JPS61105545A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To form a silver halide color photographic sensitive material capable of forming a color image durable for long-term storage by incorporating a specified cyan dye-forming coupler. CONSTITUTION:The silver halide color photographic sensitive material capable of forming a cyan dye image good in hues and superior in storage stability can be obtained by incorporating the cyan dye-forming coupler represented by formula I in which R is an optionally straight or cyclic and optionally satd. or unsatd. aliphatic group, preferably, having 1-2, such as methyl; R is an aryl or heterocyclic group, typified by phenyl or pyridyl; and X is H or the like; and Z is H or a group releasable at the time of coupling reaction with the oxidation product of a color developing agent.

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 novel cyan dye-forming coupler.

(Prior art) When a silver halide photosensitive material is exposed to light and then subjected to one color development treatment, a developing agent such as an aromatic-class amine oxidized by silver halide reacts with a dye-forming coupler, and a color image is formed. It is formed. Generally, in this method,
A subtractive color reproduction method is often used, and in order to reproduce blue, green, and red, images of yellow, magenta, and cyan, which are complementary colors, are formed, respectively.

(Problems to be Solved by the Invention) Phenols or naphthols are often used as cyan image forming couplers. However, there remain some problems with the storage stability of color images obtained from conventionally used phenols and naphthols.For example, U.S. Pat.
, 369, No. 929, :52.423.730 and No. 2.801.171, etc., the color images obtained from the 2-7 sylaminophenol cyan couplers generally have poor heat fastness, and are Patent No. 2,772.1
2.5- as described in No. 62 and No. 2,895,826.
Color images obtained from diacylaminophenolic cyan couplers generally have poor light fastness, and l-hydroxy-2
- Natsutamido cyan couplers are commonly used for light and heat (
It is insufficient in both terms of fastness (particularly in heat and humidity).

On the other hand, U.S. Patent No. 3.772.002 discloses a phenolic cyan coupler in which the meta-position of the phenol is substituted with a linear alkyl group such as an ethyl group or a pentadecyl group, but it can be stored in the dark for a longer period of time. This is insufficient considering gender.

It is an object of the present invention to contain cyan dye-forming couplers which ameliorate these shortcomings and provide color images that can be stored for longer periods of time. An object of the present invention is to provide a silver halide color photographic material.

Another object is to provide a high-quality silver halide color photographic light-sensitive material using a cyan dye-forming coupler that is easily dispersed in organic solvents and has high dispersion stability.

(Means for Solving the Problems) The above objects of the present invention can be achieved by a silver halide color photographic light-sensitive material characterized by containing a cyan dye-forming coupler represented by the following general formula [I]. .

(In the formula, R represents a substituted or unsubstituted aliphatic, 7-aryl or heterocyclic group, and X is a hydrogen atom.

represents a halogen atom, an alkyl group, an alkoxy group, or an acylamide group, Z represents a hydrogen atom or can be separated in an oxidative coupling reaction with an imaging agent),
,

In the general formula [I], the aliphatic group represented by R may be linear or cyclic, preferably has 1 to 32 carbon atoms, and may be saturated or unsaturated,
Representative examples include a methyl group, a butyl group, a hexadecyl group, an allyl group, a cyclohexyl group, a propenyl group, and a propargyl group. Representative examples of the aryl group represented by R include phenyl group and naphthyl group, and representative examples of the heterocyclic group represented by R include 2-pyridyl group, 2-furyl group, and 6-quinolyl group. These groups may have one or more substituents (including substituent atoms, the same shall apply hereinafter) as listed below. Permissible substituents include aliphatic groups (e.g. methyl group, allyl group, cyclopentyl group, etc.), aromatic group (e.g. phenyl group, naphthyl group, etc.), heterocyclic group (
For example, 2-pyridyl group, 2-imidazolyl group, 2-furyl group, 6-quinolyl group, etc.), aliphatic oxy group (such as methoxy group, 2-methoxyethoxy group, 2-propenyloxy group, etc.), aromatic oxy 2ti (e.g. 2,4-
di-tert-amylphenoxy group, 4-cyanophenoxy group, 2-chlorophenoxyl&, etc.), acyl group (
For example, acetyl group, benzoyl group, etc.), ester group (
For example, butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc.), amide group (for example, acetylamine group, methanesulfonamide group,
ethylcarbamoyl group, diethylcarbamoyl group, butylsulfamoyl group, etc.), imide group (e.g. succinimide group, hydantoinyl group, etc.), ureido group (e.g. phenylureido group, dimethylureido group, etc.), aliphatic or aromatic sulfonyl group ( (e.g. methanesulfonyl group, phenylsulfonyl group, etc.), +l)I aliphatic or aromatic oxy (e.g. phenylthio group, ethylthio group), hydroxyl group, cyano group, carboxyl group, di1.0 group, sulfone group, halogen When there are atoms (for example, fluorine atoms, chlorine atoms, bromine atoms, etc.) and two or more substituents, they may be the same or different.

In the general formula [I], ) or an acylamino group (for example, an acetamido group, a benzamide group, etc.), of which a substitutable group may be substituted with a group allowed by R.

- In the general formula [I], Z represents a hydrogen atom or a group that can be separated during a carp-2-pulling reaction with an oxidized product of a developing agent.

Specific examples of coupling-off groups include halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom, etc.), alkoxy groups (e.g. ethoxy group, dodecyloxy group, methoxyethylcarbamoylmethoxy group, carboxypropyloxysulfonylethoxynoS) ), 7-aryloxy groups (e.g. 4-chlorophenoxy group, 4-methoxyphenoxy group, 4-carboxyphenoxy group, etc.), acyloxy groups (e.g. acetoxy group, tetrazocallyloxy group,
benzoyloxy group, etc.), aliphatic or aromatic sulfonyloxy group (e.g., methanesulfonyloxy group, toluenesulfonyloxy group, etc.), acylamino group (e.g., dichloroacetylamino group, heptafluorobutyrylamino group, etc.), aliphatic or Aromatic sulfonamide groups (e.g., methanesulfonamino group, P-toluenesulfonylamino group, etc.), alkoxycarbonyloxy groups (e.g., ethoxycarbonyloxy group, benzyloxycarbonyloxy group, etc.), aryloxycarbonyloxy groups (e.g., phenoxycarbonyloxy aliphatic, aromatic or heterocyclic thio groups (e.g. ethylthio, phenylthio, tetrazolylthio, etc.)
, carbamoylamino group (e.g. N-methylcarbamoylamino group, N-phenylcarbamoylamino group, etc.)
, 5- or 6-membered nitrogen-containing heterocyclic groups (e.g. imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, 1,2-dihydro-2-oxo-1-pyridyl group, etc.), imide group (e.g. succinimide group) , hydantoinyl group, etc.), aromatic azo groups (eg, phenylazo group, etc.), and these groups may be further substituted with a group allowed as a substituent for R.

R may be a divalent group to form a bis body.

Further, the cyan dye-forming coupler represented by the general formula [I] may be in the form of a polymer coupler containing a coupler residue represented by the general formula [CI] in the main chain or side chain of the polymer, and in particular, the cyan dye-forming coupler represented by the general formula [I] Preference is given to polymers derived from ethylenically unsaturated compounds containing moieties represented by .

R represents a repeating unit contained in the main chain of the polymer chain and a connecting portion thereof.

When R becomes a divalent group to form a bis body, R is preferably a substituted or unsubstituted fullkylene group (e.g., methylene group, ethylene), 5, l, l O-decylene group, -CH2CH,, - 0-CH2CH2-, etc.), substituted or unsubstituted phenylene groups (e.g. 1, 4-phenylene Ll, 3-7 enylene groups).

-NHCO-R1-CONH- group (R1 represents a substituted or unsubstituted fullkylene group or phenylene group, for example, -NHCOCH2CH2CONH-).

H3 -S-R2-S- group (R2 represents a substituted or unsubstituted fullkylene group, for example -5-cH2cH,, -5-.

CH3 When the vinyl monomer contains what is represented by the general formula [I1, the linking group represented by Rf is an alkylene group (
Substituted or unsubstituted fullkylene group such as methylene group, ethylene 3.1.10-decylene group, -CHCHOC
H2CH2-1, etc.), phenylene group (substituted or unsubstituted phenylene group, such as 1,4-phenylene group, 1,
3-) 22dine group.

-NHCO-1-CONH-1-0-1-〇CO- and an aralkylene group (eg, t, etc.) in combination.

Preferred linking groups include the following.

-NHCO-1-CH2CH2-1 -C;, H2CH2-0-C- -CONH-CH2CH2NHCO- -CHCM 0-CH2CH2-NHCO- Note that the vinyl group has a substituent other than those in general formula [I]. A very good and preferred substituent is a hydrogen atom, a chlorine atom or a lower alkyl group having 1 to 4 carbon atoms (eg methyl group, ethyl group).

Monomers including those represented by formula [I] may be copolymerized with non-chromogenic ethylene-like monomers that do not couple with the oxidation products of aromatic-grade amine developers.

Acrylic acid, α
- Chloroacrylic acid, α-alacrylic acid (e.g. methacrylic acid, etc.) and esters or amides derived from these acrylic acids (e.g. acrylamide,
n-butyl acrylamide, t-butyl acrylamide, diacetone acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, 1SO-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), methylene dibis acrylamide, vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylate Ryl, aromatic vinyl compound (@
styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic acid, maleic anhydride,
Maleic acid ester, N-vinyl-2-pyrrolidone, N
-vinylpyridine and 2- and 4-vinylpyridine. Two or more non-color-forming ethylenically unsaturated monomers used here can be used together. For example, n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, methyl acrylate. and diacetone acrylamide.

As is well known in the polymeric color coupler art, non-chromogenic ethylenically unsaturated monomers for copolymerization with solid water-insoluble monomeric couplers depend on the physical and/or chemical properties of the copolymer formed, e.g. solubility, compatibility of the photographic colloidal composition with binders such as gelatin, its flexibility,
It can be selected so that thermal stability etc. are favorably influenced.

The polymer coupler used in the present invention may be water-soluble or water-insoluble, but polymer coupler latex is particularly preferred.

In general formula [I], preferred X is a halogen atom, with fluorine and chlorine atoms being particularly preferred.

In the general formula [I], Z is preferably a hydrogen atom, a halogen atom, an alkoxy group which may have a substituent, an aryloxy group, a sulfonamide group, or an acyloxy group, and a fluorine atom and a chlorine atom are particularly preferred.

- In general formula [I], R is preferably an it-substituted alkyl group, or an optionally substituted branched or cyclic alkyl group.

Next, specific examples of the cyan dye-forming coupler represented by the general formula [I] will be given, but the present invention is not limited to this invention. (The case where X and Z are α in general formula [I] is shown).

(''l) [I) [■] [Leopard] [v: ICvD That is, 3-isopropylphenol (1) is sulfonated with chlorinated sulfonic acid or sulfuric anhydride, and then converted to dichlorosulfonate (III) using chlorine gas, Next, the sulfo group was replaced with a nitro group using nitric acid, and the sulfo group was replaced with a nitro group.
Obtain body (■).

(IV) is reduced and acylated by a conventional method to obtain coupler (Vl).

The typical amount of cyan coupler used in this invention is 0.002 to 0.3 mole per mole of photosensitive silver halide.

The coupler of the present invention can be introduced into a photosensitive material by various known dispersion methods, such as solid dispersion method, alkali dispersion method,
Typical examples include preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. In the oil-in-water dispersion method, after dissolving either a high-boiling point organic solvent with an 's point of 175°C or higher and a low-boiling point so-called auxiliary solvent alone or in a mixture of both, the solution is dissolved in the presence of a surfactant. Finely dispersed in an aqueous medium such as water or an aqueous gelatin solution. Examples of high boiling point organic solvents are U.S. Patent No. 2.322.0
It is stated in issue 27 etc. Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, or the like before use for coating.

Specific examples of high-boiling organic solvents include phthalate esters (dibutyl phthalate, dicyclohexyl phthalate,
(di-2-ethylhexyl phthalate, decyl phthalate, etc.), esters of phosphoric or phosphonic acids M () liphenyl phosphate, tricresyl phosphate, 2-
ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tryptopyl diethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphate, etc.), benzoic acid esters ( 2-ethylhexylbenzoate,
dotecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (diethyl dodecanamide, N-tetradecyl pyrrolidone, etc.), alcohols or phenols (stearyl alcohol, ?, 4-di-tert-amyl phenol, etc.), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N,N-dibutyl-2-butoxy-5-tert- octylaniline, etc.), and hydrocarbons (paraffin, chlorinated paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). Further, as the auxiliary solvent, organic solvents having a boiling point of about 30°C to about 160°C can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-nitoxyethyl acetate, and dimethyl phosphatide. Examples include remamide.

Examples of latex dispersion process steps, effects, and latex for impregnation can be found in U.S. Pat. No. 4,199.

No. 363, West German Patent Application (OLS) No. 2.541.27
No. 4 and No. 2,541,230.

The coupler according to the present invention can be used not only by incorporating it into a light-sensitive material but also by incorporating it into a color developing bath. In this external color development method, the number of carbon atoms in the part represented by R in the general formula [I] does not need to be as large as necessary to impart diffusion resistance, and it is necessary to have a carbon number of 1O or less. It may be a group such as

In the present invention, various color couplers that form yellow or magenta color images can be used, and various cyan couplers other than those represented by the general formula [I] can also be used in combination. Here, the term "color coupler" refers to a compound that can react with the oxidized product of an aromatic primary amine developer to produce a dye. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolone or pyrazolone, etc. There are zoroazole compounds and open-chain or heterocyclic m-ring ketomethylene compounds. Specific examples of these cyano, magenta, and yellow couplers that can be used in combination or in the present invention are available in Research Φ Disclosure (RD) 17643 (December 1978)
Vll-D and the patent cited in No. 18717 (November 1979).

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized, and the coupling active position is substituted with a leaving group rather than a hydrogen atom equivalent color coupler. Two-equivalent color couplers are better because the amount of silver coated can be reduced and higher sensitivity can be obtained.Couplers in which the coloring dye has appropriate diffusivity, colorless couplers, or those that release a development-inhibiting surface upon coupling reaction. DIR couplers or couplers that release development accelerators 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. 2,40
No. 7,210, No. 2゜875.057 and No. 3
．． The use of two-equivalent yellow couplers is preferred in the present invention, as described in U.S. Pat. No. 3,408,194, U.S. Pat. No. 933,501 and No. 4,022.6
20, etc., or Japanese Patent Publication No. 58-10739, U.S. Patent No. 4
, No. 401,752, No. 4.326,024, RD
18053 (April 1979), British Patent No. 1,42
No. 5,020, West German Application No. 2,219,917,
Typical examples include the nitrogen atom separation type yellow couplers described in Japanese Patent No. 2,261.361, Japanese Patent No. 2,329,587, and Japanese Patent No. 2,433,812. α-piparoylacetanilide couplers have excellent fastness of coloring dyes, especially light fastness;
- Benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye. Chapter 2.34
No. 3,703, No. 2,600,788, No. 2.9
No. 08.573, No. 3.062.653, No. 3,
No. 152,896 and No. 3,936,015, etc. As a leaving group for a two-equivalent 5-pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or U.S. Pat.
．． The arylthio group described in European Patent No. 897 is particularly preferred, and the 5-pyrazolone coupler having a palast group described in European Patent No. 73,636 provides high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
369.879, preferably pyrazolo[5,1-c][1,2,4] as described in U.S. Patent No. 3.725.067.
Triazoles, pyrazolotetrazoles described in RD24220 (June 1984) and RD24230
(June 1984), the imidazo [I,2- b ] Pyrazoles are preferred, such as pyrazolo[I,5-b
] [I, 2, 4]) Lilliagy is particularly preferred.

Cyan couplers that can be used in combination with the present invention include oil-protected naphthol couplers and phenolic couplers, such as naphthol couplers described in U.S. Pat. No. 2,474.293, preferably U.S. Pat. No. 4,052.
, No. 212, No. 4.146,396, No. 4,22
Typical examples include two-equivalent naphthol couplers of the oxygen atom elimination type described in No. 8,233 and No. 4,296,200. Specific examples of phenolic couplers include U.S. Pat. No. 2,369,929 and U.S. Pat.
No. 01,171, No. 2,772.162, No. 2.
No. 895,826, etc. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention.

A typical example is U.S. Patent No. 3,772゜002.
Phenolic cyan couplers described in U.S. Patent Nos. 2,772,162 and 3,758,308
No. 4,126,396, No. 4,334,011, No. 4,327.173, West German Patent Publication No. 3.32
9,729 and Japanese Patent Application No. 58-42671, etc., and U.S. Patent FiS. 3,446,822, U.S. Pat. 451.559 and 4,427,767, etc., which have a phenylureido group at the 2-position and a 7-syl amino group at the 5-position.

In order to correct unnecessary absorption of short wavelengths by dyes generated from magenta and cyan couplers, it is preferable to use colored couplers in color sensitive materials for photography. 57-
Yellow-colored magenta couplers described in US Pat. No. 39413, etc. or U.S. Pat.
Typical examples include the magenta-colored cyan couplers described in US Pat. No. 38,258 and British Patent No. 1,146,368.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Examples of such blur couplers include magenta couplers in U.S. Pat. No. 4,366.237 and British Patent No. 2,125,570.
Also, European Patent No. 98.570 and West German Application No. 3
, 234.533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and special couplers described above may form conjugates of dimeric embodiments; typical examples of polymerized dye-forming couplers are described in U.S. Pat. No. 3,451,82.
No. 0 and No. 4.080.211. Specific examples of polymerized magenta couplers are described in British Patent No. 2.102.173 and US Pat. No. 4,367.2.
It is described in No. 82.

The various couplers used in the present invention can be used in combination in the same layer of the photosensitive layer in order to satisfy the characteristics required for the photosensitive material, or in two or more different layers using the same compound. It can also be introduced into

Standard usage amounts for color couplers range from 0.001 to 1 mole per mole of photosensitive I\silver halide, preferably from 0.01 to 0 for yellow couplers.
．． 5 moles, 0.003 to 0.00 for magenta couplers.
3 mol, and 0.001 to 0.3 mol in the case of a cyan coupler used in combination with the cyan coupler of general formula [I].

The present invention may also include a coupler that releases a development inhibitor upon development, a so-called DIR coupler.

As a DIR coupler, for example, U.S. Pat.
, No. 554, etc.; those releasing benzotriazole derivatives as development inhibitors, as described in Japanese Patent Publication No. 58-9942, etc.; Japanese Patent Publication No. 51-16141, etc. The so-called colorless DIR coupler described in JP-A-52-90932 releases a nitrogen-containing heterocyclic development inhibitor with decomposition of methylol after separation as described in JP-A-52-90932: U.S. Pat. No. 4,248,962
and JP-A No. 57-56837, which release a development inhibitor with an intramolecular nucleophilic reaction; No. 58-98728, No. 58
-209736, 58-209737, 58-
No. 209738, No. 58-209739 and No. 58
209740 etc. which releases a development inhibitor by electron transfer via a conjugated system after separation; JP-A-57-
151944 and 58-217932, which release a diffusible development inhibitor whose development inhibiting ability is deactivated in the developer solution; Japanese Patent Application Nos. 59-38263 and 59-39
653, etc., and generates a development inhibitor by reaction in the film during development, or deactivates the development inhibitor. Among these, those more preferable in combination with the present invention are developer deactivation type represented by JP-A No. 57-151944; U.S. Pat. No. 4,248,962.
and the timing type represented by Japanese Patent Application No. 57-154234; and the reaction type represented by Japanese Patent Application No. 59-39853. Particularly preferred among these are the
-151944, 58-217932, patent application No. 1977
No. 9-75474, No. 59-82214, No. 59-8
Developer deactivation type DIR couplers described in Oyo No. 2214 and No. 59-90438, etc. and Japanese Patent Application No. 1983-396
This is a reactive DIR coupler described in No. 53 and the like.

In the light-sensitive material of the present invention, a compound that releases a nucleating agent, a development accelerator, or a precursor thereof (hereinafter referred to as "development accelerator, etc.") in an image form during development can be used. A typical example of such a compound is British Patent No. 2,0
No. 97,140 and No. 2,131,188.

It is a coupler that releases a development inhibitor through a coupling reaction with an oxidized product of an aromatic primary amine developer, that is, a DAR coupler.

It is preferable that the development accelerator released from the DAR coupler has an adsorption group for silver halide.
No. 10 and No. 58-31611.

A sulfur or nitrogen atom separates from the coupling active site of a photographic coupler. DAR couplers that produce N-acyl-substituted hydrazines having a monocyclic or condensed heterocycle as an adsorption group are particularly preferred, and specific examples of such couplers are described in Japanese Patent Application No. 58-237101.
has been admonished.

Compounds described in Japanese Patent Application No. 58-146097 which have a development accelerator moiety in the coupler residue, or compounds described in Japanese Patent Application No. 58-214808 which release a development accelerator etc. through an oxidation-reduction reaction with a developing agent. The compounds described in 1 can also be used in the photosensitive material of the present invention.

DAR couplers are preferably incorporated into the light-sensitive silver halide emulsion layer of the light-sensitive material of the present invention, and
As described in No. 8-47601 or No. 58-237104, it is preferable to use substantially non-photosensitive silver halide grains in at least one of the photographic constituent layers.

The light-sensitive materials produced using the present invention contain hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, and sulfonamide phenols as color capri-preventing agents or color-mixing preventive agents. It may also contain a talking conductor or the like.

In the photosensitive material of the present invention, an ultraviolet absorber can be added to the wood-philic colloid layer.
, No. 553,794, No. 4,236.013, Japanese Patent Publication No. 51-6540, European Patent No. 57,160, etc. Penztriazole substituted with an aryl group, U.S. Patent: tS4,450 , 229 and 4,195.999; U.S. Pat. Nos. 3,705,805 and 3,707.
Cinnamic acid esters described in No. 375, U.S. Pat.
, 215,530 and British Patent No. 1.321,35
Benzophenones described in No. 5, U.S. Patent i3,7
61,272 and 4,431.726 can be used. A typical example of a UV absorber is RD24239 (June 1984), which may be used with the UV absorbing optical brighteners described in U.S. Pat. ) etc.

Known anti-fading agents can be used in the light-sensitive material of the present invention. Known organic anti-fading agents include hindered phenols, mainly hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, and bisphenols.
Typical examples thereof include gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Also (bissalicylaldoximad)
Nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel In the color photographic light-sensitive material of the present invention, compounds represented by the following general formulas [VI[] and [[] (ultraviolet absorber and antioxidant (antifading agent) agent))
By using one or more of these in combination, the storage stability of developed color images, particularly cyan images, can be improved.

In the formula, R, R, R and R8 may be the same or different and represent a hydrogen atom, a halogen atom, a nitro group,
It represents a cyano group, an alkyl group that may have a substituent, an alkoxy group, an aryl group, an aryloxy group, an acylamino group, or an alkoxycarbonyl group.

R and R8 may be the same or different,
Represents a hydrogen atom or an alkyl group that may have a substituent, and is not a hydrogen atom at the same time. R9 is m
represents a valent organic group, and m represents an integer.

Below, expressed by the general formula [■] or [[] (1!I
[-1) (![-2) (]lI-3) (Ic-4) C4Hsttl (II-5) (II-6) (II-7) (][-9) (II-10) (It -11) (N-12) G! [-13) t12LJ121yU 6t113(II -14
) (Dish-15) Den-16) (1!IL-17) (Beans-18) (N-19) 4H91υ G! ll-1) (II-2) (II-3) (II-4) (1!I-6) (1[-8) (l[-9) t U4H9C6)1131tl (IOL-10) (E[ -11) (fi-12) As a binder or protective colloid that can be used in an emulsion layer or an intermediate layer of an uninvented light-sensitive material.

Although it is advantageous to use gelatin, other hydrophilic colloids can also be used, such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethyl cellulose, carboxymethyl cellulose, Cellulose derivatives such as cellulose sulfur esters, sodium alginate,
Sugar derivatives such as starch derivatives; various single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, holivinylimidazole, polyvinylpyrazole, etc. Synthetic hydrophilic polymer materials can be used.

Gelatin includes general-purpose coal-processed gelatin, acid-processed gelatin, Bull, Sac, Sci, and Ph.
ot.

Japan, No. 16, p. 30 (1966)
Enzyme-treated gelatin as described in may also be used;
Furthermore, gelatin hydrolysates and enzymatically decomposed products can also be used.

The silver halide emulsion used in the present invention is usually prepared by mixing a water-soluble silver salt (for example, silver nitrate) solution and a water-soluble halide salt (for example, potassium bromide, sodium chloride, potassium iodide alone or a mixture thereof) solution with gelatin. It is produced by mixing in the presence of a water-soluble polymer solution such as In addition to silver chloride and silver bromide, typical silver halides produced in this manner include mixed silver halides such as silver chlorobromide, silver chloroiobromide, and silver iodobromide. The silver halide preferably used is silver chloroiodobromide, silver iodochloride, or silver iodobromide, which does not contain silver iodide or contains less than 3% by mole of silver iodide. Silver halide grains may have different phases inside and on the surface, may have a multiphase structure such as a bonded structure, or may consist of a uniform phase throughout the grain, or may contain a mixture of these. For example, silver chlorobromide grains with different phases may have a core or single or multiple layers within the grain that are richer in silver bromide than the average halogen composition; The grain may have a core or single or multiple layers that are richer in silver chloride than the average halogen composition; therefore, the surface layer of the grain may have a layer richer in silver bromide than the average halogen composition, or vice versa. The average grain size of silver halide grains that may be covered with a rich layer (in the case of spherical or near-spherical grains, the grain diameter is taken as the grain size, and in the case of cubic grains, the ridge length is taken as the grain size, and the projected area is also It's impossible to be average)
is 2μ, less than 0. tp or more is preferred, and particularly preferred is 1 l or less and 0.15° or more.

The particle size distribution can be narrow or wide, and the particle size distribution is narrow such that 90% or more, especially 95% or more of the total particles fall within ±40% of the average particle size in terms of particle number or weight. So-called monodisperse silver halide emulsions can be used in the present invention. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are mixed in the same layer or in separate layers in emulsion layers having substantially the same color sensitivity. Can be applied in multiple layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, dodecahedral, dodecahedral, etc.).
), or may have an irregular crystal shape such as a spherical shape, or may have a composite shape of these crystal shapes, or may be a tabular grain. In particular, an emulsion may be used in which the plate grains having a length/thickness ratio of 5 or more, especially 8 or more account for 50% or more of the total projected area of the grains, and are composed of a mixture of these various crystal forms. These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the grains.

The photographic emulsion used in the present invention is P, Glafki
Written by Chimie et Physique
Photographique (Pau1Mante1
Publishing, 1967), Photographic E+ulsion Ch by G, F, Duffin
emistry (Focal Press, 196
6 years), V. L., Zelikman et a.
Making and Caating P
Photographic Emulsion (Foc
Al Press, 1964). i.e. acid method,
Either a neutral method or an ammonia method may be used, and methods for reacting a soluble silver salt and a soluble halogen salt include a one-sided mixing method and a simultaneous mixing method.

Any combination thereof may be used.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one type of simultaneous mixing method, pag in the liquid phase in which silver halide is produced is
A method of keeping constant, that is, the so-called chondrold ψ
A double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or its 1111 salt, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present together.

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

Known silver halide solvents (for example, ammonia, Rodankali or U.S. Pat. When physical ripening is performed in the presence of 1,000-onythyl compounds and 1,000-on compounds described in Japanese Patent Application Laid-open No. 54-100717 or JP-A-54-155828, etc., the particles have a regular crystal shape and a nearly uniform particle size distribution. A monodispersed emulsion having the following properties is obtained. In order to remove soluble silver salts from the emulsion before and after physical ripening, noodle washing, flocculation sedimentation method, ultraleakage method, etc. are used.

The silver halide emulsion used in the present invention can be chemically sensitized by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination.

Namely, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g. thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g. stannous salts, amines); reduction sensitization method using noble metal compounds (e.g., total complex salts, Pt
A noble metal sensitization method using complex salts of metals of group 1 of the periodic table such as , Ir, and Pd can be used alone or in combination.

The photographic emulsion used in the present invention is spectrally sensitized with a photographic sensitizing dye. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole 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 these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, ie.

Indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxadole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, and the like can be applied.

These sensitizing dyes may be used alone or in combination, and 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,
For example, the emulsion may contain a substance exhibiting supersensitization.
Aminostyryl compounds substituted with a nitrogen-containing heterocyclic group (for example, U.S. Pat.
No. 5,721), aromatic organic acid formaldehyde condensates (such as those described in U.S. Pat. No. 3,743,510), cadmium salts, azaindene compounds, etc. No. 615,613,
The combinations described in 3,615,641, 3,617,295 and 3,635,721 are particularly useful.

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. i.e. azoles, such as benzothiazolium salts, pensiimigzolium salts, imidazoles.

Benzimidazoles (preferably 5-nitrobenzimidazoles), nitroindazoles, benzotriazoles (preferably 5-methylbenzotriazoles), triazoles, etc.; mercapto compounds, such as mercaptothiazoles, mercaptobenzothiazoles, Mercaptobenzimidazoles, mercaptobenzoxazoles, mercaptooxadiazoles, mercaptothiadiazoles, mercaptotriazoles, mercaptotetrazoles (especially!-Phenyl-5-
mercaptotetrazoles, etc.), mercaptopyrimidines, mercaptotriazines, etc.; thioketo compounds, e.g. , 3, 3a, 7) tetraazaindene), pentaazaindene, etc.; benzenethiosulfonic acids, benzenesulfinic acids, benzenesulfonic acid amides; anti-capri agents or stabilizers such as norins such as adenine, etc. Many compounds known as can be added.

For further specific examples of antifoggants or stabilizers and their use, see, for example, U.S. Pat.
．． No. 474, No. 3,982,947, Special Publication No. 52-2
No. 8660, RD17643, (December 1978
month) VIA~VIM and E, J.

``5 tabilization of P'' by Birr.
hotogrQl! 1ic 5ilverHalide
Emulsions” (Focal Press
, published in 1974).

The invention is applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The arrangement order of these layers can be arbitrarily selected as necessary. Preferred layer arrangements include, from the support system, a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer in this order, an n-sensitive layer, a green-sensitive layer and a red-sensitive layer in that order, or a blue-sensitive layer, a red-sensitive layer and a green-sensitive layer in that order. Further, any emulsion layer having the same color sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the ultimate sensitivity.
The graininess may be further improved as a layer structure, and a non-light sensitive layer may exist between two or more emulsion layers having the same color sensitivity. Emulsion layers with different color sensitivities may be inserted between them, or a reflective layer such as fine-grain silver halide may be provided below the high-speed layer, particularly the high-speed blue-sensitive layer, to improve sensitivity.

Generally, 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 example, it may be used in combination with an infrared-sensitive layer for pseudo-color photography or semiconductor laser exposure.

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

Various known coating methods such as dip coating, roller coating, curtain coating, and extrusion coating can be used to coat the photographic emulsion layer and other hydrophilic colloid layers. U.S. Patent No. 2,681,294 as appropriate
Multiple layers may be applied simultaneously by coating methods such as those described in US Pat.

The photosensitive material of the present invention can be used as a filter dye.

Alternatively, water-soluble dyes may be contained in the wood-philic colloid layer for various purposes such as preventing irradiation or halation. Examples of such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, and merocyanine dyes. , anthraquinone dyes, and azo dyes are preferably used. In addition, cyanine dyes, azomethine dyes, triarylmethane dyes, and phthalocyanine dyes are also useful. Oil-soluble dyes are emulsified and dispersed by an oil protection method to form a wood-philic colloid layer. It can also be added to.

In addition to the above-mentioned additives, the photosensitive material of the present invention further includes:
Stabilizers, development accelerators, hardeners, surfactants, antifouling agents, lubricants, optical brighteners, mordants, matting agents, antistatic agents, plasticizers, and other additives useful in photographic materials. may be added, representative examples of these additives are R
e5earchDisclosure17643 (1
December 1978) and 18716 (January 1979)
January).

In the photographic material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal that is commonly used in photographic materials. be done. Useful flexible supports include cellulose nitrate, cellulose acetate,
Cellulose acetate butyrate, polystyrene, polyvinyl chloride,
These include films made of semi-synthetic or synthetic polymers such as polyethylene terephthalate and polycarbonate, and papers coated or laminated with baryta layers or α-olefin polymers (eg, polyethylene, polypropylene, ethylene/butene copolymers), etc. The supports may be colored using dyes or pigments, or may be made black for the purpose of blocking light, and the surfaces of these supports are generally treated with an undercoat to improve adhesion with photographic emulsion layers, etc. Ru. The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper. The present invention is also applicable to black-and-white light-sensitive materials using a three-color coupler mixture described in RD17123 (July 1978) and the like.

Various exposure means can be used for the photosensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination or writing light source. Natural light (sunlight), incandescent lamps, halogen-filled lamps, mercury vapor lamps, fluorescent lamps, and flash light sources such as strobes or metal-burning flashbulbs are common. A gas, dye solution, or semiconductor laser that emits light in a wavelength range ranging from ultraviolet to infrared.

Light emitting diodes and plasma light sources can also be used as recording light sources. In addition, fluorescent screens (such as CRTs), liquid crystals (LCDs, etc.) emit light from phosphors excited by electron beams, etc.
) and lanthanum-doped lead titanium zirconate (P
It is also possible to use an exposure means that combines a linear or planar light source with a micro-shutter array using LZT) or the like. If necessary, the spectral distribution used for exposure can be adjusted using color filters.

The color light-sensitive material according to the present invention has a color image that can be obtained by forming a latent image on a silver halide emulsion using light and then performing a commonly used color development process. The basic steps include developing, bleaching, and fixing. Also, in the inversion method, h
Prior to the above 3 basic steps, it includes a first development (black and white development) and a brushing step for residual silver halide. In the development process, the above-mentioned basic steps may be independent, or a processing bath may be used in which two or more steps proceed simultaneously, such as a -bath bleach-fix solution. Furthermore, the basic steps can be carried out in two or more parts if necessary, for example, a combination such as one color development, first fixing, and bleach-fixing. In addition to the basic process, the processing process includes
If necessary, functions such as = dura mater, neutralization, water washing, image stabilization, posterior dura mater, etc. can be independently or combined 1! A treatment bath can be provided for the purpose of Furthermore, in the step of developing a photosensitive material containing a developing agent, an alkaline activation bath or the like can also be used.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Although amine phenol compounds are also useful as color developing agents, p-phenylenediamine compounds are preferably used. Representative examples include 3-methyl-4-amino-N, N-diethylaniline, 3- Methyl-4-amino-N-ethyl-N-
β-hydroxylethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methoxyethylaniline and their sulfates,
Examples include hydrochloride and p-toluenesulfonate. These diamines are generally more stable in their salt form than in their free state, and are therefore preferably used.

The color developer may contain PH buffers such as alkali metal sulfites, carbonates, borates or phosphates, development inhibitors such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds or It generally contains anti-capri agents and the like. In addition, if necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines 1 Dye-forming power pullers, competitive couplers, nucleating agents such as sodium poron hydride, auxiliary developers such as l-phenyl-3-pyrazolidone, tackifying agents, U.S. Pat. The polycarboxylic acid chelating agent described in No. 083,723, West German patent application (Ol.
, S) No. 2.622.950 may be added to the color developer.

In the development process for reversal color photosensitive materials, black and white development is usually performed and then color development is performed. This black and white developer contains dihydroxybenzenes such as hydroquinone, l-phenyl-
3-pyrazolidones such as 3-pyrazolidone or N-
Known black and white developers such as 7-minophenols such as methyl-p-7-minophenol can be used alone or in combination.

After color development, the photographic emulsion layer is usually bleached. t':
! The self-treatment may be performed simultaneously with the fixing treatment or separately. Examples of bleaching agents include polyvalent bleaching agents such as iron (■), cobalt (■), chromium (Vl), and copper (II). Metal compounds, peracids, quinones, nitrone compounds, etc. are used. 0 Typical bleaching agents include ferricyanide;
dichromate; iron (m) or cobal) (III)
Organic complex salts of, for example, 7minobocarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propatoltetraacetic acid, or complex salts of organic acids such as citric acid, tartaric acid, and malic acid; Persulfates; manganates; nitrosophels, etc. can be used. Among these, ethylenediaminetetraacetate iron (m) sodium, ethylenediaminetetraacetate iron (m) ammonium and persulfate are preferred from the viewpoint of rapid processing and environmental pollution. Furthermore, ethylenediaminetetraacetic acid iron (III) complex salt is also present in a separate bleaching solution.
It is also particularly useful in bath bleach-fix solutions.

The bleaching solution and bleach-fixing solution may contain various accelerators as needed. For example, in addition to bromide ions and iodide ions, U.S. Pat. -26586, JP-A No. 53-32735,
Thiourea compounds as shown in No. 53-36233 and No. 53-37016; JP-A-53-1244
No. 24, No. 53-95631, No. 53-57831, No. 53-32736, No. 53-65732, No. 5
No. 4-52534 and U.S. Patent No. 3°893.858
Thiol-based compounds such as those shown in JP-A-49
-59644, 50-140129, 55-2
No. 8506, No. 53-141623, No. 53-104
Heterocyclic compounds described in JP-A Nos. 232 and 54-35727; JP-A-52-20832 and JP-A-55-25
064 and 55-28506; tertiary amines described in JP-A-48-84440; thiocarbamoyl compounds described in JP-A-49-42349; Bromine ion, iodide ion, thiol-based or disulfide-based compounds, which may be used in combination or in combination of two or more, are preferred bleaching accelerators. These whitening accelerators are particularly effective when bleaching and fixing color light-sensitive materials for photography.

Thiosulfate and thiocyanate are used as fixing agents.

Thioether compounds such as thioureas and a large amount of iodides can be mentioned, but thiosulfates are generally used.

As the preservative for the bleach-fix solution and the fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

After the bleach-fixing process or the fixing process, a washing process is usually performed. In the water washing process, various known compounds may be added for the purpose of preventing precipitation and saving water. For example, to prevent precipitation, inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, etc. Water softeners, bactericidal agents and anti-piping agents that prevent the growth of various types of bacteria, algae, and mold, hardening agents such as magnesium salts and aluminum salts, and surfactants that prevent dry loads and unevenness. It can be added as needed. Orori, E, West
, “Water Quality Cr1teria”
.

Phot, Sci, Eng, Volume 6, 344-3
Compounds described on page 59 (1965) may also be added. The addition of chelating agents and anti-piping agents is particularly effective.

Further, in the washing process, the amount of washing water can be saved by performing multi-stage countercurrent washing using two or more F tanks.

For example, in the case of a 0-step process in which a multi-stage countercurrent stabilization process as described in JP-A No. 57-8543 is required, 2 to 9 countercurrent baths are required. Various compounds are added for the purpose of stabilizing the image.For example, various buffers (for example, borate, metaborate, boric acid, phosphoric acid) to adjust the membrane pH (for example, pH 3 to 8) are added. Typical examples include hardeners such as salts, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, etc.) and formalin. In addition, water softeners (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid) as needed.

Typical additions include aminopolyphospho/acids, phosphonocarboxylic acids, etc.), bactericidal agents (proxel, irithiazolone, 4-thiazolinebenzimidazole, halogenated phenols, etc.), surfactants, optical brighteners, hardeners, etc. agents may be used, or two or more of the same or different desired compounds may be used in combination.

Ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate,
It is preferable to add various ammonium salts such as ammonium sulfite and ammonium thiosulfate.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. is preferable 0 For example, U.S. Pat.
, 342,597Q, No. 3,342.599, Re5earch Disc
Losure Nos. 14850 and 15159, fuldol compounds described in U.S. Patent No. 13924, metal salt complexes described in U.S. Pat. For the beginning, JP-A No. 56-6235, No. 5
No. 6-16133, No. 56-59232, No. 56-6
No. 7842, No. 56-83734, No. 56-8373
No. 5, No. 56-83736, No. 56-89735,
No. 56-81837, No. 56-54430, No. 56
-106241, 56-107236, 57-
Examples include various salt-type precursors described in No. 97531 and No. 57-83565.

The silver halide color photosensitive material of the present invention may contain various 1-phenyl-
Typical compounds that may contain 3-pyrazolidones 44 JP-A-56-64339 No. 1 57-3.4454
No. 7, No. 57-211147, No. 58-50532, No. 5B-50536, No. 58-50533, No. 5
8-50534, 58-50535 and 58-
It is described in ti5438 etc.

Various processing solutions in the present invention are used at 10°C to 50°C. A temperature of 33°C to 38°C is standard for jeA, but higher temperatures can be used to accelerate processing and shorten the processing time, or conversely, lower temperatures can improve image quality and stability of the processing solution. be able to. Further, in order to save the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide as described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be carried out.

A heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in the various processing baths as necessary.

(Effects of the Invention) The light-sensitive material of the present invention has the effect of efficiently producing a cyan image with one good hue and excellent storage stability. That is,
The cyan coupler used in the present invention has an isopropyl group introduced into the 5-position of the phenol nucleus, and its color-developing inclusion has a good hue (maximum absorption wavelength, half-width, and extinction coefficient) almost equivalent to that of the methyl-substituted product. However, it has better storage stability than the ethyl substituted product, and its coloring effect is almost the same as that of the methyl or ethyl substituted product. By the way, the bulkier t-butyl & substituted product has 1 hue defect (approximately 20% of the half width).
% increase, extinction coefficient decrease), but also the color development efficiency decreases. Therefore, the cyan coupler of the present invention exhibits completely unexpected effects.

Furthermore, the photographic material of the present invention is characterized in that the cyan dye-forming coupler is easily dissolved and dispersed in organic solvents and has high dispersion stability.

(Synthesis Examples and Examples) Next, the present invention will be described in more detail by showing Examples and synthesis examples of cyan dye-forming couplers.

Synthesis Example 6 - (2-(2,4-di-tert-amylphenoxy)-butanoyl7mino>-2,4-dichloro-3-t
so-propylphenol (exemplary cyan coupler (4)
) Synthesis of 27.2 g of 3-iso-propylphenol was
ml of methylene chloride, 25.6 mfL of chlorinated sulfonic acid was added dropwise at 0°C over 20 minutes, and
After stirring for an hour, methylene chloride was distilled off, the residue was dissolved in 100 ml of water, and this solution was added with 31.0 ml of chlorine gas.
2g was introduced over 30 minutes and stirred at 25-30°C for 1 hour. 50 ml of methylene chloride was added to this reaction mixture, and after stirring, the layers were separated, and 25 ml of nitric acid (d=1.40) was added to the aqueous layer.
After the reaction was completed, the mixture was stirred at 50°C for 1 hour and 30 minutes, extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off. Purification was performed using a silica gel column to obtain 15 g of 2,4-dichloro-6-nitro-3-iso-propylphenol.

Then 15 g of 2,4-dichloro-6-nitro-3-i
So-propylphenol is dissolved in sodium hydroxide (
15g) - Water (200mJ1) - Methanol (40mJ
Dissolve in the solution of l) while stirring.

20g+7) Hydrosulfide soda was added little by little. After the addition, the mixture was stirred for 1 hour, and the precipitated crystals were filtered, washed with water, and dried to obtain 10 g of 6-amino-2,4-dichloro-3-iso-propylphenol.

10 g of 6-amino-2,4-dichloro- thus obtained
3-iso-7'ropyruphenol was dispersed in 70 ml of acetonitrile and 10 ml of dimethylacetamide, and while heating with a steam path, 17 g of 2-(2 chloride) was added.
, 4-di-tert-amylphenoxy)butanoyl was added dropwise over about 5 minutes, followed by heating and stirring for 20 minutes, cooling to room temperature, and adding 10 m of water to precipitate crystals. After cooling with water for another 30 minutes, filtering, washing with acetonitrile and drying, 6-(2-(2,4-di-tert)
-amylphenoxy)-butanoylamine)-2,4-
Colorless crystals of dichloro-3-iso-propylphenol were obtained. Yield fiE 23 g (yield 92%), melting point 146-148°C, original N analysis: Real 11Nfm Hnia, 95X, C: 8
B, 71$, N: 2.85g calculated value) 1 near, 91L
C: 8B, 88$, N: 2.88% Example 1 Coating layers 1 (bottom layer) to 7 (top layer) on double-sided polynyletine laminated paper as described in Table I and Table TI. A color photographic material was prepared.

(Samples A to 0) The coating solution for the first layer described in Section 2 was prepared as follows. That is, 100 g of the yellow coupler shown in Table I was mixed with 100 ml of digityl phthalate (DBP) and 2 ml of ethyl acetate.
This solution was dissolved in a 1% aqueous solution of sodium dodecylbenzenesulfonate containing 80 mM.
Next, the entire amount of this emulsified dispersion was made into a blue-sensitive silver chlorobromide emulsion (Br
80%) (contains 66.7 g of Ag) to prepare a coating solution. Coating solutions for other layers were prepared in the same manner. 2°4-dichloro-6-hydroxy-s-triazine-sodium salt was used as a hardener for each layer.

The following spectral sensitizers were used for each emulsion.

Blue-sensitive emulsion layer, 3.3'-G (γ-sulfopropyl)
- Selenacyanine sodium salt (2
-5,5°-diphenyl-9-ethyloxacarbocyanine sodium salt (2.5XlO' mol per mol of silver halide) Red-sensitive emulsion layer: 3,3°-di(γ-sulfopropyl)
-9-Methyl-thiadicarbocyanine sodium salt (2.5 x 10-' mol per 1 mol of halogenated I) The following dyes were used as itagetic inhibitor dyes in each emulsion layer.

In the table, TNP represents trinonyl phosphate, DBP represents dibutyl phthalate, and TCP represents tricresyl phosphate, and the chemical structures of the compounds (a) to (h) are as follows.

(*a) Magenta coupler (*b) Anti-fading agent (Jti) (*C) Anti-fading agent (*d) Yellow coupler (umbrella e) Anti-fading agent (*f) Cyan coupler ff1 (*g) Cyan coupler I (*h) Cyan coupler These samples were exposed to red light through a continuous wedge and then developed according to the steps IIj and JI! below.

Layer 1 Temperature Time Developing solution
33℃ 3 minutes 30 seconds Bleach-fix solution 33℃
Washing with water for 1 minute and 30 seconds at 28-35°C for 3 minutes The formulation of the treatment solution used is as follows.

Rihuang Tomb Benzyl Alcohol 15ml Diethylene Glycol 8ml Ethylene Diamine 4
Acetic acid, disodium salt 5g Sodium sulfite 2g Hydroxylamine sulfate 3g 4-Amino-N-ethyl-N- (β-methanesulfonamidoethyl)-m-toluidine 2/3 Sulfate 111 Water mound 5g Add water and 1
00 Q m Jl pHlo, adjusted to 20, filtered ethylenediaminetetraacetic acid, disodium salt 2g ethylenediaminetetraacetic acid ferric salt 40g sodium sulfite
5g ammonium thiosulfate 7
Add 0g water and make 1000ml pH 6
, 80. Each sample after development was incubated at 100°C for 2 hours and at 60°C-7.
A discoloration/fading test was performed in which the samples were stored at 0% RH for lθ weeks. After the test, the concentration of each sample was measured using a Macbeth RD-514 type densitometer at the pre-test concentrations of 1 and 0. The results are shown in Table M. From the results in Table M, it can be seen that the compounds of the present invention are significantly superior in color image fastness compared to the compounds of comparative examples.

Example 2 Silver chlorobromide emulsion (silver bromide 50 mol %, coated silver amount 250 mg/m''), gelatin y (1000 mg/rn') and cyan coupler (
Table ■) is E1m dibutyl phthalate (200mg/m
'') was coated, gelatin (1000 mg/m'') was further applied as a protective layer and dried to obtain a test HP-y.
It was created.

Table 1 These samples were exposed to red light through a continuous wedge for sensitometry, and then developed in the same manner as in Example 1.

After 8 I heat of development, each sample was kept at 0100°C for 2 weeks.

Shun) It was stored under conditions of 10 weeks at 60°C and 70% RH and 8 days in a xenon exposure machine (illuminance 130,000 lux), and a discoloration/fading test was performed. Table V shows the results of measuring the purulence of each sample after the test using a Macbeth RD-514 densitometer at a location where the pre-test concentration was 1.0.

As can be seen from the table, the couplers of the present invention exhibit very good color image fastness, especially under hot and moist heat conditions.

Procedure 7 city “p-’i #F (method) 19th April 1985

Claims (1)

[Scope of Claims] A silver halide color photographic material characterized by containing a cyan dye-forming coupler represented by the following general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・［I
] (In the formula, R represents a substituted or unsubstituted aliphatic, aryl or heterocyclic group, X represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an acylamino group, and Z represents a hydrogen atom or a developing agent. represents a group that can be separated in an oxidative coupling reaction with R, X, or Z, and may form a dimer or higher multimer.)