JPS6169065A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance a coloring property of the titled material and to improve a color-tone and a fastness of the coloring by incorporating a phenolic compd. shown by a specific formula as a coupler forming a cyan dye with a color photographic emulsion layer. CONSTITUTION:The titled material is prepared by coating and forming as the above-described coupler, a color image layer contg. a compd. shown by the formula (wherein R1 is an unsubtd. tertiary alkyl group; R2 is a hydrogen atom, a fluoro atom, an aliphat. group; Ar is a subtd. or an unsubtd. aryl group) on a flexible base material. The cyan coupler is incorporated into the photosensitive silver halide emulsion layer, preferably a red color sensitive silver halide emulsion layer. The cyan coupler shown by the formula is preferably used in an amount of 0.003-1mol, preferably 0.05-0.2mol per 1mol of silver halide.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a cyan dye-forming coupler, particularly a cyan dye-forming coupler having a fluorine-substituted aliphatic carboxylic acid amide group in the co-position and an aromatic primary amine color developing agent in the hi-position. The present invention relates to a silver monohalide color photographic light-sensitive material containing a novel phenolic cyan dye-forming coupler having a carbonamide group at the 5-position of an aryloxy group which can be separated by a coupling reaction with a silver monohalide compound.

(Prior Art) When a silver halide photographic material is exposed to light and then subjected to color development, an oxidized aromatic primary amine developer and a dye-forming coupler react to form a color image. Generally, in this method, the decrease (0″″′”″: p; m*”
08.1."."'50, yellow, magenta, and cyan color images, which are complementary colors, are formed. For the formation of cyan images, phenol derivatives or naphthol derivatives are used as cyan dye-forming couplers (
It is often used as a cyan coupler (hereinafter referred to as a cyan coupler). In color photography, color-forming couplers are added to the developer solution or incorporated into light-sensitive photographic emulsion layers or other color image-forming layers, and react with the oxidized product of the color developer formed by development. to form a non-diffusible dye.

The reaction between the coupler and the oxidized form of the color developing agent takes place at the active site of the coupler, and couplers that have a hydrogen atom at the active site are hi-equivalent couplers, i.e., they have a stoichiometric ratio of 1 to 3 to form 1 mole of dye. moles of silver halide. On the other hand, those having a group capable of leaving as an anion at the active site are 2-equivalent couplers, that is, couplers that require only λ mole of silver halide stoichiometrically to form 1 mole of dye. Therefore, compared to μ-equivalent couplers, the amount of silver halide in the photosensitive layer can generally be reduced and the film thickness can be made thinner, making it possible to shorten the processing time of the photosensitive material and further improving the sharpness of the color image formed. .

In recent years, in photosensitive materials with high sensitivity or high image quality, and in systems with simplified development processing, cyan couplers do more than just form cyan dyes (
For example, high solubility in organic solvents, good dispersibility in the emulsion dispersion or silver halide emulsion layer, good developability, good chemical stability of the coupler, and formation. The pigment must be robust to light, heat, and humidity, and the color density, gradation, and sensitivity must be high, and the color development property must be good.
A cyan coupler having various characteristics such as a desirable color hue is desired, and efforts are being made to find cyan couplers having such characteristics.

For example, U.S. Pat. No. 2,772,162 discloses cyan couplers consisting of λ,j-cyacylated noaenols. Although these couplers have excellent characteristics such as their color-forming dyes being particularly fast to heat and humidity, they have the disadvantage that their hues are shorter in wavelength than desirable hues.

In contrast, U.S. Patent No. 2. ≠ The coupler made of copmylamino-t-chloro-monosubstituted phenols described in the specification of No. However, the coloring dye had the disadvantage of insufficient fastness to heat and humidity.

Furthermore, for example, US Patent No. 2! The phenolic cyan coupler having a perfluoroalkylcarbonamide group at the 1-position as described in the specification has excellent properties such as the hue of the coloring dye at long wavelengths and being particularly fast to heat. It had characteristics. However, many of these couplers are ≠ equivalent couplers, and their color development is not necessarily sufficient (and their solubility in organic solvents and their dispersion in emulsions for oil protection dispersion or photographic emulsions) are not necessarily sufficient. Stability was also not always sufficient.

Attempts have been made to improve color development, particularly with naphthol-based cyan couplers, and U.S. Pat.
No. 4c74,143 describes naphthol couplers having 7 arylox groups as the leaving group. However, the coloring properties of this type of couplers were still insufficient. Furthermore, Tokukai Akira! In the specification of Ko-44/Kota, carboxymethyloxy groups, 3-carboxymethyloxy groups, etc. are removed, and in VC of JP-A-4-27/Ko-7, ni(carboxymethylthio)ethoxy groups, etc. are removed. An alkoxy group is disclosed as the group, and as described, these couplers had extremely excellent color forming properties.The 2-equivalent naphthol-based cyan coupler with an alkoxy group as the leaving group had excellent color development properties. It is currently widely used in light-sensitive materials, mainly color negative films, due to its color-forming properties and the long-wavelength hue of the color-forming dye.

However, the color development f of Su7tall couplers is
In addition to the low fastness of the dye to heat, it also has the disadvantage that the color density decreases when a tired bleaching solution or a bleaching solution with weak oxidizing power is used in the development process.

Furthermore, the hue of the coloring dye of the naphthol coupler is on the relatively long wavelength side, which is certainly a preferable hue for color negative film-based light-sensitive materials, but it is also suitable for so-called color positive film-based light-sensitive materials such as color reversal film and color paper. For example, the hue at longer wavelengths is not necessarily preferable (- it lacks film properties).

(Problems to be Solved by the Invention) The first object of the present invention is to provide a silver halide color photographic light-sensitive material using a novel phenolic cyan coupler that has excellent color-forming properties and excellent hue and fastness of the color-forming dye. Our goal is to provide the following.

A third object of the present invention is to provide a silver halide color photographic light-sensitive material using a novel phenolic cyan coupler that has excellent solubility in organic solvents and dispersion stability in emulsified dispersions or photographic emulsion layers. There is a particular thing. - (Means for Solving the Problems) The objects of the present invention have been achieved in a cyan dye-forming coupler represented by the following general formula (IJ) and a silver halide color photographic light-sensitive material containing the same.

General formula CI) r represents a substituted or unsubstituted tertiary alkyl group or a group represented by the following general formula (IIJ), where %R2 is a hydrogen atom, a fluorine atom or an aliphatic group, and Ar is a Represents a substituted or unsubstituted group.

General formula ([] [wherein,
Nitro group, cyano group, sulfo group or -R, -OR, -
8R1-8O2R1-COR, -COOR, -8o20
R, -0COR.

represents the group shown. However, R is an aliphatic group, an aromatic group, or a heterocyclic group, and R' and R'' are a hydrogen atom, an aliphatic group,
Ding represents an aromatic or heterocyclic group. m represents an integer from / to j, and when m is plural, asit may be the same or different. However, out of R5 of (Rs)m, a small amount (tomo/@
Substitute at the position ortho to It@X. ] Here, the aliphatic group represents a linear, branched, or cyclic alkyl group, alkenyl group, or alkenyl group, and may be substituted.

The aromatic group refers to a substituted or unsubstituted monocyclic or condensed ring aryl group, and the heterocyclic group refers to a substituted or unsubstituted monocyclic or condensed ring heteroatom-containing group.

Next, preferred substituents in general formula (I) will be described. R
1 is preferably a substituted or unsubstituted tertiary alkyl group having a total carbon number of μ to 32 (e.g. t-butyl group, /, l-dimethylbutyl group, /-methyl, l-ethylpropyl JL
i t i-si'y--chloroethyl group, adamantyl group, etc.) or a general formula (II
).

R2 is preferably a fluorine atom or an alkyl group substituted with at least one fluorine atom of ~20 carbon atoms, such as -CzF's%-C6Fl35-C3F17, -
CF2H5(CF2)3H5-(CF2)5H,-(C
F, )7H1-(CF2)9H, etc. Ar is preferably a substituted or unsubstituted aryl group having a total carbon number of 6 to 0 (1°·t!lag(7)flL!=L,, 1pa/
y'=yKpublished猷°"'Tsurous atom, chlorine atom, bromine atom, etc.), hydroxy group, carboxy group, nitro group, cyano group, sulfo group, aliphatic group (e.g. methyl group, ethyl group, i
-propyl group, t-butyl group, 5ec-amyl group, t
-amyl group, n-hegycyl group, cyclohexyl group, t-
hexyl group, t-octyl group, t-acyl group, n-dodecyl group, n-1tadecyl group, trifluoromethyl group,
(allyl group, benzyl group, etc.), aromatic group (e.g. phenyl group, p-to-IJ group, etc.), alkoxy group (e.g. methoxy group, ethoxy group, n-7toxy group, n-octyloxy group%n-dodecyloxy group), 7 groups, methoxyethoxy groups, etc.), aryloxy groups (e.g., phenoxy groups, methoxy groups, diphenol groups, etc.), arylthio groups (e.g., methylthio groups, etc.), arylthio groups (e.g., phenylthio groups, etc.), alkylsulfonyl groups (e.g., methylsulfonyl group, ethylsulfonyl group, flobylsulfonyl group, butylsulfonyl group, benzylsulfonyl group, etc.), arylsulfonyl & (e.g., phenylsulfonyl group, p-
7-chlorophenylsulfonyl group in hydro, diphenylsulfonyl group in p-benzylo group, 3-chlorophenylsulfonyl group in Hirobenzilo group, etc.), acyl group (e.g. acetyl group, benzoyl ring group, alkoxycarbonyl group (e.g. methoxycarbonyl group), group, ethylsulfonyl group, dodecyloxycarbonyl group, etc.), alkoxysulfonyl group (e.g., ethoxysulfonyl group, ethoxysulfonyl group, etc.), acyloxy group (e.g., acyloxy group, benzoyloxy group, etc.), carbonamide group (e.g., acetamido group, tetradecane group, etc.) Amide group, Co(λ1 μm
ert-amylphenoxy]butanamide group, trifluoroacetamide group, etc.), sulfonamide group (e.g. methanesulfonamide group, hexadecanesulfonamide group, toluenesulfonamide group, etc.), carbamoyl group (e.g. carbamoyl group, dimethylcarbamoyl group, dodecylcarbamoyl group) etc.), sulfamoyl groups (e.g., sulfamoyl group, dimethylfur7amoyl group, hexadecylsulfamoyl group), Vide groups (e.g., methylureido group, phenylureido group), etc. As Ar, A substituted aryl group is preferred, and when a plurality of substituents are present, the substituents may be the same or different.The number of substituents is preferably 1 to 3, and at least one substituent is an aliphatic group or an alkoxy group. It is preferable that

The most preferred Ar is one in which one of the substituents is an aliphatic group and is substituted at a position para to the oxygen atom bonded to the active position, that is, the diagonal position of the phenol nucleus of the coupler.

Preferred substituents in general formula (II) are as follows. R3 and R4 are preferably a hydrogen atom or an aliphatic group having a total carbon number of 1--hiro (e.g., methyl group, ethyl group, t
-propyl group, n-butyl group, n-hexyl group, n-decyl group, n-dodecyl group or aromatic group (e.g. phenyl group, μ-acetamidophenyl group, sulfonamidophenyl group, etc.) Preferably, one of R3 and R4 is an aliphatic group or an aromatic group. X is preferably an oxygen atom. Substituents up to subatomic ureido groups can be mentioned.However, among (Rs)m, only a few (all 7 R5) are substituted at the position ortho to X, and in this case, R5 is an aliphatic group. preferable.

Among the groups represented by the general formula (II), a group represented by the following general formula (III) is more preferable.

General formula (III) In the formula, R6 and R7 are linear or branched alkyl groups having 1-hi carbon atoms (e.g. methyl group, ethyl group, i-propyl group, 5ec-butyl group, t-butyl group, 5ec-butyl group, -amyl group, t-amyl group, -hexyl group, t-octyl group, n-nonyl L -decyl group, n-dodecyl group, t
-pentadecyl group, etc.], and R8 is the number of carbon atoms/-22
Straight chain f ″″″6″″″″109°″″1゛7
'' group, n-propyl group, i-propyl group, n-butyl group, n-hexyl group, n-octyl group, n-decyl group, n
-Represents a dodecyl group.

The coupler of the present invention has a fluorine-substituted aliphatic carboxylic acid amide group at the co-position, an aryloxy group as a leaving group at the hi-position,
It is a phenolic cyan coupler whose main feature is that it has a carbonamide group at the 5th position.

Conventionally known couplers having a fluorine-substituted aliphatic carboxylic acid amide group at the 2-position and a carbonamide group at the 5-position, or their φ-substituted versions, have long-wavelength hues and are fast to heat. It also had the feature that the color density did not decrease even when bleaching was performed using a tired bleaching solution or a bleaching solution with weak oxidizing power. On the other hand, it had drawbacks such as insufficient color development and low solubility of the coupler in organic solvents (particularly low dispersion stability).

In particular, for the purpose of improving color development, 2-equivalent couplers, in particular couplers with an alkoxy group as a leaving group, have been studied in the same way as naphthol couplers. Tokukai Shoj≦−core 1
No. 7 discloses a coupler having a λ,3-di(calcexymethylthionepropyloxy group), and JP-A No. 7 discloses a coupler having a cyanobenzyloxy group as a leaving group. It is true that this stronger alkoxy group was effective in improving the coloring properties of 7-tole couplers, but surprisingly no such effect could be observed with this type of phenolic coupler. The inventors investigated a coupler having an aryloxy group as a leaving group at the top position and found that it had excellent coloring properties.This fact is similar to that of naphthol, which is similar in structure and chemical properties. This was completely unexpected and surprising considering the behavior of the couplers of the present invention.The couplers of the present invention can also be used in low-boiling organic solvents such as ethyl acetate and butyl acetate, as well as in dibutyl phthalate, dioctyl phthalate, didodecylphthalate, and tricresyl. It was also found that it has excellent solubility in high-boiling solvents such as phosphenol and trioctyl phthalate, and has excellent dispersion stability in emulsified dispersions or silver halide emulsion layers.The reasons for this are as follows. For example, this may be considered to be an effect of a relatively hydrophobic, or in other words, lipophilic, aryloxy group in the positive position.

Couplers of similar construction to the couplers of the present invention are disclosed in US Pat. The difference between this coupler and the coupler of the present invention is that there is no substituent at the ortho position of the phenol group substituted at the 2-position of the carbonamide group at the 5-position, and the hue of the coloring dye of this coupler is The wavelength was shorter than the preferred spectral absorption region.

The preferable hue or spectral absorption of the coloring dye of the coupler of the present invention is brought about only when R1 is a tertiary alkyl group or a group represented by the general formula (IJ).

Examples of the appearance of the phenolic cyan coupler according to the present invention are shown below.

r The coupler of the present invention can be synthesized, for example, by the synthetic route shown below.

A r A r A B r r Compound A is a patent application! It is synthesized by the method described in the specification of 2211≦θ. Compound B is compound A and acid anhydride (R2CF2CO)20 or acid chloride R2CF
2coα or in the presence of a base (e.g. pyridine, triethylamine, etc.) between the compound and compound B,
It is synthesized by adding thionyl chloride and reacting.

Compound C can be obtained by reducing compound B with iron powder or with hydrogen in the presence of ζ radium carbon. The final coupler is compound C and acid chloride R.
ICOα and acetonitrile, dimethylformamide,
React in a polar bath medium such as dimethylacetamide, or
It is synthesized by reacting Compound C and carminic acid RICOOH in the presence of a condensing agent such as dicyclohexylzediimide or carbonyldiimidazole. Examples of synthesis of couplers of the present invention are shown below.

Synthesis Example 1 Synthesis of Exemplary Coupler (3) Compound (3A), namely -mono-amino-y-nitro≠-
(4!-tert-Octylphenoxy) phenol was synthesized by the method described in the specification of patent application Sho!ter/-2≠60.Melting point /17~/rta0C compound<3h) 3z, rg and pyridine Dissolve in 3゜71 dimethylformamide λ00tttt and cool with water to add 2J of butafluorobutanoic acid,! Then, thionyl chloride I was added dropwise over about 30 minutes. After dropping, stir at room temperature for 3 hours, add 100 d of water and add ethyl acetate JOO.
Extracted with ml. The ethyl acetate layer was washed twice with JOOIItl water and then concentrated using an evaporator. Concentrate contains n-
QOytl was added to the mixture, heated and dissolved, and then crystallized. The precipitated yellow crystals were filtered, washed with n-hexane, and dried to give compound (3B), ie, λ-hebutafluorobutanamide-yo-nitrog-(tA-ter
t-octylphenoxy)phenol≠f
lr,! /i got it. Melting point/Hiroshi 5~/4c7°C Iron powder 2! , u, @ were added with water//ml, acetic acid jrttl and isopropyl alcohol, and heated to reflux. Compound (3B
) to J! , 3fi were added, and the mixture was heated under reflux for 2 hours.

The reaction solution was filtered, and the p solution was concentrated. Ethyl acetate and n-hemisan were added to the concentrate, dissolved by heating, and then crystallized. The precipitated crystals were filtered, washed with n-heimisosan, and dried to form compound (3C), ie! -amino-λ-hebutafluorobutanamide-tA-(IA-t er t
-Octylphenoxy)fer was obtained as JO. Melting point: 16 λ~l The compound (JC)/J,/fi was dissolved in dimethylacetamide and stirred at room temperature, followed by 2-(2, Tart-amylphenoxy)butanoyl chloride. /i was added dropwise. 30
After stirring for a minute, JOOrttl water was added, and the mixture was extracted with Co00d vinegar/ethyl acetate. The ethyl acetate layer was diluted with 200%
After washing twice with rnl water, it was concentrated. Methanol/jOml was added to the concentrate and the mixture was dissolved by heating, followed by crystallization. The precipitated crystals were filtered, washed with methanol, and dried to obtain the desired exemplary coupler (3) /7.44I.

Melting point/l4cm/It'C Synthesis Example 2 Synthesis of Exemplary Coupler (4) 7 g of the above compound (JC)/j was dissolved in dimethylacetamide rOmlK, and 2-(2,I
A-tert-amylphenoxy) to sanoyl chloride/2. /i was added dropwise.

After stirring for 30 minutes, JOOml of water was added and extracted with 200ml of ethyl acetate. Coat the ethyl acetate layer.
After washing twice with water, the solution was concentrated. 2 methanol to concentrate
oovtl was added and dissolved by heating, followed by crystallization.

The precipitated crystals were filtered, washed with methanol, and dried to obtain 3 g of the desired exemplary coupler at 23°. The cyan coupler of the present invention can be used in various color photographic materials. Typical examples include color negative film for photography (for general use, movies, etc.), color τ reversal film (for slides, movies, etc.), color photographic paper, color positive film (for movies, etc.), and color reversal photographic paper. By mixing, it can also be used in black and white photographic materials (for example, for X-ray, general photography, etc.).

The coupler of the present invention or the couplers that can be used in combination as described below can be introduced into the light-sensitive material by various known dispersion methods.
Typical examples include a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. In the oil-in-water dispersion method, the boiling point is /
7! After dissolving in either a high boiling point organic solvent of 0C or higher and a low boiling point so-called auxiliary solvent, either alone or in a mixture of both, it is finely dispersed in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant. Examples of high boiling point organic solvents are described in U.S. Pat. Dispersion may be accompanied by phase inversion (and, if necessary, auxiliary solvents may be removed or reduced by distillation, noodle washing, or ultraponic methods before use for coating).

More detailed examples of high-boiling organic solvents include phthalate esters (dibutyl phthalate, dicyclohexyl phthalate, dicoethylhexyl phthalate, didodecyl phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, co-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate), tri-J-ethylhexyl phosphate, tridodecyl phosphate, trypto-diethyl phosphate, trichloropropyl phosphate, di-λ-ethylhexyl phenyl phosphate, etc.), Benzoic acid esters M (2-ethylhexyl benzoate, dotesyl benzoate, coethylhexyl-p-troxybenzoate, etc.), amides (diethyl dodecanamide, N-tetradecyl pyrrolidone, etc.), alcohols or phenols ( instearyl alcohol, co1μm di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, instearyl lactate, trioctyl citrate, etc.)
, aniline derivative (N, N-dibutyl-cobutoxyj-tert-octyl, /I/7= +7 y
ttE) % *(lz＊＊＊(/497(:/, )
(decylbenzene, diinopropyl naphthalene, etc.), and as co-solvents, solvents with a boiling point of about 30'
to about 16°C, examples of which include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, λ-ethoxyethyl acetate, dimethylformamide, and the like.

The process and effects of the latex dispersion method and specific examples of latex for impregnation are described in U.S. Pat. .

No. 363, OLS Daiichi #j Hiro/, = No. 74A and OL
It is described in S No. Ko, jIAg, No. 238, etc.

The cyan coupler of the present invention is incorporated into a light-sensitive silver halide emulsion layer, preferably a red-sensitive silver halide emulsion layer. 0°003-1 mole per 7 moles of silver halide, preferably 0.003-1 mole. DO! Preference is given to using -0.2 mol of the cyan coupler of the invention.

In the present invention, various color couplers can be used in combination with general formula (I). The term "color coupler" as used herein refers to a compound that can react with an oxidized product of an aromatic primary azun developer to form a dye. Typical examples of useful color couplers include naphthol or other phenolic compounds, pyrazolones or pyrazoloazole compounds, and open chain or heterocyclic ketomethylene compounds. Specific examples of cyan, magenta, and yellow couplers that can be used in the present invention are RD/74 Hiro
Section D, described in the patent cited in 17/7//y72///.

Preferably, these couplers have ballast groups or are polymerized and diffusion resistant. It is preferable that the coupling position is substituted with a leaving group rather than a hydrogen atom. Couplers in which the chromophoric dye exhibits brightening diffusivity, colored couplers, colorless couplers, or couplers which release development inhibitors or accelerators upon the 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 U.S. Patent No. 2,44
No. 07,210, No. 2.1r7j, 0! It is described in R7 Oni and J, No. 211,104. The F14Vc) family-equivalent yellow couplers of the present invention can be preferably used and are described in US Pat. No. J, tAOr, /Fll-, US Pat. z
Oxygen atom separation type yellow couplers described in No. oi No. Oyo and No. II-, (40/, 7j2, etc.) or Japanese Patent Publication No. 1!-10732, U.S. Patent No. Hiroshi, Oko λ, 620
No., Hiroshi No. 32t, No. oλj, RT)/l0jJ (J
(Hirozuki, 1997), British Patent No. I, IAxz, 117λO
No., West German Application Publication No. 21λ/? , Def No. 7, No. 2.2
1. /, Jla1, same cylinder λ, 32? ,! No. 17 and No. 2゜μs3. A representative example of this is the nitrogen atom separation type yellow coupler described in RI No. 2, etc.
Le. The .alpha.-pivaloylacetanilide coupler i5- is characterized by the fastness of the chromophore, while the .alpha.-benzoylacetanilide coupler is characterized by good color-forming properties.

Examples of the magenta coupler that can be used in the present invention include indazolo or cyanoacetyl couplers such as those of oil protector, preferably pyrazoloazole couplers such as j-pyrazolone and pyrazolotriazoles. ! The -pyrazolone coupler is preferably one in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color development rate of the chromophore, and typical examples thereof include:
U.S. Patent No. 2,31/,012, U.S. Patent No. 2,3≠3゜7
No. 03, No. 2. ≦00,7tt No. 2゜201.
No. 173, No. 3,042.43; No. 3, No. 3. /j
No. 2,116 and No. 31, No. 34 ois, etc. 2 equivalents! - Pyrazolone couplers are preferred, and the leaving group is preferably a nitrogen atom leaving group as described in U.S. Pat. . Furthermore, pyrazolone couplers having a ballast group as described in European Patent No. 73 and AJJ have high color-forming reactivity. As a pyrazoloazole coupler, rice f
National Patent No. 3,362. ryZ, preferably the pyrazolobenzimidazoles described in US Pat. No. 3,72!
, Pyrazolo (j, /-C) C/ described in 0 Otsu No. 7
+2. Examples include the pyrazolotetrazoles described in Hiro J Triazoles, RI) 2 Hiro 220 (/RI r Hiro year 220) VC and the pyrazolopyrazole described in RD214230 (/911I-Year 220).

The imidazo(//
, 2-b] Pyrazoles are preferred, and pyrazolo(/,j-t)J (/
, 2. [Hiroshi] triazole is particularly preferred.

Cyan couplers that can be used in combination with the present invention include naphthol-based and phenol-based couplers from Oil Protect Kochi, and US Pat. 71A, 223, preferably U.S. Pat.
1 Co., No. 212, Hiroshi No. 1, /444. Jri No. 4, No. 1
A, 22! r, 2J, No. 3 and the same No. 3, λri≦, 20
A typical example is the highly active 2-equivalent 7-toll coupler of the oxygen atom elimination type described in No. 0. Specific examples of phenolic couplers include U.S. Pat.
No. 2. Piλj, No. 730, No. 772.1
No. 6-, No. 2, 10/171 and No. 2. It is described in rriyo, +26 issue, etc.

Cyan couplers that are robust to humidity and temperature are preferably used in the present invention, typical examples being the phenolic cyan couplers described in U.S. Pat. No. 3,772,002, U.S. Pat. No. 2,772.142; 3rd and 7th I
, No. 301, Hiroshi.

12 &, J Riwo No., same No. 13 IA, oii No., same No. 1, 327. /73, West German Patent Publication No. 3゜327.
722 and Japanese Patent Application No. 2677, etc., and U.S. Patent No. 3. Hirohiro A, Aλλ issue, same issue μ, 33
! , Tatata No., Hirohiro, Hirori, Sr., and Mu, No. 1127,767, etc., which have a phenylureido group at the λ-position and! A phenolic coupler having an acylamino group at the - position.

The coupler of the present invention and the couplers described above can be used in combination of two or more types in the same layer in order to satisfy the characteristics required of a photosensitive material, or the same compound can be added to two or more different layers. Of course it doesn't matter.

In order to correct unnecessary absorption in the short wavelength region of the magenta and cyan coupler chromophores, it is preferable to use a colored coupler in combination with the color photosensitive material for photographing. U.S. Patent No.≠, /Aj, j70 and Special Publication Shory-iy
Yellow-colored magenta coupler described in μ73, etc. or U.S. Patent No. e, ooa, Octopus No. 2, No. 4c, /
31,2J-1 and British Patent No. 1. /Hiroshi 4.361
A typical example is the magenta-colored cyan coupler described in No.

These color couplers may form a polymer of No. 2 or higher. Typical examples of polymerized couplers (Eng., U.S. Patent No. 3. Reference!/, r-0 and Douhiro).

oro, No. 2ii. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102/73 and US Pat. No. 1I-,347,21! It is listed in No.

In addition, the graininess can be improved by using a chromophore diffusing coupler in combination, and such coupler 1 is disclosed in U.S. Patent No. tt.
, st&, co 37 and British Patent No. λ.

/, 2j, 170, and European Patent No. 173 and West German Patent Publication (OLS).
) 3.32 Hiroshi, J-JJ) describes specific examples of yellow, magenta and cyan.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used alone or together with gelatin.

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. Preferred silver monohalide is l! Silver iodobromide containing silver iodide with f less than molti 1 to 6 is particularly preferred.Silver iodobromide containing silver iodide from 011 comolti to 72 comolti is preferred.

The average grain size of silver halide grains in photographic emulsions (in the case of spherical or approximately spherical grains, the grain diameter is expressed as a ridged grain size in the case of cubic grains, and the average grain size is expressed as a percentage of the projected area) is particularly important. Although it does not matter, it is preferably 3μ or less.

The particle size distribution can be narrow or wide.

Silver halide grains in photographic emulsions may have regular crystal structures such as cubic or hexagonal (also spherical,
It may have an irregular crystalline shape such as a plate shape, or it may have a composite shape of these crystalline shapes. It may also consist of a mixture of particles of various crystalline forms.

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

The silver halide grains may have different phases inside and on the surface. Further, it may be a flow particle in which latent blinds are mainly formed on the surface, or a particle in which latent blinds are mainly formed inside the particles.

The photographic emulsion used in the present invention is I', Glafkide.
Written by Chimia et Physique Photo
graphique (published by Paul monte1,
/ri 47 years) Photogra by G. F. Duffin
phicEmulsion Chemistry (T
he Focal Press, /'146), V
, L., Zel ikmanat al. Mak
Ingand CoatingPhotography
c Emulsion (The Focal Pre
It can be adjusted using the method described in, for example, published by SS, /yi4I-year. That is, any of the acidic method, neutral method, ammonia method, etc. may be used (Also, the method for reacting the soluble silver salt with the soluble halogen salt may be one-sided mixing method, simultaneous mixing method, or a combination thereof. Good too.

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

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase from which silver halide is removed can be kept constant, ie, the so-called Chondrald double jet method can also be used.

According to this method, a silver halide emulsion with a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, sulfur salts or complex salts thereof, iron salts or iron complex salts, etc. may be allowed to coexist. .

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example H, Frleser la
@Die Grundlagender Photog
raphischenprozesse mit S
ilber-halogeniden'' (Akadem
ische VerlagsgesellschafL
/Y41) The method described in A7 Yo-7373 Hiroshi can be used.

Namely, sulfur sensitization using sulfur-containing compounds that can react with activated gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); , amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); noble metal compounds (for example, total complex salts as well as pt, I
A noble metal sensitization method using complex salts of metals of group 1 of the periodic table such as r, Pd, etc. can be used alone or in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, beromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles1. Aminotriazoles, benzotriazoles, nitro, benzotriazoles, mercaptotetrazoles (especially /-phenyl-!-mercaptoteto” 5l-y) txt
;'ykaiht'J i 77yu;7゜captotriazines; thioketo compounds such as oxadolinthione; azaindenes, such as triazaindenes, tetraazaindenes (especially μm hydroxy-substituted (/, J, Ja, 7) Tetraazaindenes), Pentaazaindenes, etc.; Many compounds known as anti-capri agents or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. can be added.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide, tt ether, ester, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development.
It may also include derivatives such as amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or releasable synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability.

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar-cyanine dyes, hemicyanine dyes, styryl dyes and hemioquinol dyes. Particularly useful pigments are pigments belonging to cyanine pigments, melonanine pigments, and complex merocyanine pigments. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes.

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

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostyl compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Pat. No. 233.390, 433',
72/), aromatic organic acid formaldehyde condensates (e.g. those described in U.S. Pat. No. 3.7≠3,110), cadmium salts, azaindene compounds, etc. It can also be applied to multilayer, multicolor photographic materials with different spectral sensitivities on a support. Each layer has a small number of layers (each has one layer. The order of these layers can be arbitrarily selected according to needs. The red-sensitive emulsion layer has a cyan-forming coupler, the green-sensitive emulsion layer has a magenta-forming coupler, and the blue-sensitive emulsion layer has a yellow-forming coupler. Typically, each of the forming couplers is included, but different combinations may be used depending on the case.

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

For example, activated vinyl compounds (/, J.

! -triacryloyl-s-triazine, 7,3-vinylsulfonyl-copro/ξnor), active halogen compound (2,41-dichloro-t-hydro-s-t'J-azine), Mucohalogen acids (mucochloric acid, mucophenol dichloroic acid, etc.), etc. can be used alone or in combination.

The light-sensitive material produced using the present invention may contain a hyde non-derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.

The photosensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, U.S. Patent No. J,! J.J.
, No. 72φ, No. 14.2Jt, No. 0/J, Tokko Akira!
Aryl group-substituted benzotriazoles described in /-474CO and European Patent No. 7.160, etc.; Butadienes, US Patent J, 70j.

101 and J, 707,37, U.S. Patent No. 3. Kol! ,yo f J
O, Oyo U'jA5** / , j 2 / , J
Benzophenones described in U.S. Pat. Nos. 3,741.27- and 4c, 443/, 7J
A polymer compound having ultraviolet absorbing residues as described in No. 4 can be used. U.S. Patent No. 3. Pitata, 7
jλ and same j, 700, ≠j! Ultraviolet-absorbing fluorescent brighteners described in this issue may also be used. Typical examples of ultraviolet absorbers are described in RD2 Ko 23 (/ri rtA, February 2013).

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioquinol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, osanonol dyes; hemiononol dyes and merocyanine dyes are useful.

In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of one or more. Known anti-fading agents include hyde non-derivatives, gallic acid derivatives, p-alkoxyphenols, p-o-diphenol derivatives, and hibisphenols.

The color photographic emulsion layer forming the dye image layer according to the present invention is coated on a flexible support such as plastic film, paper, or cloth commonly used in photographic light-sensitive materials. Useful as flexible supports are films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose acetate butyrate, polystyrene, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers (e.g. polyethylene, polypropylene, etc.). ) etc. Fully coated or opaque paper etc. The support is dyed.

It may be colored using dyes or pigments. It may be made black for the purpose of blocking light.

When these supports are used for reflective materials, it is preferable to add a white pigment to the support or laminate layer. White pigments include titanium dioxide, barium sulfate,
Examples include zinc oxide, zinc sulfide, calcium carbonate, antimony dioxide, silica white, alumina white, titanium phosphate, etc., and titanium dioxide, barium sulfate, and zinc oxide are particularly useful.

The surface of these supports is generally treated with an undercoat to improve adhesion with photographic emulsions, etc.The surface of the support may be treated with corona discharge, ultraviolet irradiation, etc. before or after the undercoat treatment. good.

When these supports are used for reflective materials, a hydrophilic colloid layer containing a high density of white pigment may be further provided between the support and the emulsion layer to improve the whiteness and sharpness of the photographic image. can.

In the reflective material having the magenta coupler of the present invention, a paper support laminated with a polymer is often used as the support, but if a synthetic resin film kneaded with a white pigment is used, smoothness, gloss, sharpness, In addition to improving the degree of
This is particularly preferable since it provides a photographic image with particularly well-defined saturation and dark areas. In this case, the synthetic resin film raw material is
Polyethylene terephthalate and cellulose acetate are particularly useful as white pigments, and barium sulfate and titanium oxide are particularly useful.

In addition to the above, various photographic additives known in this field, such as stabilizers, antifoggants, surfactants, antistatic agents, developing agents, etc., may be added to the color photographic material of the present invention as necessary. Examples can be found in Research Disclosure/7ttAJ.

Furthermore, in some cases - a fine-grain silver halide emulsion having substantially no photosensitivity in the silver halide emulsion layer or other hydrophilic colloid layer (e.g., silver chloride, silver bromide with an average grain size of Q or less) , silver chlorobromide emulsion) may be added.

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, ≠-amino-N, N-diethylaniline, 3-methyl-≠-amino-N, N-diethylaniline, μmamino-N-ethyl-N-β-H (F,.ya7.f2 A=1,7.7-~
2-7-77 No N-ethyl-N-β-hydroxyethylaniline, 3-methyl-Hiro-amino-N-ethyl-N
-β-methanesulfamide ethylaniline, Hiro-a 1)
Representative examples include -3-methyl-N-ethyl-N-β-methoxyethylaniline.

The color developing solution contains pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors such as bromides, iodides, and organic anti-capri agents, and antifoggants. can be included. In addition, if necessary, water softeners, preservatives such as hydrolyzylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competition coupler,
Fogging agents such as sodium boron hydride, l-
Auxiliary developers such as phenyl-J-pyrazolidone, viscosity-imparting agents, polycarboxylic acid chelating agents as described in U.S. Pat.
22. It may also contain antioxidants as described in No. 1.

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 (■),
Compounds of polyvalent metals such as cobalt (■), chromium (■), and copper (II), peracids, quinones, and nitroso compounds are used. For example, ferricyanide, dichromate, iron(III) or cobalt(I[I) organic complex salts,
For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, l
, 3-diamino-1-propanoltetraacetic acid, and other aminopolycarboxylic acids, or complex salts of organic acids such as citric acid, tartaric acid, and malic acid: persulfates, manganates, and nitrosophenols.

Of these, potassium ferricyanide, sodium iron(III) ethylenediaminetetraacetate, and ammonium iron(II) ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron (In) complex salts are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

The cyan coupler of the present invention has the feature that the cyan coloring density does not decrease even when a light-sensitive material is processed in a bleach-fix bath using a bleaching agent with weak oxidizing power or in a tired bleach-fix bath.

After color development or bleach-fixing treatment (may be washed with water).

Color development can be carried out at any temperature between /r'c and zz 0c. Preferably 30°C or higher, particularly preferably 30°C or higher
Color development is performed at 10c or higher.

The development time is preferably as short as about 3 minutes to about 7 minutes. For continuous development processing, liquid replenishment is preferred, and the processing area is 330QC to 40CC per square meter.
, preferably refill nights below /QOQC. Benzyl alcohol in the developer! ml/j or less is preferable. Bleach and fix from /r'c! Although it can be carried out at any temperature of 0'C, it is preferably 3o0C or higher. When it is 3j0c or more, 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 washing can be done within 1 minute 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 color images are particularly susceptible to deterioration due to mold (it is preferable to use a mold preventive agent. Specific examples of mold preventive agents are given in Japanese Patent Application Laid-Open No. 7-112333).
There are =-thiazolylbenzimidazoles as described in 72 Hirohiro. The antifungal agent may be built into the photosensitive material (or may be added externally during the development process, or may be added at any step if it coexists with the processed photosensitive material).

The present invention will be described below with reference to Reference Examples and Examples, but the present invention is not limited thereto.

Reference Example Coupler of the present invention (1) Dibutyl phthalate 2 in J-F
．． Add 5d and ethyl acetate/tubo and heat to 7o0c. The resulting solution is mixed with 10g of gelatin and tr water gi g containing dodecyl benzenesulfonic acid o, rg.

, 'IM71Cfi"ゝ・＆u゛"C-i'-
)f! A fine coupler emulsified dispersion was obtained by stirring at high speed. A gelatin hardening agent was added to the emulsified dispersion and applied to a cellulose triacetate film.
And so. Similarly, couplers of the present invention (21, (3),
Samples were collected for (5) and the following comparative couplers C-/ and C-1, and designated as samples 10λ, io3, IQ Hiro, 10j, and 106, respectively. Sample 10/~107 too
c. When the samples were observed after being left for a week under the condition of 70% relative humidity, it was observed that Comparative Samples 10j and 104 had film defects due to fine precipitation of the coupler. On the other hand, in the sample /θ/~10tA in which the coupler of the present invention was dispersed, the film Nito 9 was not observed.
It can be seen that the coupler of the present invention has excellent dispersion stability in the film and excellent dispersion stability under high humidity conditions.

H C5H11-t H Example 1 Coupler (1) r4. Dibutyl phthalate ≠ 388' in λJ, tricundyl phosphate μJCC
and ethyl acetate rtsaa were added and dissolved in a heating bath with TOOC, and this solution was mixed with 10100 O of an aqueous solution of sOOC containing gelatin ioo, li [and log sodium dodecylbenzenesulfonate. A fine coupler emulsion dispersion was obtained by stirring at high speed with a homogenizer.

Tog of silver was added to 310 g of this coupler emulsified dispersion, and a silver iodobromide emulsion/Kp was prepared in which the molar ratio of silver iodide to silver bromide was z to hiro.
on the cellulose triacetate film support at a coupler coverage of 7 X/0-' mol/rIL.
It was applied so that A gelatin protective layer having a dry film thickness of lμ was applied on this layer to prepare sample λ07.

Couplers of the present invention (3), (41,
(5), (7) and for comparison the above C-/%C-2,
C-j described in JP-A Shoyo+-too4ctA issue, C-Hiroshi described in JP-A No. 22, JP-A Shoj Hiro-A A/22,
4-Core/C-Z described in No. 4c7, U.S. Patent gglL
Sample 2 was prepared by using C-4 described in No.
0/0/ and each sample is 02.20.
3.2011-, Ko Oj, 2041,2 (77,20″
r%2Q resin, 10%, 2// was prepared.

-j 0H C-Hiro-r -A Sensitomet I7 for obtained sample 20/-λ//
- After the exposure for
It was done in c.

1. Color development 3 minutes/j seconds 2 Bleaching White 6 minutes 30 seconds 3. Wash with water 3 minutes/j seconds 4. Fixed arrival μ minutes λO seconds & Water wash 3 minutes/! seconds 6. Stability 3 minutes 71 seconds The composition of the treatment liquid used in each treatment step is as follows.

Color developer sodium nitrilotriacetate /, 01 sodium sulfite, OI sodium carbonate
JO, Oll Potassium Bromide
1.4Afi Hydrobovine Dylamine arR
Salt 2, 4' g Hiro-(N-ethyl-N-β-hydroxyethylamino)-1-methylaniline sulfate Hiro, jI Add water l! Bleach solution ammonium bromide 160,077 ammonia water (λtqlI) Coj, Oxl ethylenediaminetetraacetic acid sodium iron salt /J0. O9 glacial acetic acid
Add water
/1 fixer sodium tetrapolyphosphate, Oy, sodium sulfite, QI thiosulfate 7y%=
um (70%) / 7 j, 0ml sodium bisulfite hiro, t9 add water
/1 Stabilizing solutions Hol, Lin J, and Oral water were added. /1 The concentration of each processed sample was measured using red light. The results are shown in Table 1.

Table 1 As is clear from Table 1, the aryloxy-eliminating couplers of the present invention have higher sensitivity and maximum concentration than 2-equivalent couplers such as μ-equivalent couplers, I. Rodan atom-eliminating couplers, and alkoxy-eliminating couplers. (It can be seen that it has excellent color development.

Table 1 also lists λmaX (unit: nm) determined from the spectral absorption spectrum at the maximum color density.

Comparative coupler C-j had relatively hard color development, but λmax was on the short wavelength side, and the hue was not preferred for practical use.

Example 2 A multilayer color photosensitive material sample was prepared on a cellulose triacetate film support and was designated as sample 30/, having each layer having the composition shown below.

7th layer: anti-halation layer Gelatin layer containing black colloidal silver λth layer: middle layer f　　　Yu,ry-tart-OIf-ni/,I,.

Ya.

Gelatin layer I containing an emulsified dispersion of 3 layers: 1st red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide molar ratio) Silver coating amount / , J 9/m2 Sensitizing dye ■ For 1 mole of silver ≠,! X10 molar sensitizing dye ■ per mole of silver /, Jxlo-' molar coupler E
X-/ o, oil mole coupler E for 1 mole of silver
X-co For 1 mole of silver o, oir molar coupler E
X-3 CD, OOJ moles per mole of silver Coupler EX-μ o, ooor moles per mole of silver μth layer: 4th red-sensitive emulsion layer Silver iodobromide emulsion (10 moles of silver iodide) Silver coating amount 1. μl/Ex 2 Sensitizing dye I J, 0x10 moles per mole of silver Sensitizing dye ■ i, oxio molar coupler EX-j per mole of silver o, oor moles of the present invention Coupler (3) 0.0/7 mole Casolar E for 7 moles of silver
X-j o, ooit mole for 7 moles of silver! Layer: Intermediate layer Same as 2nd layer 6th layer: 1st green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide Hiromorchi) Silver coating amount /, 277/m2 Sensitizing dye■ Per mole of silver Ji , 0X10-'Mole Sensitizing Dye ■ For 1 mole of silver x, oxio-'Coupler EX-
4 0.0 r mol coupler E per 1 mol of silver
X-7 o, oor mole coupler E for 1 mole of silver
X-r 0.00/I mole relative to 1 mole of silver 7th layer: 2nd green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide t mole) Silver coating amount 7.3 g/2 sensitizing dye ■ J, 0X10 moles per mole of silver Sensitizing dye ■ /, JX/ 0 mole coupler EX-2 per mole of silver 0.0/7 mole coupler E per mole of silver
X-10 o, oos moles per mole of silver:
2. Yellow filter with yellow colloidal silver in gelatin aqueous solution. ! -G-t
Gelatin layer containing emulsified dispersion of art-octylhydroquinone Second layer Second first blue-sensitive emulsion layer Silver iodobromide (silver iodide mole %) Silver coating amount 0.7 p/m2 Coupler EX-J/ Silver 1 0.2j mole coupler E per mole
X-/2 0.0/j mole per mole of silver 10th layer:
λth blue-sensitive emulsion layer Silver iodobromide (silver iodide 3 mol S) Silver coating amount o, tg 7 and 2 coupler E
X-// 0.01 mol per 1 mol of silver 11th layer 2@l Protective layer Silver iodobromide (1 mol of silver iodide, average grain size 0.07μ) Silver coating amount o, zp7 horse 2 ultraviolet light Absorbent U
Gelatin layer 72 containing an emulsified dispersion of polymethylmethanoacrylate particles (diameter approx. l).

gelatin layer containing lμ) (. [)’! F Yes, one. Engineering, 2 52 ke, F.

For emulsifying and dispersing 3-divinylsulfonyl-λ-proA-nol, coupler, etc., a high-boiling point organic hexamedia (for example, tricresyl 7-mole 7-ate, dibutyl 7-talate, etc.) and a surfactant were used. The prepared sample was designated as sample 30/.

Compound sensitizing dye m used to prepare the sample: Anhydrotor ethyl! l! '-Dichloro-3,3'-di(r-sulfozolopyl)oxacarbocyanine sodium salt sensitizing dye ■: Anhydro I'! ' l ' l 4'-tetrachloro-
/, l'-diethyl-3,3'-di(β-[β-(r
-Sulfopropoquine]ethoxy]ethylimita'Zolocarbocyanine hydroxide sodium salt EX-/CaHrx(t) EX-J EX-, r EX-4 α EX-4 Coupler of the invention in the μth layer of sample JO/ Samples JO2, 303 and JOIA were prepared by replacing 3) with equimolar amounts of the coupler (5) of the present invention, comparative coupler C-/, and comparative coupler C-Hiroshi. The obtained samples 30/-30≠ were exposed to light for centometry, and then developed in the same manner as in Example 1.

The results of measuring the concentration using red light are summarized in the table.

Table 2 From Table 2, it can be seen that the coupler of the present invention has high sensitivity and gradation (excellent color development).

Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment 1. Incident display: 1st patent application from Showa era/3j≠
No. 26 Name of invention “Silver halide color photographic material 3.
Relationship with the case of the person making the amendment Patent applicant 4, the subject of the amendment, specification 5, and a declaration of amendment (no change in content) of the specification will be submitted.

Procedural amendment December 7, 1965

Claims (1)

[Scope of Claims] A silver halide color photographic material characterized by containing a compound represented by the following general formula [I] as a cyan dye-forming coupler. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 represents a substituted or unsubstituted tertiary alkyl group or a group represented by the following general formula [II],
represents a hydrogen atom, a fluorine atom or an aliphatic group, and Ar represents a substituted or unsubstituted aryl group. General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, atom, hydroxy group, carboxy group, nitro group, cyano group, sulfo group or -R, -O
R, -SR, -SO_2R, -COR, -COOR, -
SO_2OR, -OCOR, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. Represents the group indicated by ▼. However, R is an aliphatic group, an aromatic group, or a heterocyclic group, and R' and R'' are a hydrogen atom, an aliphatic group,
Represents an aromatic group or a heterocyclic group. m represents an integer from 1 to 5, and when m is plural, R_5 may be the same or different. However, at least one of R_5 in (R_5)_m is substituted at a position ortho to X. ]