.

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

The photosensitive material of the present invention can be used as a color fog preventive agent.

Hydroquinone derivatives, aminophenol derivatives.

It may contain gallic acid derivatives, ascorbic acid derivatives, etc., and specific examples thereof include U.S. Pat.

1103.7J/No. 2. L/r, /y/3, same 2
．． 1.7ta, 3/II issue, same, 70/, / 17th issue, 2,70tA, 7/3 issue, 2,721j', /,
! No. 9, same, 7J, No. 2.300, same, 73ri, 7
ts issue, Tokukai Akira O-? Kota GG, 5o-229f
? Issue, same to-23? -r No. 30-/10337, No. 51-/1It2Jj, %Koakiri θ-, 2311
It is stated in No. 3, etc.

In addition to the above, the color photographic material of the present invention may contain various photographic additives known in this field, such as Stabilizer 11, antifoggants, surfactants, couplers other than those of the present invention, filter dyes, and anti-irradiation agents. Dyes, developing agents, etc. can be added as necessary, and a typical example is Ributé.
Disclosure/7 to 4t3 (December 1971)
It is described in.

The color developing solution that can be used in the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As a color developing agent, 4t-amino-N, N-diethylaniline, 3-methyl-Hiro-amino-N, N-jetera-IJ, Hiro-aminohehef-N-β-hydroxyethylaniline, 3-methyl- ≠-Amino-N-ether-N-β-hydroxyethylaniline, 3-methyl-Hiro-amino-N-ethyl-
Typical examples include N-β-methanesulfamide etheraniline and Hiro-amino-3-methoxyenalaniline.

The color developer may contain pH buffering agents such as alkali metal myelites, carbonates, borates, and acid salts, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants. It can also contain agents such as Also, if necessary, water softeners, preservatives such as hydroxylamine, and benzyl alcohol.

Organic solvents such as diethylene glycol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, abrasions such as sodium polion hydride, /-phenyl-
3-pyrazolidone as an auxiliary developer, a viscosity-imparting agent, and a polycarboxylic acid chelate as described in US Pat. No. 3,723.

It may also contain an antioxidant as described in OLS, 2.7 Co., No. 250.

After color development, the photographic emulsion layer is usually subjected to whitening treatment.

The silver white process may be performed simultaneously with the fixing process, or may be performed separately. As a whitening agent, for example, iron (III
), compounds of polyvalent metals such as cobalt (■), chromium (■), copper (II), peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide 1M chromate, iron (Ill) or cobalt (■) organic complex salt 1
For example, ethylenediami/tetraacetic acid, nitrilotriacetic acid,
, 1-minopolycarzenes such as 3-diamino-coprobanol tetrasoric acid, or complex salts of organic acids such as citric acid, paleolitic acid, malic acid, etc. Can be used.

Among these, potassium ferricyanide, sodium ethylenediaminetetraacetate (I[l), and ammonium ethylenediaminetetraacetate (Ill) are particularly suitable for southern use. Ethylenediaminetetraacetic acid iron(III) complex salts are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

It may be washed with water after color development or bleach-fixing treatment.

Color development can be carried out at any temperature between /f'c and jt,'c. Preferably 300C or higher.

Particularly preferably, color development is carried out at 35'C or higher.

The development time is preferably as short as about 3 minutes to about 1 minute. For continuous image processing, liquid replenishment is preferred, and the amount of liquid to be replenished is 33 Oct to 1 Oα, preferably 100 ct or less per square meter of processing area. It is preferable that the benzyl alcohol content in the developer is not more than jmO,/l.

Bleach-fixing can be carried out at any temperature from /roc to ooC, but preferably 30 aC or higher. When the temperature is 3f0C or higher, the processing time can be reduced to 1 minute or less, and the amount of liquid replenishment can be reduced. The time required for washing with water after color development or bleach-fixing is usually 3 minutes or less, and it is also possible to wash with water within 7 minutes using a stabilizing bath.

Colored pigments not only deteriorate due to light, heat, or temperature, but also deteriorate and fade due to mold during storage. Cyan images are particularly susceptible to severe deterioration due to mold, so it is preferable to use a mold inhibitor. Specific examples of antifungal agents are disclosed in JP-A-57-/! ;72
There are more corchiazolylbenzimidazoles described by Hirohiro. The antifungal agent may be built into the photosensitive material, or may be added from the outside during the development process, and it can be added at any process if it coexists with the processed photosensitive material.0 The following 5 inventions Although the present invention will be specifically explained with reference to examples, the present invention is not limited thereto.

Example l) Coupler according to the invention (1)/77 g, trioctyl phosphate iog and ff+4 ethyl, 20 mfl s
Aqueous solution 1 containing gelatin 109 and dodecylbenzenesulfone MO, +9
00 mQ, stirred, heated in advance, passed through a colloid mill, and finely emulsified and dispersed.

The entire emulsion was added to a photographic emulsion containing 2g9 of silver iodobromide and 30g gelatin, and as a hardening agent ≠I
The pH of the 6-dichlorohiro-p-hydroxytriazine 2 water bath solution was set to 30. After adjusting to O, it was coated uniformly on a cellulose triacetate film base. This is designated as sample IN.

tetramolar coupler (3) instead of coupler (1) above
, (5), and the film was prepared by the same operation. These are designated as samples /B and /C, respectively.

For comparison, four moles of comparative couplers (10/) and (102) were used in place of the above coupler (1).

(103) and a film was prepared by the same procedure. These are designated as samples /D, /E, and /F, respectively.

α (10λ) H (t)C5H□□ (103) (1011-) OCH2CH2SCHC12H25(n)〇〇 2H (10 Color development process - [Procedure (31 0C) 1 Oak development...・3 minutes 1 second 2 mark white...
・・・・・・ Wash with water for 30 minutes 30 seconds ・・・・・・
... 3 minutes/second 4, steady Graduation...... 3 minutes/30 seconds 5, washing with water... 3 minutes/evening second 6, stable... ...3 minutes 75 seconds The composition of the processing liquid used in each step is as follows.

Sword uu hood. Image solution Sodium nitrotriacetate 7.09 Sodium melonite ψ. Og Sodium carbonate 3θ. θ9 Potassium bromide /. ≠9 Hydroxylamine W acid 1n a. ag≠-(N-ethyl-N-βhydroxyethylamino)-! -Methylaniline value salt ψ. j9 Add water and bleach / (nightbromide ambromide / 609 Ammonia water (2 g) 25.0mQ ethylenediamine-4-a-dosodium salt / 309 Ice vinegar / Add Hongshu water / Constant N liquid sodium tetrapolyphosphate 2.09 Sodium sulfite ψ, 09 Thio-p ammonium (70%) /7 m11 Sodium bisulfite ≠, add water /l Stable liquid Hoya, 7 1.0 mC Water A fastness test was conducted on the sample obtained after treatment with /.When the sample was left in the dark at 1000C and when exposed to light in a xenon tester (100,000 lux) for several days. Table 1 shows the fastness of each sample as the initial concentration/the rate of decrease in concentration at 0.

Table 1 From these results, the cyan coupler according to the present invention shows that heat,
It can be seen that color images with good stability on both sides of the light are formed.

Example 2) A multilayer photosensitive material consisting of each layer having the composition shown below was prepared on a cellulose triacetate film support.

1st layer; antihalation layer; gelatin layer containing black colloidal silver; 21st layer; intermediate layer 2; gelatin layer containing an emulsified dispersion of j-g-1ert-octylhydroquinone.

3rd; i; 1st red-sensitive emulsion layer Broken iodobromide emulsion (silver iodide; molar ratio) ...... Silver coating amount /, A9r/m" Sensitizing dye ■... ...Hiroshi, Yu x 1 for 1 mole of button
0 molar sensitizing dye ■・・・・・・Z/, 10 molar coupler (1011) for 1 mol of silver, Oψ molar coupler EX- /...Old...0.003 moles per 7 moles of button Coupler EX-7...O for -1 mole
, ooo to mole 1st layer; 2nd red-sensitized milk cutting layer fertilized button milk 4 (iodized bud: 10 mol)...
・・Silver coating amount / , IA gong / m2 Sensitizing dye■・・
......Sensitizing dye for 1 mole of button...
..../x/(7 mole coupler (21))......0.0.22 mole coupler EX-/......91 mole・@0.00/6 mol per 1 mol Second layer; 〇th layer same as the second intermediate layer; th/green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; V mol) ・...... Silver coating amount /, λ9 / rn2 sensitizing dye ■ ...... sx / per mole of complex
0 mol sensitizing dye ■・・・・・・7 mol silver ((for λX
10 Molar coupler EX-2......O, OS per 1 mole of J; Molar coupler EX-3......0.00 r mole coupler gX-7 per 1 mole of silver・・・・・・・O, ooir moles per 1 mole of iron 7th layer; 1st evening-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; r mol) ・・・・・・・・・・＠Coating amount /, 39/m2 Sensitizing dye■・・・・・・3xi o mole for 7 moles of silver Sensitizing dye■・・・・・・・・・For 7 moles of silver /, ko Molar coupler EX-4...0.0003 mole r-th layer per 1 mole of silver; Yellow filter 1 layer with yellow colloidal silver in gelate/aqueous solution. tahji te
a gelatin layer comprising an emulsified dispersion of rt-octylhydroquinone.

1st light sensitive emulsion layer Silver iodobromide emulsion (iodide @: t mol ratio) ......Amount of silver coated 0.79/m2 Ira EX-7... ...0.2j per mole of silver
Molar coupler E, X-7...0.0/3 mol per 1 mol of complex 10th layer: 1st layer? # Emulsion layer Silver iodobromide emulsion (silver iodide; t mol ratio) ...... Silver coating amount 0.49/m2 Coupler EX-A ...... Silver 1 mol for o, ot
Molar 1st/layer; First protective layer silver iodobromide (silver iodide 1 mole, average grain size 0.07μ) ......Silver coating amount o, 5g7m2 Ultraviolet absorber UV-/ A gelatin layer containing an emulsified dispersion of.

72nd layer; No. 1 protective layer trimethylmethanoacrylate particles (diameter approximately i, rμ)
Apply a gelatin layer containing.

In addition to the above composition, gelatin hardener 11-/ and a surfactant were added to each layer. The sample prepared as described above was designated as sample 2A.

Instead of the above coupler (10 Hiro), the same molar coupler (
8) and the same procedure was used to prepare the sample. This is designated as sample 2B.

For comparison, a sample was prepared by the same procedure using the same molar coupler (10/) instead of the above coupler (IO≠) and the same molar coupler (10/) instead of Kabuji (21). , sample, 2C.

Compound E used to prepare the sample) (-/ X-2 α X-3 EX-s EX-,!' CH2=CH-802CH2CONHCH2CH2=C
H5O2CH2C (JNHCH2CHa CH3 UV-/ Sensitizing Dye I Sensitizing Dye I Sensitizing Dye ■ Sensitizing Dye ■ The development used here was carried out at 3ruC as follows.

1. Color development... Old... 3 minutes/j seconds 2, white...... minutes 30 seconds 3, washing with water
・・・・・・・・・ 3 minutes/, 5-seconds 4, fixed...
・・・・・・ 6 minutes 30 seconds 5, wash with water ・Yu・・
- 3 minutes/j seconds 6, female fixed ...... 3 minutes/even seconds The treatment tL composition used in each step is as follows.

Color developer Sodium nitrilotriacetate /, O Sodium sulfite Sodium carbonate 30.0"1 Potassium bromide /, Hiro9 Hydroxylamine sulfate 2.4'9 Hiro-(N-ether-N-β -Hydroxyethylamino)-λ-Methylaniline sulfate ψ, 5g Add water /l Bleach Liquid ammonium bromide /1,0.0g Aqueous ammonia (2J' section) -! j, Om? .

Ethylenediamine-ferric sodium tetraacetate /30.09 Glacial acetic acid /≠, add Om water / to fixer Sodium tetrapolyphosphate 2.09 Sodium sulfite v, og Ammonium thiosulfate (704) 17! , 0 ml Sodium biphosphate ≠, 6 g Add water ll Stabilizing liquid formalin 1.0 rn9 Add water / liter A fastness test was conducted on the sample obtained after treatment. When the sample was left in the dark at /θO0C for r days, and when it was left in the dark at 0C and humidity 70C4,
Table 2 shows the fastness of each sample in terms of the rate of decrease in concentration at an initial concentration of 1.0.

These results show that the cyan coupler according to the present invention has excellent fastness against heat and moist heat.

Patent applicant Fuji Photo Film Co., Ltd. Procedural amendment:
Mr. Kou, Commissioner of the Japan Patent Office, dated 72nd October, 1919, 1. Indication of the case: Japanese Patent Application No. 73606, 1992. 2. Name of the invention: Silver halide color photographic light-sensitive material 3. Relationship with the amended person's case. Patent. Applicant Address: 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of amendment: "Detailed Description of the Invention" column 5 of the specification, "Detailed Description of the Invention" section of the description of the contents of the amendment as follows: Correct through.

1) Page 1, line 76 [≠-chlorophenoxycarbonyloxy group, etc.),”
followed by "arylazo group (e.g. λ-ethoxycarbonylphenylazo group, Hiro-methylphenylazo group, ≠-piparoylaminophenylazo group, etc.), alkylthio group (e.g. dodecylthio group, benzylthio group, etc.), arylthio group (e.g. ≠ -t-butylphenylthio group, ≠
-dodecylphenylthio group, etc.), heterocyclic oxy group (e.g., Hiropyridyloxy group, !-pyrazolyloxy group, etc.), heterocyclic thio group (e.g., /-phenylnato-dizoylthio group, comethylthio/, 3. ≠-thiadiazole-y-ylthio group, etc.)," is inserted.

2) The isth page Insert.

H2 1 (3g) (3ri) C5Hi1(t) 3) In the 6th to 7th lines of the first page, "O07~/, contains 0 mol, preferably 0.1 to 0.3 mol" is replaced with "o , ooλ~i, o mol, preferably Q, OO!~0
．． It is corrected to ``contains 2 moles.''

4) Page 30, line 1 "!go" “1!nlJ and correct it.

Procedural amendment 600t/Mr. Tsubohi, Commissioner of the Japan Patent Office 1, Indication of the case Showa! 2nd year patent application No. 2360! No. 2,
Title of the invention Halogen roux color photographic light-sensitive material 3, relationship to the case of the person making the amendment Appointment of patent applicant Location 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (52)
0) Fuji Photo Film Co., Ltd. Representative Minoru Ohnishi 4
To 77, ゛・355. 4. Subject of amendment Column 5 of "Detailed Description of the Invention" of the description Contents of the amendment The description in the "Detailed Description of the Invention" section of the description will be amended as follows.

(1) Change -C(CHa)CH2C(CH3)3 on page 10, line λ to -C(CHa
) 2 CH2C (CHa ) a.

(2) The chemical structural formula on page io and correct it.

(3) Chemical structural formula of page 1/B and correct it.

(4) The chemical structure of the 4th page EX-/ is EX-/ and correct it.

(5) The chemical structural formula of EX-1' on page ≠ is EX-r and correct it.

(6) Correct the chemical structural formula of UV-/ on page 1j.

Procedural amendment (voluntary) August 9, 1985 1, Indication of the case 1989 Patent Application No. 93605 2, Name of the invention Silver halide color photographic light-sensitive material 3, Person making the amendment Relationship to the case Patent application Address: 6, 7th Floor, Midoriya 2nd Building, 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Number of inventions to be increased by the amendment 0 7. "Detailed description of the invention column" in the specification subject to the amendment 8. Contents of the amendment (1) Add the following statement between lines 7 and 8 on page 4 of the statement.

"On the other hand, when an image dye is contacted with a polyvalent metal ion, this method requires the use of a specific metal chelating group as a color developer or coupler such that a multidentate metallized dye can be formed." Moreover, the process of metallizing the dye image was added as a processing step, which was not satisfactory in practical terms.'' (2)
) In the same book, page 4, line 9, [Improve the defects and add r next to j.
does not require post-chelation treatment.

(3) Next to "It is a hydrogen atom" on page 9, line 8 of the same book, r In the present invention, it is more preferable that R1 is -CONRR, R3 is a substituted alkyl group, and 4 R4 is a hydrogen atom. -I'll join J.

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material characterized by containing a cyan dye-forming coupler represented by the following general formula (I). General formula (1) where R1 is -CONR3R4, -NHCOR3 or -
NHCONR3R4, where R3 is substituted or unsubstituted aliphatic (including both saturated and unsaturated colors; the same applies hereinafter);
represents an aryl or a heterocyclic group, R4 represents a hydrogen atom, a substituted or unsubstituted aliphatic group, an aliphatic group, or a heterocyclic group; R2 represents -COR5, -CONH2R6, -3
represents O2R5 or -5o2NR5R6, R5 represents a substituted or unsubstituted aliphatic, aryl, or heterocyclic group, and R6 represents a hydrogen atom, substituted or unsubstituted,
It represents an aliphatic group, a ring group, or a heterocyclic group, and X represents a hydrogen atom or a group that can be eliminated by an oxidative coupling reaction with a developing agent. R3 and R4 may be combined to form a nitrogen-containing heterocycle, and R5 and R6 may be combined to form a nitrogen-containing heterocycle.