JPS5991442A - Silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photosensitive material superior in color reproductivity and stability by incorporating a phenol and cyan coupler dissolved in one of phosphate type coupler solvents represented by a specified general formula and having moisture content at a specified value or less, or in a mixture of them in a specified proportion. CONSTITUTION:A coupler solvent of a phosphate type is controlled to <=1wt% moisture content and one or more kinds of solvent represented by formula I in which R<1>, R<2>, R<3> are each 4-18C alkyl optionally substd. by aryl, alkoxycarbonyl, or alkyloxy, or 6-18C aryl optionally substd. by alkyl, alkoxycarbonyl, or alkyloxy. A weight ratio of coupler solvent/coupler is set to <=2. The coupler is a phenol and cyan coupler substd. by an amino group at the 5-position and by a ureido group at the 2-position, preferably, a cyan coupler represented by formula II in which R is alkyl, aryl, or heterocyclic; X is a group releasable at the time of oxidation coupling with a developing agent; and Y is alkyl, phenyl, or heterocyclic.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photographic material containing a cyan dye-forming coupler having a ureido group. More specifically, the present invention includes:
This invention relates to a silver halide color photographic material with good color reproducibility, which contains a cyan coupler having a ureido group with excellent fading resistance.

After exposing the silver halide photographic light-sensitive material to light, color development is performed to cause the oxidized aromatic primary amine developing agent to react with the dye-forming coupler to form a color image.

Generally, in this method, subtractive color reproduction is used, and in order to reproduce blue, green, and red, images of yellow, magenta, and cyan, which are complementary colors, are formed, respectively. In this case, phenols or naphthols are often used as cyan dye-forming couplers.
There is. However, there remain some problems with the storage stability of color images obtained when conventionally used phenols and naphthols are used. For example, the color images obtained from the 2-acylaminophenolic cyan couplers described in U.S. Pat. Nos. 2,367.531 and 2.423.730 generally have poor heat fastness; The color images obtained from the 2,5-diacylaminophenol cyan coupler described in 2,772,162 generally have poor light fastness, and the 1-
Hydroxy-2-natutamido cyan coverrs are generally unsatisfactory in terms of both light and heat fastness.

On the other hand, in recent years, it has been discovered that cyan couplers having ureido groups have excellent properties such as good light and heat fastness, and many developments have been made (for example, U.S. Patent No. 3.446, No. 622, No. 3,996,253, No. 3.758.308, No. 3,880. (i6
No. 1, JP-A-56-65-134 specification).

In particular, Japanese Patent Application No. 56-196,676, No. 57-1
, 620 and 57-72, 202 have excellent solubility in high-boiling organic solvents, good dispersion stability and transparency in photographic emulsions, and also The preservation of the resulting color image, i.e.
It has extremely excellent performance such as excellent fastness to heat and light.

As a result of further research into cyan couplers having such ureido groups, the present inventors discovered that when the coupler is dissolved in a coupler solvent and introduced into a silver halide emulsion layer, the coupler is dissolved in a coupler solvent. Depending on the type of dye and the ratio of coupler solvent to coupler (hereinafter referred to as coupler solvent/coupler ratio), the absorption maximum of the image dye formed by color development after exposure may be large (moved, and in some cases the wavelength may be significantly shortened). Color reproduction may deteriorate.

This tendency is particularly strong when a phosphate ester coupler solvent is used, so it is necessary to maintain the absorption maximum of the image dye formed at a wavelength similar to that of known couplers and prevent deterioration of color reproducibility. The present invention was achieved by discovering that the water content of the coupler solvent and the coupler solvent/coupler ratio must be within a certain range.

Therefore, a first object of the present invention is to provide a photographic material in which a cyan coupler having a ureido group can cause the maximum absorption of an image dye formed by color development to be within a preferable range for a cyan image. That's true.

A second object of the present invention is to provide a silver halide color photosensitive material that has excellent color reproducibility and excellent storage stability of the produced color images.

That is, the present invention uses any of the phosphoric acid ester coupler solvents represented by the general formula (1) having a water content of 1% by weight or less,
Or, two or more of these are dissolved in a mixed coupler solvent at a weight ratio of (coupler solvent/coupler) of 2 or less.
This is a silver halide color photographic light-sensitive material characterized by containing at least one phenol-cyan coupler substituted with an acylamino group at the 5th position and a urethane group at the 2nd position.

General formula (1) In the formula, R', F', F? 3 has 4 to 4 carbon atoms and can be optionally substituted with aryl, alkoxycarbonyl or alkyloxy
18 substituted or unsubstituted alkyl groups, or substituted or unsubstituted aryl groups having 6 to 18 carbon atoms that can be optionally substituted with alkyl, alkoxycarbonyl, or alkyloxy.

If the coupler solvent used in the present invention has a water content of 1% by weight or less, the general formula [! ] Any coupler solvent can be selected from among the coupler solvents represented by the following formulas, and can be used alone or in combination of two or more.

In the present invention, the water content of the coupler solvent is the solubility of water in the coupler solvent expressed in weight percent, and its value is determined using a CA-Of pear-shaped Karl Fischer trace moisture analyzer (Mitsubishi Chemical Corporation). This is the value measured at 25°C.

In the case of the coupler having a ureido group used in the present invention, as a result of detailed research, it was found that the absorption maximum (λma It has been found that the dispersion in the emulsion layer varies greatly depending on the type of coupler solvent used and the coupler solvent/coupler ratio.
More detailed research revealed that the cyan dye formed by color development forms intermolecular hydrogen bonds, and that these hydrogen bonds are broken or weakened by the coupler solvent or water dissolved in the coupler solvent. It has become clear that the absorption maximum is thought to shift toward shorter wavelengths.

Generally, in the case of a combination of a phosphate ester coupler solvent and a coupler, absorption is higher than in the case of other coupler solvents (e.g., phthalate esters, amides, fatty acid esters, benzo 8M esters, benzyl alcohol esters, etc.). The maximum often moves significantly. Therefore, in the present invention, not all coupler solvents represented by general formula (1) can be used unconditionally. That is, the movement of the absorption maximum of the cyan dye is partly caused by the coupler solvent itself, and partly by the water dissolved in the coupler solvent, but from the perspective of color reproduction,
Coupler solvents can be used as long as they have a water content of about 1% or less. Specific examples of such coupler solvents represented by general formula (1) and having a water content of 1% by weight or less include the following.

Below margin 6, 0=P (-0(iso-C+3H27
) 3cH2=CHCH2 However, [8H17: 2-ethylhexyl group Among these, coupler solvents of ranks 1.2.6 and 12 are preferred;
In particular, coupler solvents represented by the structural formulas 11 to 1.1 and Nn12 are preferred because of their low water content.

In the present invention, if the coupler solvent/coupler ratio is 2 or less, color reproduction equivalent to that of known couplers can be achieved. The use of one or more coupler solvents other than phosphate coupler solvents, such as coupler solvents, fatty acid ester-based Kab-Lar solvents, benzoate-based coupler solvents, or Hensyl alcohol-based esters. You can also do it.

Specific examples of these coupler solvents that can be mixed include the following.

Blank space below Phthalate ester coupler solvent Fatty acid ester coupler solvent Benzoic acid ester coupler solvent Amide coupler solvent Benzyl alcohol coupler solvent Below Blank space Next, the couplers used in the present invention will be described in detail below.

In the present invention, all phenol cyan couplers substituted with an acylamino group at the 5th position and a ureido group at the 2nd position can be used, but in particular, the following general formula (II
) is preferred.

General formula (II) In the formula (II), R represents an optionally substituted alkyl group, aryl group, or heterocyclic group, X represents a group that can be separated during oxidative coupling with a developing agent, and Y represents a group that can be separated during oxidative coupling with a developing agent. , represents an optionally substituted alkyl group, phenyl group, or heterocyclic group.

The above R, , x1Y of general formula (ff) will be explained in detail below.

In the general formula (It), R is a chain or cyclic alkino G group having preferably 1 to 22 carbon atoms (e.g. methyl group,
butyl group, pencudecyl group, cyclohexyl group, etc.),
Aryl group (e.g. phenyl group, naphthyl group, etc.),
or a heterocyclic group (e.g., 2-pyridyl group, 4-pyridyl group, 2-furanyl group, 2-oxazolyl group, 2-imidazolyl group, etc.), which are alkyl groups, aryl groups, heterocyclic groups, alkoxy groups (e.g. methoxy group,
dodecyloxy group, 2-methoxyethoxy group, etc.), aryloxy group (e.g., phenoxy group, 2,4-di-tert-amylphenoxy group, 3-Lert-butyl-4-hydroxyphenoxy group, naphthyloxy group, etc.), Carboxy group, carbonyl group (e.g., acetyl group, tetradecanoyl 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, methanesulfonylamide group, butylsulfamoyl group, etc.), imide group (e.g., succinimide group, hydantoinyl group, etc.), sulfonyl group (e.g., methanesulfonyl group) , a sulfamide group (eg, dimethylsulfamide group), a hydroxy group, a cyano group, a nitro group, and a halogen atom.

In general formula (II), X is a hydrogen atom, a halogen atom (
For example, fluorine atom, chlorine atom, bromine atom, etc.), as well as leaving groups represented by ethoxy group, etc.), aryloxy group (e.g., phenoxy group, naphthyloxy group, 4-carboxyphenoxy group, etc.), acyloxy group (e.g., acetoxy group, tetrazocallyoxy group, benzoyloxy group, etc.), sulfonyloxy group ( For example, methanesulfonyloxy group, toluenesulfonyloxy group), amide group (for example, dichloroacetylamino group, heptafluorobutyrylamino group, methanesulfonyl"1-mino group,
toluenesulfonylamino group, etc.), alkoxycarbonyloxy group (e.g., ethoxycarbonyloxy group,
(benzyloxycarbonyloxy group, etc.), aryloxy group (eg, phenoxycarbonyloxy group, etc.), and imide group (eg, succinimide group, hydantoinyl group, etc.).

In the general formula (II), Y represents a chain or cyclic alkyl group, preferably a C1-C22 alkyl group, a ring group, or a heterocyclic group, and is substituted with the substituent described for R. While reading.

Preferred Y is a phenyl group, and a preferred cyan coupler is represented by the following general formula (III).

General formula (I[[] In the formula, R and groups (e.g., methoxy group, octyloxy group, etc.), aryloxy group (e.g., phenoxy group, etc.), carboxyl group, carbonyl group (e.g., acetyl group, benzoyl group, etc.), ester group (e.g., methoxycarbonyl group, phenoxycarbonyl group) , acetoxy group, benzoyloxy group, butoxysulfonyl ink,
toluenesulfonyloxy group, etc.), amide group (e.g., acetylamide group, ethylcarbamoyl group, methanesulfonamide group, butylsulfamoyl group, etc.), imide group (e.g., succinimide group, hydantoinyl group, etc.), sulfonyl group (e.g. methanesulfonyl group, propanesulfonyl group, etc.), sulfamide group (e.g. dimethylsulfamide group, diethylsulfamide group, etc.)
, a cyano group, or a nitro group, n represents an integer from 1 to 5, and when multiple substitutions are made, each may be the same or different.

In general formula (III), particularly preferred R4 is a halogen atom, sulfonyl group, sulfonamide group, sulfamoyl group, polyfluoroalkyl group, acyl group, alkoxycarbonyl group, or cyan group, and particularly preferred n is 1 or 2. and the substitution position is m or p position.

Next, some specific examples of cyan couplers used in the present invention will be shown.

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o ○OOOO DAY41e'J4JC'J畢1 Among these, the melting points of typical couplers are shown below.

2.130~133℃ 12.148~151'C3,
130~135℃ xa, t5'5~157℃4.16
6~169℃ 15.166~167℃5.209~2
11℃ 16.189~190'C6,228~231
"C17, 175-176℃ 7.153-155℃ 1
8; 152-154°C 10.117-119°C 19.
122-134℃11, 88-92℃ 21.19
Typical synthesis examples of the couplers of the present invention are shown below.

Synthesis Example 1 Synthesis of Exemplary Coupler (1) 1) 2-(4
-Methylsulfonylphenylureido) -Synthesis of -5-ditrophenol 19.3 g of 4-methylsulfonylaniline was added to 60 m
j! of tetrahydrofuran and 11 ml of pyridine, and 19.8 g of phenyl chloroformate was added dropwise under water cooling. After stirring for 30 minutes, the mixture was diluted with 12 ml of hydrochloric acid.
The precipitated crystals were collected by filtration and dried, weighing 32.8 g.

32.8 g of 1η crystals, 17.9 g of 2-amino-5-nitrophenol and 0.8 g of imidazole were suspended in xylene and heated under reflux for 3 hours.

After cooling, the precipitated crystals were collected by filtration and dried, yielding 33.5 g.
The title compound was obtained.

ii) Synthesis of Exemplary Coupler (1) 32 g of 2-(4-methylsulfonylphenylureido)-5-nitrophenol obtained in i), 30 g of reduced iron, and 2 g of ammonium chloride were mixed with 200 m of isopropanol.
The mixture was added to 20 ml of water and heated under reflux for 3 hours. After cooling, 5.5 g of sodium hydroxide was dissolved in 10 mJ of water and added thereto, and then the iron powder was filtered off. The crystals precipitated by neutralization with acetic acid were collected by filtration and dried to yield 16.2 g.

14.6 g of the obtained crystals were melted in 10 ml of acetonitrile, and 16.9 g of 2-(2,4-di-tert-phenoxy)butanoyl chloride was added dropwise while heating under reflux, followed by refluxing for 2 hours. After cooling, the mixture was poured into water, extracted with ethyl acetate, washed with water, and the solvent was distilled off under reduced pressure. The resulting oil was crystallized from acetonitrile to yield 20.0 g of the title coupler (melting point 129-131 DEG C.).

Elemental analysis value C; 65.21% Ni 7.03% Ni 6.91% Calculated value C165.46% 1.1.7.27% N, 6.74% Other couplers were prepared in the same manner as the example coupler (1). I was able to synthesize it with

As a method for introducing a coupler into a silver halide emulsion layer, known methods such as those described in US Pat. No. 2,322,027 are generally used.

However, in the case of the cyan dye-forming coupler having a ureido group used in the present invention, the cyan dyes formed by color development after exposure form intermolecular hydrogen bonds, and these hydrogen bonds are broken due to some reason. , or is weakened, the absorption maximum of the formed cyan dye shifts to the shorter wavelength side, resulting in insufficient color reproduction.

. Therefore, when the coupler used in the present invention is dissolved in a coupler solvent, it is preferable to use a high concentration so that the cyan dyes produced by color development are close to each other and easy to form intermolecular hydrogen bonds.

Therefore, the coupler solvent/coupler ratio is 2.0 or less, preferably 1.5 or less, and more preferably 1.0 or less.

The phosphate coupler solvent used in the present invention generally has very good solubility for ureido couplers, but in cases where the coupler is insufficiently dissolved due to the small coupler solvent/coupler ratio. For example, a coupler solvent such as a phthalate ester coupler solvent can be used in combination. In addition, in the present invention, when the coupler is dissolved in the coupler solvent, the boiling point is about 30 to 15
Organic solvents such as ethyl acetate, lower alkyl acetates such as butyl acetate, ethyl propionate, 2
It may be dissolved in butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, and the like.

Even when a coupler dissolved in a coupler solvent is introduced into a silver halide emulsion layer by these methods, for example, Japanese Patent Publication No. 51-39,853, Japanese Patent Application Laid-Open No. 51-59
The dispersion method using a polymer described in , No. 943 can also be used in combination.

The photographic emulsion prepared according to the present invention contains not only color image-forming couplers other than the ureido couplers used in the present invention, but also colored couplers for color correction, so-called DIR couplers, and additives for improving the hue of sensitive materials. It may also contain commonly added additives such as color-forming couplers, ultraviolet absorbers, and stabilizers for photographic performance.

Next, additives such as couplers that can be added in the present invention will be explained in detail.

As the yellow color-forming coupler, a known open-chain ketomethylene coupler can be used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow couplers that can be used include U.S. Pat.
No. 506, No. 3 408.194, No. 3,551.1
No. 55, No. 3.582,322, No. 3,725,07
No. 2, No. 3,891,445, West German Patent No. 1,547°868, West German Patent Application No. 2,219,917, No. 2,
No. 261,361, No. 2,414,006, British Patent No. 1,425,020, Japanese Patent Publication No. 51-10783, Japanese Patent Publication No. 47-26133, No. 4B-73147, No. 5
No. 1-102636, No. 50-6341, No. 50-1
No. 23342, No. 50-130,442, No. 51-2
No. 1827, No. 50-87650, No. 52-8242
No. 4, No. 52-115219, etc.

Magenta coloring couplers include pyrazolone compounds,
- fdazolone compounds, cyanoas, cetyl 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.
Same 3. 062. No. 653, No. 3,127,269, No. 3,311゜476, No. 3,419.391,
No. 3,519, '429, No. 3,558.319,
3.582.322, 3.615,506, 3.834,908, 3.891,445, West German Patent No. 1,810,464, West German Patent Application (OLS) 2
, No. 408.665, No. 2,417゜945, No. 2,
No. 418,959, No. 2,424.467, Special Publication No. 4
No. 0-6031, JP-A-51-20826, JP-A No. 52-
No. 58922, No. 49-129538', No. 49-7
No. 4027, No. 50-159336, No. 52-421
No. 21, No. 49-74028, No. 50-60233, No. 51-26541, No. 53-55122, etc.

Cyan coloring coupler Toji-ζ is a phenolic compound,
Nafl-based compounds and the like can be used. Specific examples are U.S. Pat. Nos. 2,369,929 and 2,434,
No. 272, 2. 474. No. 293, 2,521
, No. 908, No. 2,895°826, No. 3,034.
No. 892, No. 3,311.476, No. 3.458,3
No. 15, No. 3 476.563, No. 3,583,97
No. 1, No. 3.591,383, No. 3,767.411
No. 4,004,929, West German patent application (OLS)
2,414.830, 2,454,329, JP-A-48-59838, JP-A No. 1-26034, JP-A-4B
-5055, 51-146828, 52-69
No. 624 and No. 52-90932.

As a colored coupler, for example, U.S. Patent No. 3.47
No. 6.560, No. 2,521,908, No. 3,034
．． No. 892, Special Publication No. 44-2016, No. 3B-223
No. 35, No. 42-11304, No. 44-32461, JP-A No. 51-26034, No. 52-4212
Specification No. 1, West German patent application (OLS,) 2,418,9
Those described in No. 59 can be used.

As a DIR coupler, for example, U.S. Pat.
No. 7.554, No. 3,617,291, No. 3.701
, No. 783, No. 3,790,384, No. 3,632.
No. 345, West German Patent Application (OLS) 2,414.006
No. 2,454,301, No. 2,454,329, British Patent No. 953゜454, JP-A-52-69624
No. 49-122335, Special Publication No. 51-16141
Items listed in the number 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, U.S. Pat. Nos. 3,297,445 and 3,379,529
It is possible to use those described in OLS No. 2,417.914, JP-A-51-15271, and JP-A-53-9116.

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

The same compound may be contained in two or more different layers.

These couplers generally range from 2xlσ3 moles to 5x161 moles per mole of silver in the emulsion layer, preferably ]
x 162 moles to 5 x lo-' moles are added.

The photosensitive material produced using the present invention has a hydrophilic copolymer. The coid layer may contain an ultraviolet absorber. For example, benzotriazole compounds substituted with aryl groups (e.g., those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (e.g., those described in U.S. Pat. No. 3,314,794,
3,352゜681), benzophenone compounds (e.g., those described in JP-A-46-2784), cinnamic acid ester compounds (e.g., U.S. Pat. No. 3,70-2784),
5.805, as described in 3,707,375)
, butadiene compounds (e.g. U.S. Pat. No. 4,045.22)
9), or benzoxidol compounds (eg, those described in US Pat. No. 3,700,455) can be used. Additionally, U.S. Patent No. 3,49
Those described in No. 9.762 and JP-A-54-48535 can also be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers.

The photographic emulsion used in the present invention is P, Glafkide.
Chimle et Physlque P
photographque (Paul Mon
(1967), G, F.

Written by Duffin
hIcEmulsion Chemistry
(T'heFocal Press, 1966)
,■.

Making by L. Zellkman et al.
and CoatinHPPhotography
c Emulsion (The Focal P
(Res., 1964). That is, acidic method, neutral method,
Any method such as the ammonia method may be used, and the method for reacting the soluble silver salt with the soluble silver salt may include a one-sided mixing method, a simultaneous mixing method, and a combination thereof.
ζ is also good.

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 form of the simultaneous mixing method, a method of keeping p to g constant in the liquid phase in which silver halide is produced, ie, the so-called Chondrald 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.

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

In the process of silver halide grain formation or physical ripening,
Cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or their complex salts, rhodium salts or their complex salts, iron salts, iron complex salts, etc. may coexist.

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters; sugar derivatives such as sodium alginate and carrier derivatives; polyvinyl Alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like.

As for gelatin, in addition to lime-processed ceratin, acid-processed gelatin, Bull, Soc, and Sci.

Photo, Japan, No. 16. P30 (19
Enzyme-treated gelatin as described in 66) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. Gelatin derivatives include various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds. The product obtained by reacting ζ can be used. A specific example is US Patent 2
, No. 614.928, No. 3,132,945, No. 3,
1.86,846, 3. 312. No. 553, British Patent No. 861.414, British Patent No. 033.189, British Patent No. 1,005,784, Japanese Patent Publication No. 42-26845, etc.

The seratin graft polymer may be a single (homo) or copolymer of vinyl monomers such as gelatin, acrylic acid, methacrylic acid, their esters, derivatives such as amides, acrylic monomers, sutylene, etc. A grafted graft can be used. Particularly preferred are graft polymers with polymers which are compatible with gelatin to some extent, such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylates and the like. Examples of these are U.S. Pat.
It is described in No. 7, No. 2,956,884, etc.

Typical synthetic hydrophilic polymer substances include, for example, West German Patent Application (OLS) No. 2,312,708 and U.S. Patent No. 3,62.
No. 0.751, No. 3,879.205, Special Publication No. 1973-
It is described in No. 7561.

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. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles,
J mohensimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole M (special number, 21)
-Soenyl-5-mercaptotetrazolecaptotriazines; thioke 1 compounds such as oxinatrindione;
Hi't + xy substitution mouth, 3, 3a, ? ), pentarr9' indenes, etc.; benzene thiosulsonic acid, benzene J resin/acid, . It is possible to add a number of compounds known as antifoggants or stabilizers, such as sullefonic acid amide F and the like. For example, U.S. Patent 3,954.4
No. 74, No. 3,982,947, Special Publication No. 52 28
．． 660 can be used.

In the photographic photosensitive material of the present invention, for the purpose of increasing sensitivity, increasing contrast, or accelerating development, the additive layer of the material contains, for example, polyalkylene oxide or ether.
Derivatives such as C stell, amine, th ether compound,
It may also include thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazoli F-containing compounds, and the like. For example, US Patent 2,
No. 400,532, No. 2,423,549, No. 2.7
No. 16.062, No. 3,617,280, No. 3,77
Those described in British Patent No. 2.021, British Patent No. 3.808.003, British Patent No. 1.488.991, etc. can be used.

The photographic emulsions used in this invention may be spectrally sensitized with medium dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. For these dyes, any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus. That is, pyridine nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus,
Pyridine nuclei, etc.; nuclei 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, pensuoxa Dole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. can be used repeatedly. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-nithioxazolidine-2 nucleus as a nucleus having a ketomedylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, diobarbituric acid nucleus, and the like can be applied.

Useful sensitizing dyes include, for example, German Patent No. 929.0
No. 80, U.S. Patent No. 2,231,658, U.S. Patent No. 2,493
．． No. 748, No. 2,503.776, No. 2,519,
No. 001, 2. 912. 32ri No. 1, 3,65
No. 6,959, No. 3,672゜897, No. 3,694
, No. 217, No. 4,025.349, No. 4,046,
No. 572, British Patent No. 1,242,588, Special Publication No. 1972
Examples include those described in No. 14030 and No. 52-24844.

These sensitizing dyes may be used alone or in combination, and the sensitizing dye combination -U is particularly often used for the purpose of supersensitization.

A typical example is US Pat. No. 2.6 (No. 18,545).
No. 977.229, No. 3,397,060, No. 3,5
22. (No. 152, No. 3,527,641, No. 3,6
No. 17,293, 3. 628. No. 964, 3,
No. 666.480, 3. (i72゜898, same 3,
No. 679,428, No. 3,703.377, No. 7
No. 69,301, No. 3゜814.609, No. 3,83
No. 7.862, No. 4.026,707, British Patent No. 1,
No. 344.281, No. 1,507,803, Special Publication No. 4
3-4936, No. 53-12.375, JP-A-1973
-110,618 and No. 52-109.925.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminosujiru compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Pat. Nos. 2,933,390 and 3,635,7)
21), aromatic organic acid formaldehy 1
-condensates (such as those described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds, etc. U.S. Patent No. 3,615,613;
No. 615,641, 3. Ei17,295 group, same 3,
The combinations described in No. 635,721 are particularly useful.

The photosensitive material produced using the present invention may contain a water-soluble dye as a filter dye in the hydrophilic colloid layer or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, stisal dyes, monocyanine dyes, cyanine dyes and ab dyes. Also useful are oxonol dyes; hemioxonol dyes and cyanine qsu°I. Specific examples of dyes that can be used are:
British Patent No. 584,609, British Patent No. 1,177.429,
JP-A-48-85130, JP-A No. 49-! No. 39620, No. 49-114420, No. 52-108°115, U.S. Patent No. 2.274. 782b4, 2゜533.
No. 472, No. 2,956,879, No. 3.1411.
No. 187, 1 Tsukasa 3,177.018, 3,247.
No. 127, No. 3,540,887, No. 3, ',
+75, No. 704, 3,65. 'L905,
This is described in No. 3,718,472, No. 4,071°312, and No. 4,070,352.
In the light-sensitive material produced using the present invention, a whitening agent such as a stilt-based, triazine-based, oxazole-based, or coumarin-based brightener is added to the hydrophilic layer of the rotated emulsion layer. May include. These brighteners may be water-soluble, or water-insoluble brighteners may be used in the form of a dispersion.

Specific examples of fluorescent whitening agents are given in U.S. Patent No. 2,632.70f,
3,1 (i9,840, 3,359゜102,
It is described in British Patent No. 852,075, British Patent No. 1,319.7635, etc.

When carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizer used in the present invention may be used alone or 2f! J-, (71) can also be used.

Known anti-fading agents 'ζ are, for example, U.S. Pat.
360.290 Tsukasa, 2,418゜613, 2,6
No. 75.314, No. 2,701.197, No. 2,70
No. 4,713, No. 2゜728.659, No. 2,732
, No. 300, No. 2,735,765, No. 2,710,
No. 801, No. 2,816,028, British Patent No. 1,36
Hydroquinone derivatives described in US Pat. No. 3,457,079, gallic acid derivatives described in US Pat. No. 3,069,262, etc., US Pat.
No. 765, No. 3,698,909, Special Publication No. 1976-20
No. 977, No. 52-6623] p-alkoxyphenols, US Pat. No. 3,432,300;
p- described in JP-A No. 3,573°050, JP-A No. 3,574.627, JP-A No. 3,764.337, JP-A No. 52-35633, JP-A No. 52-+ 47434, No. 52-152225 Oxyphenol derivatives, US patents 3, 7
There are bisphenols described in No. 00,455.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, a sunilupic acid derivative, etc. as a color antifoggant. Patent 2,360.2
No. 90, 2.33 [i.

No. 327, No. 2,403,721, No. 2,418.6
No. 13, No. 2,675,314, No. 2゜701.19
No. 7, No. 2,704,713, No. 2.728,65
No. 9, 2,732.3 + 10 inches, 2,735,76
No. 5, JP-A No. 50-92988, JP-A No. 50-92989
No. 50-93928, No. 50-110337,
52-146235, and is described in Japanese Patent Publication No. 50-231113.

The present invention is also applicable to multilayer, multicolor photographic materials in which the support-1-1 has at least two different spectral sensitivities. Multilayer natural color photographic materials usually include a red-sensitive emulsion layer on a support,
The green-sensitive emulsion layer and the blue-sensitive emulsion layer are each small (both
have one. The order of these layers can be arbitrarily selected as required. Normally, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a 71in inter-forming coupler, and the blue-sensitive emulsion layer contains a Yeff-forming coupler, but different combinations may be used depending on the case. You can also do that.

Photographic processing of the photosensitive material of the present invention can be carried out using any known method.
You can also use it! l! Known liquids can be used as the liquid. Also, the processing temperature is j111'
, θ are selected between 18°C and 50°C, but the temperature may be lower than 18°C or higher than 50°C. Development processing to form a spear image depending on the purpose (black and white photo processing)
, or any of the color photographic processes consisting of a development process that forms a dye image can also be applied.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. Color development'gA (?! Herbal medicines are known primary aromatic amine developers, such as phenylene diamines (e.g. 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N~diethylaniline, 4- Amino-N-ethyl-N-β-human I” xyedylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N
-ethyl-N-β-methanesulfamide 1-thylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyconitylaniline, etc. can be used.

In addition to this, Photo-grap by F. A. Mason
hlcProcesSingChemiqtry
(Focal Press, 1966) P22
6-229, U.S. Patent No. 2゜193.015, No. 2,5
92,364-, JP-A-48-64933, etc. may be used.

Color developers may also contain p II buffers such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants. etc. can be included. Mataze・
If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as Hensyl alcohol and diethyl glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, and dye-forming couplers. ,
Competitive couplers, fogging agents such as sodium boron hydride, auxiliary developers such as 1-phenyl-3-pyrazolidone, tackifiers, polycarboxylic acid clearing agents as described in U.S. Pat. No. 4,083,723, West Germany Public (OLS
) 2,622.950, etc. may also be included.

After color development, the photographic emulsion layer is subjected to a tπ bleaching process.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents include iron (■),
Compounds of polyvalent metals such as cobalt (■), chromium (■), and copper (■), peracids, quinones, and 21-roso compounds are used. For example, ferricyanide, organic complex salts of iron (■) or cobal) (III), e.g. 7) Aminopolycarboxylic acids such as -2-propatoltetraacetic acid or complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfates, permanganates; nitrosophenols, etc. can be used. Of these, potassium ferricyanide, sodium iron ethylenediaminetetraacetate (ITI) and ammonium iron (Ill) ethylenediaminetetraacetate are particularly useful.

Ethylenediaminetetraacetic acid iron (Ill[) complex salt is present in both the independent bleach solution C and the -bath bleach-fix solution ζ1J11
It is. Additionally, bleaching solutions or bleach-fixing solutions include U.S. Pat.
, 042.520, same 3. 241. In addition to bleaching accelerators described in Japanese Patent Publication No. 966, Japanese Patent Publication No. 45-8506, and Japanese Patent Publication No. 45-8836, thiol compounds described in Japanese Patent Application Laid-open No. 53-65732, various additives can also be added.

According to the present invention, since the ureido cyan coupler can be dissolved in a very small amount of a coupler solvent with high dissolving performance and introduced into the photographic emulsion layer, the dispersion of the coupler in the emulsion layer is particularly stable. You can increase your sexuality.

Since the photographic light-sensitive material produced according to the present invention uses a coupler having a ureido group, the image has high fastness to light and heat, and the maximum absorption wavelength of the image dye is minimized. The color Pr appearance is also good.

Furthermore, when a coupler of general formula (II 3 or (m)) is used, the above effects can be further improved, and when processed with a weakly oxidizing bleaching solution or a tired bleaching solution, However, a sufficiently high image density can be obtained.

Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited thereto.

Actual can row 1゜As shown in Table 1 below, couplers (example coupler No.
, 1) and the coupler solvent in 10 m# of ethyl acetate.

6 with 0.25g of F-decylbenzenesulfonate sodium
Completely dissolved by heating to 0°C.

This solution was mixed with 3.5 m6 of a 10% aqueous solution of Alkanol B (alkylnaphthalene sulfonate manufactured by DuPont),
1 ml of 10% citric acid and 1 ml of 10% geladine aqueous solution
00mβ and emulsified using a colloid mill to form a coupler dispersion liquid. Next, this solution was added to a negative red-sensitive silver iodobromide emulsion (silver iodide; 5 mol %, average grain size: 0°5/I) at a ratio of 0.08 mol of coupler to 1 mol of IN. The amount of coated silver was 2. It was applied at a ratio of Og/rd. The obtained samples 101 to 106 were wedge exposed to white light and subjected to the following development treatment at 38°C.

1. Color development---3 minutes 15 seconds 2.
fq white -------------6 minutes 30 seconds 3,
Washing with water -------3 minutes 15 seconds 4, Fixing ------6 minutes 30 seconds 5, Washing with water
-1--・--11--3 minutes 15 seconds 6, Stable ---3 minutes 15 seconds The composition of the processing solution used in each of these steps is as follows. .

Color developer sodium nitrilotriacetate 1. ．． 0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide
1.4g hydroxylamine sulfate 2.4g 4-(N-ethyl-N-βhydroxyethylamino)-2-methyl-aniline sulfate 4.5g water added 11 Bleach solution Ammonium bromide 160.0g aqueous ammonia (28%) 25.0m# ethylenediamine-tetraacetic acid sodium iron salt 130.0g glacial acetic acid
14.0mI! add water
lI2 Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium diosulfate (70%)'+75.0m/Sodium bisulfite 4.6g Add water ζ
1,2 Stabilizing liquid Polmarin 8.0 ml of water was added and ζ 1z After each of these treatments, the spectral absorption characteristics of a portion close to the maximum image density (Dmax) were measured and the results are shown in Table 1.

Table 1 shows that the maximum absorption wavelength (λmax) of the photographic light-sensitive materials 101 to 105 of the present invention is a preferable spectral absorption wavelength equivalent to that of the conventionally used naphthol type coupler 106, and the photographic light-sensitive materials of the present invention Although it is a photographic light-sensitive material containing cyankazolar having a ureido group, it is demonstrated that it achieves color reproduction equivalent to Photo-2 & 1 photosensitive materials containing naphthol-type cyan couplers from IJt. be.

Example 2 Cellulose 1-Lyacetate Film Support Second, a multilayer color photosensitive material having each layer having the composition shown below was prepared.

'KSIM: Antihalation layer between gelatin containing black co-t1-ide silver 2nd N: Intermediate layer 2, gelatin layer containing an emulsified dispersion of 1-quinone with 2.5-di-t-octyl hydride 3rd WI: red-sensitive low-speed emulsion layer Silver iodobromide emulsion (silver iodide = 5 mol%, average grain size: 0
．． 5u) Coated silver amount---1,79g/♂sensitizing dye I
-1~---~IN 6XIO-5 moles per 1 mole of sensitizing dye ■--1.5X] m5 mole per mole of silver 0,06 Mozuki coupler c ------1 0.00 per mole of silver
3 mole coupler D -------0.00 per mole of silver
3 mole tricresyl phosphate ------- Couvler A
2.5cc per 1g 4th layer: Red-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion (1N!4T nyl iodide, average grain size 0.7μ) 111---Amount of coated silver 1 .4g/n (sensitizing dye 1-・
- 3X10-5 moles per mole of silver Sensitizing dye■ -.-1.2X10-5 moles per mole of silver Coupler Δ---0.012 per mole of 811
5 mole coupler c ----0.00 per mole of silver
16 mole tricresyl phosphate - 2 for 1 g of coupler A
．． 5cc No. 51@: Same as the second intermediate layer No. ey*: Green-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion (Silver iodide: 4T nyl%, average grain size o
, 5p> 1---Amount of coated silver 1. Og/++ (sensitizing dye n1
---3XIO-5 moles per mole of silver sensitizing dye IV ---1XIO- per mole of silver
5 mole coupler B ------- per 1 mole of silver (0,0B
, molar coupler M---#J! For 1 mole” (0,00
0.00 for 8 mole coupler D------ silver ITnil
15 mole tricresyl phosphate ----1, 4c c Z
rd 7th 7th green! Green-sensitive highly sensitive layer silver iodobromide emulsion (M iodide: 5 mol%, average grain size: 0
．． 6. u) 111---Amount of coated silver 1.6g/po sensitizing dye m---2.5XIO per mole of silver
-5 moles of sensitizing dye 1v...-0.8XiO- per mole of silver
5 moles Coupler B ----0.02 moles per mole of silver Coupler M -m--0.003 moles per mole of silver Coupler D----0 per mole of silver .003
T-nitricresyl phosphate-1--1,4cc/I No. 8Wi
: Yellow filter layer 9th gelatin layer containing an emulsified dispersion of yellow 1' silver and 2° 5-di-t-octylhydroquinone in an aqueous gelatin solution: Blue-sensitive low-sensitivity emulsion layer Silver iodobromide Emulsion (silver iodide: 6 mol%, average grain nice: 0
．． 3μ) - Coated silver amount 1.5g/nf Coupler Y ----#N 0.25 per mol
Moltricresyl phosphate-1・-O,l c c7 r+
(No. 1019: Blue-sensitive high-sensitivity emulsion layer iodobromide (iodide plate: 6 mol%, average grain nice 0, 8μ
) 111---Coated silver amount 0.6g/nf coupler Y-1111---0, 04 per mole of silver Upper row/tricresyl phosphate---0, 1c c
/% 11th layer: Protective layer) - Dimethyl methacrylate - 1 - 7 - grains (approx. 1.5μ in diameter)
) coated with gelatin scum.

To prepare the coupler for each layer, add the coupler to a solution of tricresyl phosphate and ethyl acetate, add P-F decylbenzenesulfonate sodium as an emulsifier, heat and melt, and then mix with heated 10% 1i4i latin melt. and emulsified using a colloid mill. In addition to the composition mentioned above, a gelatin hardening agent and a sea surfactant were added to each layer.

The sample prepared as described above was designated as sample 201.

The compounds used to prepare this test fl are as follows.

Sensitizing dye 1: Anhydro-5.5゛ ~ Dichloro-3.
3゛-di(γ-sulfopropyl)-9-ethyl-thiacarpocyanin hydroxide pyridinium, salt sensitized color I■: Anhydro 9-ethyl-3, 3゛-di(γ-sulbopropyl)-4・5・4゛-5゛-dibenzodialylpocyanine hydroxyl F・l・ethylamine salt sensitizing dye sulbopropyl)oxycarbocyanine/sodium salt sensitizing dye 1v: anhydro-5, 6, 5° ・6゛ -tetrachloro 1-1'
-Diethyl-3.3゛-di(β-(β-(γ-sulfopropoxy)1toxy)ethyl)imidazolocarpocyanine hydroxide sodium salt coupler Δ Coupler D Coupler M Preparation of Samples 202 to 206: Sample 201 Samples 202 to 20 were prepared in the same manner as in sample 201, except that coupler A and tricresyl phosphate in the third and fourth rr4 were changed as shown in Table 2 below.
6 was produced.

The obtained samples 201 to 206 were exposed to wedge n light using a red filter, and developed in the same manner as in Example 1.

Table 2 shows the results of measuring the spectral absorption in the area close to the maximum image density (Dmax) after development, and the stability of color images when the developed film was stored at 60°C and 70% humidity for 14 days. This is the result of an investigation.

These results demonstrate that the photographic material obtained by the present invention not only has good spectral absorption characteristics but also extremely excellent color image stability.

Patent Applicant Fuji Photo Film Co., Ltd. Agent Patent Attorney Taki 1) Written amendment to the proceedings dated December 14, 1980 Kazuo Wakasugi, Commissioner of the Patent Office 1, Indication of the case 1982 Patent Application No. 201168 2, Invention Name: Silver halide color photographic light-sensitive material 3, relationship with the person making the amendment Patent applicant: Minamia Shigara Nakanuma Address: 210 i1h, Minamiashigara Higashi, Kanagawa Prefecture Name (5)
20) Fuji Photo Film Co., Ltd. Minoru Onishi Representative Minoru Ohnishi 4, Agent ■ 166 Address Koenji Kita 4-29-11-6, Suginami-ku, Tokyo
, Subject of amendment Column 7 of "Detailed Description of the Invention" of the specification, Contents of amendment 1) Page 76, line lo, "Surfactant" is corrected to "Surfactant."

2) On page 81, in the column "1 maximum absorption wavelength" of "Table 2", r
Correct mnJ to rnmJ.

21

Claims (1)

[Scope of Claims] 1) Any coupler solvent represented by the following general formula (1) with a water content of 1% by weight or less, or a mixed coupler solvent thereof (coupler solvent) A silver halide characterized by containing at least one phenolic cyan coupler substituted with an acylamino group at the 5th position and a ureido group at the 2nd position, dissolved in a ratio of 2 or less. Color photographic material. General formula (1) ORI In the formula, ri'', F?2, and Bi3 are substituted or unsubstituted alkyl groups of A8, or can be optionally substituted with alkyl, alkoxycarbonyl, or alkyloxy. , is a substituted or unsubstituted aryl group having 6 to 18 carbon atoms. 2) A phenol-cyan coupler in which the 5th position is an °r sylamino group and the 2nd position is a ureido group has the following general formula (11). A silver halide color photographic material according to claim 1, characterized in that it is represented by general formula (II), where R is an optionally substituted alkyl group, an aryl group, or represents a heterocyclic group, X represents a group that can be separated during oxidative coupling with a developing agent, and Y represents an optionally substituted alkyl group, phenyl group, or heterocyclic group. 3) General formula ( The silver halide color photographic light-sensitive material described in item 2) of the scope of the patent request, wherein II) is particularly a phenol cyan coupler represented by the following general formula (III).General formula CI'll) In the formula, RX is the same as RX in the general formula ([I), and R4
is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an aryloxy group, an aryloxy group, a carboxyl group, a carbonyl group, an ester group, an amide group, an imido group, a sulfonyl group, a sulfamide group, a cyano group , represents a nitro group. n represents an integer of 1 to 5, and when a plurality of n are substituted, they may be the same or different. 4) In general formula (III), - is a halogen atom, a sulfonyl group, a sulfonamide group, a sulfamoyl group, a polyfluoroalkyl group, an acyl group, an alkoxycarbonyl group, or a cyano group, particularly substituted at the m or p position, and n is 1 or 2) Claim 3)
The silver halide color photographic light-sensitive material described in .