JPS59174838A - Silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photosensitive material having superior fastness to light and heat and sharp absorption desirable for color reproduction by incorporating a specified cyan dye forming coupler. CONSTITUTION:A silver halide color photosensitive material contains a cyan dye forming coupler represented by the formula shown here in which R<1> is optionally substd. alkyl, aryl, or heterocyclic, preferably, optionally substd. alkyl; Y is optionally substd. alkyl, aryl, or heterocyclic, preferably, optionally substd. aryl or unsaubstd. heterocyclic; and X is R<3> is a group capable of substituting a benzene ring, preferably, H, halogen, nitro, or the like; and X is a group releasable on oxidation coupling reaction with a developing agent, preferably, H, halogen, alkoxy, aryloxy, thio, or azo.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material containing a novel cyan dye-forming coupler.

After the silver halide light-sensitive material is exposed to light, it is subjected to color development treatment, whereby the oxidized aromatic-amine developing agent reacts with the dye-forming coupler to form a color image.

Generally, in this method, a subtractive color reproduction method is used.In order to reproduce blue, green, and red, color images of yellow, magenta, and cyan, which are complementary colors, are formed, respectively.0 Cyan dye Phenols or naphthols are often used as couplers.

However, several problems remain in the storage stability of color images obtained from conventionally used phenols and naphthols. For example, U.S. Patent Co., 3t7, 33/
The color images obtained from the mono-acylaminophenolic cyan couplers described in 2,4123.730 generally have poor heat fastness and are disclosed in U.S. Pat. 2 described in the specification of No. t2. ! The color images obtained from -diacylaminophenolic cyan couplers generally have poor light fastness, and the /-hydroxy-2-naphthamide cyan cyanazoles generally have poor both light and heat fastness.

On the other hand, British Patent No. 0//, 2110 and US IH Patent: j'fj, '111t, /, 2.2, 3.
FF&, , 233.3.7Jtl, 308', 3.
J'IO, t// issue Oyobi Tokukaisho! t-t3;/3'l
, Methane-2011,! 4Lj, 3l-3324t, J-11'-332! Phenolic cyan couplers having a ureido group at the 2-position as described in the specification of No. Although phenolic cyan couplers are said to have better light fastness than the cyan couplers mentioned above, their fastness is by no means sufficient when long-term storage is considered. Further, the absorption of the developed color images obtained by these couplers is broad, and the absorption is large in picture areas that are unfavorable in terms of color reproduction.

? The object of the present invention is to improve these drawbacks and provide a color photographic material using a cyan dye-forming coupler which has excellent fastness to light and heat and has sharp absorption which is favorable for color reproduction.

Another object of the present invention is to provide a coupler which has a high dye formation rate and a maximum color density in a color developer, and in particular, has a sufficiently high rate even in a color developer excluding benzyl alcohol. On the other hand, it is an object of the present invention to provide a coupler that shows almost no decrease in concentration when treated with a bleaching solution having weak oxidizing power or a bleaching solution that is tired.
Another object of the present invention is to provide a coupler that has high solubility in organic solvents and is difficult to crystallize when added to silver halide photographic materials.

The object of the present invention is achieved by a cyan dye-forming coupler represented by the following general formula CI)↑ and a silver halide color photographic light-sensitive material containing the same.

General formula CI) In the formula, R represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group, Y represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group, and X represents a developing A group that can be separated by an oxidative coupling reaction with the main drug.

Hereinafter, R, X, and Y in general formula (I) will be explained in detail.

In the general formula [■], R is a chain or cyclic alkyl group preferably having 1&/~32 carbon atoms (e.g., methyl group,
butyl group, tridecyl group, cyclohexyl group, etc.), aryl group (e.g., phenyl group, naphthyl group, etc.), or heterocyclic group (e.g., 2-pyridyl group, λ-imidazolyl group, λ-furyl group, 6 -quinolyl group, etc.), and these represent an alkyl group, an aryl group, a heterocyclic group, an alkoxy group (e.g., a methoxy group, a 2-methoxyethoxy group, etc.), an aryloxy group (e.g., a phenoxy group,
λ, 4L-di-tert-amylphenoxy group, cochlorophenoxy group, etc.), carboxy group, carbonyl group (e.g., acetyl group, benzoyl group, etc.), ester group (e.g., methanesulfonyl group, phenoxycarbonyl group, (acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc.), amide group (e.g., acetylamino group, ethylcarbamoyl group, dimethylalbamoyl group, methanesulfonamide group, butylsulfamoyl group, etc.) , sulfamide group (e.g., dipropylsulfamoylamino group), imide group (e.g., succinimide group, hydantoinyl group, etc.), ureido group (e.g., phenylureido group, dimethylureido group, etc.), sulfonyl group (e.g., methane group, etc.). A sulfonyl group or the like may be substituted with a substituent selected from a hydroxy group, a cyan group, a nitro group, a 10-gen atom, a thio group (eg, an ethylthio group, a phenylthio group, etc.), and the like.

In the general formula [I], Y is a chain or cyclic alkyl group preferably having 7 to 32 carbon atoms (e.g., methyl group, butyl group, tridecyl group, cyclohexyl group, etc.), aryol group (e.g., phenyl group)・S7,000 group, etc.), or a heterocyclic group (e.g., -1 pyridyl group, -1 imidazolyl group, λ-furyl group, O-quinolyl group, etc.), and these represent an alkyl group, an aryl group, a hetero cyclic group, alkoxy group (e.g., methoxy group, λ-methoxy group, etc.), aryloxy group (e.g., phenoxy group, -2
, 4'-diter t-amylphenoxy group, λ-chlorophenoxy group, etc.), carboxy group, carbonyl group (e.g., acetyl group, benzoyl group, etc.), ester group (e.g., methoxycarbonyl group, phenoxycarbonyl group) , acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc.), amide group (e.g., acetylamino group, ethylcarbamoyl group, dimethylcarbamoyl group, methanesulfonamide group, 1,000sulfamoyl group, etc.), sulfamide group (
For example, 1 imide group (such as dipropylsulfamoyl group)
For example, succinimide group, higntoynyl group, etc.)
Ureido group (e.g., phenylureido group, dimethylureido group, etc.), sulfonyl group (e.g., methanesulfonyl group, etc.), hydroxy group, cyano group, nitro group, halogen atom, thio group [e.g., ethylthio group, phenylthio group, etc.] It may be substituted with a substituent selected from the following.

In the general formula CII, X is a hydrogen atom, a halogen atom (
For example, a fluorine atom, a chlorine atom, a bromine atom, etc.], leaving groups represented by Ethoxy group, aryloxy group (e.g., phenoxy group, naphthyloxy group, Hirocarboxymethoxy group, etc.), acyloxy group (e.g., acetoxy group,
(tetrazokayloxy group, benzoyloxy group, etc.)
, sulfonyloxy group (e.g., methanesulfonyloxy group, toluenesulfonyloxy group, etc.), amide group (
For example, dichloroacetylamino group, heptafluorobutyrylamino group, methanesulfonylamino group, toluenesulfonylamino group, etc.), alkoxycarbonyloxy group (for example, ethoxycarbonyloxy group, pen-
Noroxycarbonyl group, etc.)・Aryloxy 7J
H'nyl group (e.g. phenoxycarbonyl, 1-
These include thio groups (for example, phenylthio groups, tetrazolylthio groups, etc.), imido groups (for example, succinimide groups, hydantoinyl groups), azo groups (for example, phenylazo groups, etc.), and these include May contain useful groups.

In the general formula [■], RG is preferably a substituted or unsubstituted alkyl group.

In the general formula CI, Y is preferably a substituted aryl group or a substituted or unsubstituted heterocyclic group, and preferred substituents for the aryl group include a halogen atom, a nitro group, a cyano group, a sulfamoyl group, and a sulfonamide group. , a carbamoyl group, an acylamino group, a sulfonyl group, a ureido group, an oxycarboxylamino group, a trifluoromethyl group, and at least one of these is substituted,
Furthermore, other substituents may be substituted.

In general formula CI), preferable X is a hydrogen atom/halogen atom, an alkoxy group, an aryloxy group, a thio group, or an azo group.

Particularly preferred as the aryl group represented by Y is a phenyl group, which has a nitro group, a cyanogen group, a sulfamoyl group, a carbamoyl group, a sulfonyl group, a trifluoromethyl group, or a nitro group at the m position relative to the ureido group. , a cyan group, a sulfonamide group, an acylamino group, a ureido group, an oxycarbonylamino group, a trifluoromethyl group, or a halogen group.

What is particularly preferable as the heterocyclic group represented by Y? −
A benzothiazole group substituted with a halogen atom is more preferred.

The compound represented by the above general formula (hereinafter referred to as the coupler of the present invention) has a ureido group at the 2-position of the phenol, and
It is characterized by having an oxycarbonylamino group in the position, and this combination provides various good properties.
Think of it as something.

That is, the coupler of the present invention has good solubility, the resulting color image has good spectral absorption characteristics, and has excellent storage stability, that is, the fastness of the color image to heat and light. It has an excellent property that there is almost no decrease in concentration when treated with a weak clean solution or a tired bleach solution.

Is these immediate t′ characteristics the technique of the above-mentioned known cyan coupler? The effect exhibited by the coupler of the present invention was surprising, as can be seen by analogy from the patent specification describing III.

Next, specific couplers included in the scope of the present invention will be illustrated, but the couplers of the present invention used in the present invention are not limited to these.

Synthesis Example (Synthesis of Illustrative Zoller) 3 g of p-methylsulfonylaniline and GI were dissolved in 100 rrtl of acetonitrile and 3 ml of pyridine 24', and 3+2.2 g of phenyl chloroformate was added dropwise under water cooling. 7
After stirring for a few hours, it was poured into water containing hydrochloric acid/zol, the precipitated crystals 2P were collected, and dried to give 57g of white crystals 2.
Obtained ◎ Co(D Crystals and Coamino! Nitrophenol 301
'i Niacetonitrile was suspended in 200ml VC, triethylamine-1♂hemp was added, and heated under reflux for 5 hours.Cold:
After MJ, the precipitated crystals were acidified with hydrochloric acid, collected, and dried to obtain 2 grams of yellow crystals.

4 tons of this crystal! Improper tool with reduced iron of 9 and ammonium chloride of GI, 200m1! , water tOyn
The mixture was heated under reflux for 2 hours.

After separating the iron powder, the precipitated crystals were collected to obtain pale reddish-purple crystals 37jif.

Suspend the crystals in acetonitrile and
-di-tert-amylphenoxy)butanol33.
A chloroformic acid ester prepared from ♂1 and phosgene was added dropwise to the mixture under reflux. After the addition, the mixture was roughly heated under reflux for 2 hours. After cooling, ethyl acetate was added, the mixture was washed with water three times, and the solvent was distilled off under reduced pressure. The residue was separated and purified using silica gel chromatography (ethyl acetate-n-hexane), and recrystallized from acetic acid-containing hexane to obtain crystals of ttri. .

Melting point/octopus! OC elemental analysis value; C: 4J-, J'J-, ) (near, t,
2. N: 11% calculated value; C: tj, 9.0. H
Near, 11-3. N: t, j9% Other couplers were also synthesized in the same manner as coupler (1).

To introduce the coupler into the silver halide emulsion layer, known methods such as those described in US Pat. No. 322,027 can be used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.)
, phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl 7 phosphate,
Dioctyl butyl phosphate) citric acid ester (
(e.g. tributyl citrate) S benzoate esters (e.g. offmoles benzoate), alkylamides (e.g. tributyl citrate),
(e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), trimesine m esters (e.g. tributyl trisucinate), etc., or with a boiling point of about 3°C to /
Organic solvents at 0C, such as lower alkyl acetates such as ethyl acetate and butyl acetate, propionic acid, λ-class futhyl alcohol, methyl isobutyl ketone, β
- After being dissolved in ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid.

The above-mentioned high point organic solvent and low boiling point organic solvent may be used in combination.

The amount of the coupler of the invention to be added is generally from 1.times.10 to 7.times.10@-1 mole, preferably from /.times.10@-2 to .times.10@-2 mole per 7 moles of silver in the emulsion layer.

The color photographic light-sensitive material of the present invention includes not only color image-forming couplers other than the above-mentioned ureido couplers, but also colored couplers for color correction, MDIR couplers, colorless couplers for improving the hue of the light-sensitive material, Or, it may contain additives that are normally added, such as ultraviolet absorbers and stabilizers for photographic performance.)

Next, the additives such as couplers that can be added in the present invention will be described in detail. As the yellow coloring coupler, a known open-chain ketomethylene coupler can be used. Among these, benzoylacetanilide and hivaloylacetanilide compounds are advantageous. Specific examples of yellow coloring couplers that can be used are given in US Patent No. 7! , No. 037, 3, 27. ! ;、! Ot issue,
Same 3゜≠Or, /9≠ issue, Same 3. Ta! /, /3j No. 3, IT No. 2,322, No. 3,723,07λ, No. 3. Zari/, Gu≠! No., West German patent/, J′≠7゜za61
No. r, West German Application Publication λ, 2/Ri, Ri No. 77, 2. ．． 2
t/, 3t/ issue, i, aia, oo4, British patent/
, 4A2j, No. 020, Special Publication Show J-/-10713
No., Tokukai Sho+7-. 2t/33 issue, same tzaichi 73/44
No. 7, same! /-10 Colo No. 36, same! 0-431iL1
No., jTO-/23341.2, same! 0-/30.
≠Hiro d issue, same J-/-2/♂27, same to-za 7 otsu
It is described in issues such as No. O, No. λ-h, No.

Magenta coloring couplers include pyrazolone compounds,
Indacylon compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are particularly advantageous. Specific examples of magenta color-forming couplers that can be used include U.S. Pat.
No. 3. OA2. A! No. 3, same 3. /27. ．． 2t No. 3, 3//.

≠7 and 3. t/ri, issue 39, same 3. ! /ri,≠
Kota, same 3. ! 3g, 3/ri issue, same 3゜! ♂2,32
No. 2, No. 3, 1. /j,! OA No. 3, 1r31/
-, Riotr issue, same 3. Niri／, Hiro≠! No., West German patent/
, I10, 1ltj, West German patent application (OLS) 2.
4Log, ttr issue, same 2. II/7゜Tag No. 1, 2,4L/I, RiJri No., Koko, Ri2≠, ≠t7 No., Special Public Shoμ0-t03/No., Special Public Sho! F/-, 20r2
A, same! 2-! ! Octopus λ, same≠tar/2ri! 3♂ issue, same ≠ Turf 4tO core issue, same! 0-/! Issue 93.3, same! 2-112/2/issue, same # Turf 4tO, 21
No., same, j-0-t0233, same ta/-21. ! ≠／
No., r3-6. ! As the cyan color-forming coupler described in -/C, etc., phenolic compounds, sodium compounds, etc. can be used. A specific example is U.S. Pat.
34t, 272, 2I≠7≠, Kota 3, 2
, 32/, No. 901, same, 2. rri 3゜za, 2 & issue,
Same 3.03g, Zari 2, same 3,3 no/, 4!7/;, same 3 Go J, 13 no! No. 3゜ll-71,543, No. 3,313,271, same! ,,tri/ ,31r
, No. 3, J, 767, No. II-11, f8J
'l, 004', No. 929, West Unique FI4B Application (OLS
) Ko, ≠/4tl♂ No. 30, same 2. ≠! ≠, 3 Kota issue,
Japanese Patent Publication No. 4J'-49131, No. J/-2t034, Same≠Zaichi! 0! No. j, No. 31-/No. Jfλr, No. J
-,! -t9L day issue, same! As the colored coupler, for example, U.S. Pat. No. 3, F.
7! , jtO issue, 2.32/, 901, 3
．． 034t, No. 19.2, Special public show 1141-2'0/l
.

No. 3f-, 2uj3 No. 4', 2'-//30
No. 4, FF-3211t1, JP-A-Sho J-/-2
A.O.

No. 3 specification, same! 2-Hiro No. 272 specification, West German patent application (OLS), 2. ≠/I, those listed in Rijri No. can be used.

As a DIR coupler, for example, US patent 3゜2νLj
! μ issue, same 3. t/7. Kota/No., same J, 70/,
No. 713, No. 3,790.31rl1, No. 3, A
32, 34tj, West German Fl-[a (OLS
) λ, ti4A, oot issue, same λ, ≠jg, 307 issue,
Same λ, ≠! 4A, No. 3.2, British Patent No. 33. lll
V issue, Tokukai Akira! No. 2-677.2+, same≠Turf 2.2
Those described in No. JJJ- and Japanese Patent Publication No. J-/-/l/4t/ can be used.

In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor upon development, for example, as disclosed in US Pat. No. 3,207,4t4t! No., 1+”j]3..
379,! No. 2Y, West German Patent Application (OLS) 2, II
/7,9'/4' issue, JP-A-Shoter-/yo 277 issue, same j
Those described in No. 3-T//1 can be used.

Two or more of the above couplers may be contained in the same layer.

The same compound may be contained in λ or more different layers. These couplers are generally used per mole of silver in the emulsion layer!
×10-3 mole~! ×/.

-1 mol, preferably l×l0-2 mol~! ×10-1
molar added.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with an oryl group (e.g. those described in U.S. Pat. No. 3. issue,
3.3!2゜1.1/], benzophenone compounds (e.g., those described in JP-A No. 4L7-27g≠), cinnamate ester compounds (e.g., U.S. Pat.
706,! 0! @, 3,707.37. ) and butadiene compounds (for example, those described in the US Special Edition).

011-! , 2λO1), or benzoxidol compounds (e.g., those described in
≠! Items listed in item j) can be used.

The photographic emulsion used in the present invention may be spectrally sensitized by methine color chips or the like. The oil dye used is
Cyanine dyes, merocyanine dyes, complex cyanine dyes,
Included are complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes/styrine dyes, and hemioxonol dyes. Particularly useful dyes include cyanine color chart,
It is a pigment belonging to merocyanine pigments and complex merocyanine pigments. Any of the nuclei commonly used for cyanine color patches can be used as basic heterocyclic nuclei for these color patches. Namely, pyridine nucleus, oxazoline nucleus, azoline cedar, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and Nuclei in which aromatic hydrocarbon rings are fused to these nuclei, i.e., indolenine nucleus, benzindolenine nucleus,
Indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted with KW on the carbon atom.・Merocyanine dyes or complex merocyanine dyes Nuclei having a nihaketomethylene structure 2 include a pyrazoline-terone nucleus, a thiohydantoin nucleus, a 2-thousand oxazolidine nucleus, a 7-dione nucleus, Thiazolidi>-2,
It is possible to apply j-shell heterocyclic nuclei such as μm dione nuclei, logenine nuclei, and thiobarbyl scatterings.

Useful sensitizing dyes include, for example, the German Patent Octopus y, o
io, U.S. Pat. No. 2,23/, +3I, U.S. Pat. ll
-93,7111, 2. ! ;01,77 No., same co, 3-/ri, 00/@, same co, ri/2,329, same 3
, &j, 4, L? j5', same 3. j7J.

Zari No. 7, same, 3. AP'1.2/7, same≠, θλyo, 3≠ri, Dohiro, Ohiro 1,37λ, British Patent 7.2
≠2. ! Ryog No., Tokuko Shoφhiro-/'l-03θ No., same!
2-2≠, r1. There are many examples of things that have been recorded in hirogo etc.

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

A typical example is U.S. Patent λ, Otsu! ? ♂, 34'! No. 1, No. 977.229, No. 3,397. OtO No. 3.322.032, No. 3, , t, 27, &
+/No. 3. t/7. ．． No. 293, 3. t, 2g,
? z4L, same 3. t1. l,, 4#0 issue, same 3,1,
72゜gg＠, same 3. t7ri, ≠2 and number, 3,70
3. No. 377, No. 3,7 Otori, No. 307, No. 3゜r/4
1. +09, 3,137. lft, No. 2, same/A,
0.2t, No. 707, UK special if/, 3a a
, J, l-7, same / ,! 07. No. 103, Special Public Shogu 3-≠73 Otsu No., same, +3-/2,37! No., JP-A No. 7IO167g, J2-/θ-RI, RI-2J, etc.

Along with the sensitizing dye, the emulsion may contain a dye that itself has no spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostyl compounds equipped with nitrogen-containing heterocyclic groups (
For example, U.S. Patent No. 733.390, J, t3
r, No. 7.2/), aromatic organic acid formaldehyde condensates (for example, those described in U.S. Pat. No. 3,7413.
610), cadmium salts, azaindene compounds, and the like. US Patent 3. T-no! , 47
No. 3, same 3. A/j, Otsu≠7, same 3. t/7. ．． 2ri! Particularly useful are the combinations described in No. 1, Clause 3, 1.33', No. 72/.

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, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes: hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used are British patented! I
II, No. 40, same/, /77.1. A29, JP-A-Sho' Al-13130, same #! i'-ta9t20, getter//41'120, same, t, 2-10, etc.

No. 116, U.S. Patent λ-, 274', 7gλ, No. 2
゜633.4t72, same 2. rijJ, do 7ri issue, same J
, /III, /17 issue, 3. /77.071 No. 3
．． ．． 2417. /27 issue, same 3, 61/LO, 1r1
No. 7, same 3. J-7J-, No. 70'1, 3. tjt-
3, Rios issue, 3, 7/1, 4172, Dohiro, 07
/.

It is described in No. 37λ, No. 070, and No. JJ-2.

In the photographic material produced using the present invention, the photographic emulsion layer and other hydrophilic colloid layers may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener. These may be water-soluble,
A water-insoluble brightener may also be used in the form of a dispersion.

Specific examples of fluorescent brighteners include U.S. Patent No. 2,432,70/;
Same 3. /1? , II/-0 No. 3, 33-9゜10
,! No., British patent♂! λ, o7! No., 1.3/ri, 7
It is not stated in Otsu No. 3 etc.

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 two or more. Known anti-fading agents include, for example, U.S. patent, 2,3tO,2
ri No. 0, same 2 Igu/♂.

A13, same 2. t7! , J/41, same, 2,70/
, /ri No. 7, No. 2,7017.71J, Same Co.

721,t,! No. f, No. 2, 73, No. 300, No. 2
．． 733.7tj, same, 2j710, 10/, same 2.1/A, Orr, British special Ff/, 3t3゜ri 2/
Hydroquinone derivatives described in US Pat. No. 3, etc.
Gallic acid derivatives described in 4tj No. 7,072, No. 3.012゜2 No. λ, etc., US Pat. No. 2,733,71.
! No., same, 3. t91.90 issue, Tokko Sho tter, 20
No. 277, same! p-alkoxyphenols described in Cott No. 23, U.S. Patent No. 3.4t32.300,
3, 373.

oro issue, same 3. j7≠, A27, 3,7tII,
No. 337, JP-A-32-3JtE3, S2-/≠7
4t31A, Sameta x-ir, 222! p-oxyphenol derivatives described in U.S. Patent No. 3. yoo, r
There are bisphenols listed in ats@.

The photosensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifogging agent, and specific examples thereof include U.S. Pat. Otsu O1, 2ri No. 0, 2.33t.

No. 327, 2. l1L03, 72/No. 2. ψ/1
, No. A13, same 2. t7jJ-, 3/41 issue, same! .

70/, No. 197, No. 2,701/-, No. 7/3, No. 2, 721, Otsu No. 59, No. λ, 73.2. 30
No. 0, 2,73. t, 7 otsu j issue, JP-A-30-7.2
7rg issue, same, 5'0-ta Jriri issue, same! O-ta 3ri λr, same! rO-/10337, 32-/+,
<23 Evening issue, Tokko Akira! 0-. 2J♂/No. 3 specification etc.

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. A multilayer natural color photographic material usually has at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

For photographic processing of the light-sensitive material of the present invention, any known method can be used, and known processing solutions can be used. In addition, the processing temperature usually ranges from /f00 to t
o"C, but the temperature may be lower than /Is"C or higher than zoooc. Depending on the purpose, development processing that forms a silver image (black and white photographic processing) or a color image may be performed. It is possible to apply any color photographic process consisting of a photo-development process.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylenediamines (e.g., guamino-N, N-diethylaniline, 3-methyl-≠-
Amino-N, N-diethylaniline, t-amino-N-
two-handed Ru N-β-hydroxyethylaniline 3-methyl-guamino-N-ethyl-N-β-hydroxyethylaniline 3-methyl-Hiroshi-amino-N-okute Ru N-β-methanesulfamide ethylaniline, ≠-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used. In addition, photo-grap by F.A0MaSOn
hjc processingchemistry(
Published by Focal press, 1996) (DP22
t N22? , U.S. Patent Co.

/ri No. 3, 01j, same 2. ! The color developer described in Tako, No. 37.4A, JP-A No. 6-233, etc. may be used. In addition, the color developer may include alkali metal sulfites, carbonates, borates, and phosphates. It may contain pH buffering agents such as bromides, iodides, and development inhibitors or antifoggants such as organic antifoggants. Also, if necessary, water softeners, preservatives such as hydroxylamine,
Organic solvents such as benzyl alcohol, diethylene glycol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron Hytry F, auxiliary developers such as /-phenyl-3-pyrazolidone, tackifying agents, US Pat.

The polycarbonate MM chelating agent described in No. 613.723, the antioxidant described in OLS, J, G, Z, Z, No. 230, and the like may be included.

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

The bleaching treatment may be carried out simultaneously with the fixing treatment or may be carried out separately. As a bleaching agent, for example, iron (III
), compounds of polyvalent metals such as cobalt (■), chromium (VI), copper (■), peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide/dichromate/iron(III) or 44:2 Hult(III)
), for example, complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, /,3-diadi'/-2-propaturtetraacetic acid, or organic acids such as citric acid, tartaric acid, malic acid, etc. sulfur salt,
Permanganate; nitrosophenol, etc. can be used. Of these, potassium ferricyanide, sodium iron(III) ethylenediaminetetraacetate, and ammonium iron(m) ethylenediaminetetraacetate are particularly useful.

Ethylenediaminetetraacetic acid iron(III) complex salts are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

Furthermore, the bleaching solution or bleach-fixing solution includes U.S. Patent 3.04L.
2, r20, same 3,2g/, F74, special public show t
ts-trtot issue, Sukyu Fp.

≠j-A# Bleach accelerator described in Jt issue etc., JP-A-Sho J-
In addition to the thiol compounds described in J-tA-732, various additives may also be added.

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

Example-7 Coupler according to the present invention (1) log, trioctyl phosphate 101 and 20 vtl x tyl acetate at 50°C
The resulting solution was added to 100g of an aqueous solution containing 10II of gelatin and 1≠g of dodecylbenzenesulfonic acid, stirred, and then preheated and placed in a colloid mill for 55 minutes.
The mixture was circulated and finely emulsified and dispersed.

All of this emulsion 2 Silver chlorobromide 2/9 and gelatin, 2≠y
and as a hardening agent to the photographic emulsion lθOg containing
, after adding 30 ml of 2% aqueous solution of dichloro≠-hydroxytriazine ・pHfA of the turbidity,
After adjusting the OVc, it was coated uniformly on a triacetic acid fiber-based film base. This will be referred to as E-feed A.

In place of the above coupler (1), the same molar coupler (-?)
,(4)'? i: A film was prepared by the same procedure. These were designated as Samples B and C, respectively. For comparison, films were prepared by the same procedure using the same mole of comparative couplers (10/2) and (10,2) in place of the above coupler (1). Take this sample and call it E.

6.6 These samples were subjected to continuous exposure using a sensitometry wedge, and then subjected to the following development treatment.

Color development process (330C) /, Color development...3 minutes 30 seconds λ, Bleach fixing...7 minutes 30 seconds 3, Washing... ......2 minutes 30 seconds The processing steps used in each step are as follows.

Color developer benzyl alcohol / j, 0yr
tl diethylene glycol 1. Oml!
Ethylenediamine acetic acid s, og sodium sulfite 2.09 anhydrous potassium carbonate 30 9 hydroxylamine sulfur (
7143,09 Triumium bromide
o, tg≠-amino-N-two-handed RuN- (β-methanesulfonamidoethyl)-m-toluidine sesquisulfate monohytre)! , C# Add water /7 (PH10,j) Bleach-fix solution ethylenediamine ≠ acetic acid ≠, oy Kosenre Oteshimin ≠ ferric acetate Shiohiro OI sodium sulfite
-t+ op sodium periosulfate
(70%) / J-Add 0ml water
Regarding the sample obtained after the treatment,
-f:n When the optical density for red light was measured, the first
The results shown in the table were obtained.

@Table 7 In addition, when the absorption coefficient of these films was measured, the couplers of the present invention were sharp and showed absorption favorable for color reproduction.□ Next, the developed films were tested for fastness. Sample 7j: left in the dark at 1000C for 6 days.
When left in the dark at 70% RH at oC for 2 weeks and when exposed to light for 2 days in a xenon tester (100,000 lux), the concentration decrease rate at initial concentration 2/, 0 of n, respectively. The results are as shown in Table 2.

Procedural amendments Commissioner of the Patent Office, Mr.■, Indication of the case Showa SR year patent application No. 9? No. 2. Title of the invention: Halogen ratio silver color photographic light-sensitive material 3. Relationship with the amended person's case Patent applicant Location: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (5)
20) Fuji Photo Film Co., Ltd. 4. Target of correction
Specification 5. We will submit a clean copy of the detailed statement of amendments (no changes to the contents).

Claims (1)

[Scope of Claims] A silver halide color light-sensitive material containing a cyan dye-forming coupler represented by the following general formula [i]-+=. , X, → wipe [I] In the formula, R represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group, and Y represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group. represents a group 2 which can be separated by an oxidative coupling reaction with a developing agent.