JPH0139575B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <<Industrial Application Field>> The present invention relates to a photographic material containing a cyan dye-forming coupler having a ureido group. More specifically, the present invention relates to a silver halide color photographic light-sensitive material with good color reproducibility, which contains a cyan coupler having a ureido group with excellent fading resistance. <Prior Art> After exposing a silver halide color photographic light-sensitive material to light, color development is performed, whereby an oxidized aromatic primary amine developing agent and a dye-forming coupler react 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. However, there remain several problems with the storage stability of color images obtained when conventionally used phenols and naphthols are used. For example, US Patent 2367531 and
The color images obtained with the 2-acylaminophenol cyan coupler described in US Pat. No. 2,423,730 generally have poor heat fastness, and are
The color images obtained from the 2,5-diacylaminophenol cyan coupler described in No. 2772162 generally have poor light fastness;
- Naphthamide cyan couplers are generally unsatisfactory both in terms of 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. Pat. No. 3,446,622;
No. 3996253, No. 3758308, No. 3880661, JP-A-Sho
56-65134). In particular, the couplers disclosed in Japanese Patent Application No. 56-196676, No. 57-1620, and No. 57-72202 have excellent solubility in high-boiling organic solvents;
These couplers have good dispersion stability and transparency in photographic emulsions, and also have good storage stability of color images obtained from these couplers.
That is, it has extremely excellent performance such as excellent fastness to heat and light. <<Problems to be Solved by the Invention>> As a result of further research into cyan couplers having such ureido groups, the present inventors have discovered that when dissolving the coupler in a coupler solvent and introducing it into a silver halide emulsion layer. The type of coupler solvent that dissolves the coupler and the ratio of the coupler solvent to the coupler (hereinafter referred to as coupler solvent/coupler ratio).
As a result, the maximum absorption of the image dye formed by color development after exposure shifts significantly, and in some cases, the wavelength may become significantly shorter, resulting in poor color reproduction. This tendency is particularly strong when using phosphate ester coupler solvents, so in order to prevent deterioration of color reproducibility by keeping the absorption maximum of the image dye formed at a wavelength similar to that of known couplers, ,
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, the first object of the present invention is to provide a photographic material in which a cyan coupler having a ureido group can cause the absorption maximum of an image dye formed by color development treatment to be within a preferable range for a cyan image. It is to be. 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. <<Means for Solving the Problems>> That is, the present invention provides a coupler solvent represented by the general formula [ ], which has a water content of 1% by weight or more, or a mixed coupler solvent thereof. , the coupler solvent/coupler weight ratio is
This photographic light-sensitive material is characterized in that it contains at least one kind of phenol cyan coupler substituted with an acylamino group at the 5th position and a ureido group at the 2nd position, dissolved in an amount of 0.7 or less. General formula [] In the formula, R ¹ , R ² and R ³ are each a substituted or unsubstituted alkyl group having 4 to 18 carbon atoms, which can be optionally substituted with aryl, alkoxycarbonyl or alkyloxy, or alkyl , alkoxycarbonyl, or alkyloxy, and is a substituted or unsubstituted aryl group having 6 to 18 carbon atoms. In the present invention, the water content of the coupler solvent refers to the solubility of water in the coupler solvent expressed in % by weight, and its value is measured using a CA-01 Karl Fischer trace moisture analyzer (manufactured by Mitsubishi Chemical Corporation). ) at 25℃. Specific examples of coupler solvents represented by the general formula [ ] and having a water content of 1% or more include coupler solvents having the following structural formula. Phosphate coupler solvent Among these coupler solvents, Illustrative No.
(1) and (3) are preferred. 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 (λmax) of the cyan dye formed by color development is the same as that of silver halide when the coupler is dissolved in a coupler solvent. Although it was found that it varies greatly depending on the type of coupler solvent used when dispersing it in the emulsion layer and the coupler solvent/coupler ratio, further detailed research revealed that the cyan dye formed during color development processing creates intermolecular hydrogen bonds. It has also been revealed that the absorption maximum shifts to the shorter wavelength side when this hydrogen bond is broken or weakened by the coupler solvent or water dissolved in the coupler solvent. In the case of a combination of the phosphate coupler solvent of the present invention and the coupler, other coupler solvents (e.g., phthalate coupler solvent, amide coupler solvent, fatty acid ester coupler solvent,
The absorption maximum often shifts more than in the case of benzoic acid ester coupler solvents, benzyl alcohol esters, etc.). The absorption maximum shift of the cyan dye is partly caused by the coupler solvent itself, and partly by water dissolved in the coupler solvent, but in any case, the concentration of the coupler is sufficiently increased, If the coupler solvent/coupler ratio is made sufficiently small, the concentration of the cyan dye formed by the color development process will also increase, which will not only facilitate the formation of hydrogen bonds between dye molecules, but also facilitate the breaking of the formed hydrogen bonds. Since the number of molecules involved is also reduced, the movement of the absorption maximum of the cyan dye can be suppressed to a sufficiently small level. In the case of a phosphate ester coupler solvent with a water content of 1% or more expressed by the general formula [ ] used in the present invention, the coupler solvent/coupler ratio is a weight ratio (hereinafter, weight ratio unless otherwise specified). This is achieved when the ratio (abbreviated simply as ratio) is 1.0 or less. In the present invention, not only can a phosphate ester coupler solvent represented by the general formula [] with a water content of 1% or more be used alone or in combination, but also other coupler solvents can be used. It is also possible to use a mixture of them. Examples of such other coupler solvents include phthalate coupler solvents, amide coupler solvents, fatty acid ester coupler solvents, benzoate coupler solvents, benzyl alcohol esters, etc. Specific examples thereof include: For example, coupler solvents having the following structural formula can be mentioned. Next, the coupler used in the present invention will be explained in detail below. In the present invention, the 5th position is an acylamino group,
All phenol cyan couplers having the 2-position substituted with a ureido group can be used, but cyan couplers represented by the following general formula [] are particularly preferred. General formula [] In the formula, R represents an optionally substituted alkyl group, aryl group, or heterocyclic group, and X represents a group that can be separated during oxidative coupling with a developing agent,
Y represents an optionally substituted alkyl group, phenyl group, or heterocyclic group. The above R, X, and Y of the general formula [] will be explained in detail below. In the general formula [], R is a chain or cyclic,
Preferably, an alkyl group having 1 to 22 carbon atoms (for example, a methyl group, a butyl group, a pentadecyl group, a cyclohexyl group, etc.), an aryl group (for example, a phenyl group,
naphthyl group, etc.), or heterocyclic group (e.g., 2-
Pyridyl group, 4-pyridyl group, 2-furanyl group,
2-oxazolyl group, 2-imidazolyl group, etc.)
represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group (e.g., a methoxy group, a dodecyloxy group, a 2-methoxyethoxy group, etc.),
Aryloxy group (e.g. phenoxy group, 2,
4-di-tert-amylphenoxy group, 3-tert-
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) group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc.), amide group (e.g., acetylamide group, ethylcarbamoyl group, methanesulfonylamide group, butylsulfamoyl group, etc.), imide group (e.g. , succinimide group, hydantoinyl group, etc.), sulfonyl group (e.g. methanesulfonyl group), sulfamide group (e.g. dimethylsulfamide group),
It may be substituted with a substituent selected from a hydroxy group, a cyano group, a nitro group, and a halogen atom. In the general formula [], X is a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), and the leaving group represented by X is:
Alkoxy groups (e.g., ethoxy group, dodecyloxy group, methoxyethylcarbamoylmethoxy group, carboxymethoxy group, methylsulfonylethoxy group, etc.), aryloxy group (e.g., phenoxy group, naphthyloxy group, 4-carboxyphenoxy group, etc.) , acyloxy groups (e.g., acetoxy, tetradecanoyloxy, benzoyloxy, etc.), sulfonyloxy groups (e.g., methanesulfonyloxy, toluenesulfonyloxy, etc.), amide groups (e.g., dichloroacetylamino, hepta- fluorobutyrylamino group, methanesulfonylamino group, toluenesulfonylamino group, etc.), alkoxycarbonyloxy group (e.g., ethoxycarbonyloxy group, benzyloxycarbonyloxy group, etc.),
Examples include aryloxycarbonyloxy groups (eg, phenoxycarbonyloxy groups) and imide groups (eg, succinimide groups, hydantoinyl groups, etc.). In the general formula [], Y represents a chain or cyclic alkyl group, aryl group, or heterocyclic group preferably having 1 to 22 carbon atoms, and may be substituted with the substituent described for R. Preferred Y is a phenyl group, and a preferred cyan coupler is represented by the following general formula []. General formula [] In the formula, R and X are the same as the substituents described in the general formula [], and R ⁴ is a hydrogen atom, an alkyl group,
Aryl groups, heterocyclic groups, alkoxy 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 group, toluenesulfonyloxy group, etc.), amide group (e.g., acetylamide group, ethylcarbamoyl group, methanesulfonamide group, butylsulfamoyl group, etc.), imide group (e.g., succinimide group, etc.) group, hydantoinyl group, etc.), sulfonyl group (e.g., methanesulfonyl group, propanesulfonyl group, etc.), sulfamide group (e.g., dimethylsulfamide group, diethylsulfamide group, etc.), cyano group, nitro group, and n represents 1 to 5
represents an integer, and when multiple substitutions are made, they may be the same or different. In the general formula [], particularly preferred R ⁴ is:
A halogen atom, a sulfonyl group, a sulfonamide group, a sulfamoyl group, a polyfluoroalkyl group, an acyl group, an alkoxycarbonyl group, and a cyano group, and particularly preferably n is 1 or 2;
The substitution position is m or p position. Next, the cyan coupler used in the present invention,
Some specific examples are shown below. Among these, the melting points of typical couplers are shown below. 2 130-133℃ 12 148-151℃ 3 130-135℃ 13 155-157℃ 4 166-169℃ 15 166-167℃ 5 209-211℃ 16 189-190℃ 6 228-231℃ 17 175-176℃ 7 153-155°C 18 152-154°C 10 117-119°C 19 122-134°C 11 88-92°C 21 199-200°C Typical synthesis examples of the couplers of the present invention are shown below. Synthesis Example 1 Synthesis of exemplified coupler (1) Synthesis of 2-(4-methylsulfonylphenylureido)-5-nitrophenol 19.3 g of 4-methylsulfonylaniline was added to 60 ml
of tetrahydrofuran and 11 ml of pyridine, and 19.8 g of phenyl chloroformate was added dropwise under ice cooling. After stirring for 30 minutes, the mixture was poured into ice water containing 12 ml of hydrochloric acid, and the precipitated crystals were collected by filtration and dried, weighing 32.8 g. 32.8 g of the obtained 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 to obtain 33.5 g of the title compound. Synthesis of Exemplary Coupler (1) 32 g of 2-(4-methylsulfonylphenylureido)-5-nitrophenol obtained in ), 30 g of reduced iron, and 2 g of ammonium chloride were added to 200 ml of isopropanol and 20 ml of water for 3 hours. The mixture was heated to reflux. After cooling, add 5.5 g of sodium hydroxide to 10 ml of water.
After adding the iron powder to the solution, the iron powder was filtered out. After neutralizing with acetic acid, the precipitated crystals were collected by filtration and dried to yield 16.2 g.
Crystals were obtained. 14.6 g of the obtained crystals were dissolved in 100 ml of acetonitrile, and while heating under reflux, 16.9 g of 2-(2,4-di-tert-phenoxy)butanoyl chloride was added dropwise, 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°C). Elemental analysis value C; 65.21% H; 7.03% N; 6.91% Calculated value C; 65.46% H; 7.27% N; 6.74% Other couplers could also be synthesized in the same manner as example coupler (1). As a method for introducing a coupler into a silver halide emulsion layer, a known method such as that described in US Pat. No. 2,322,027 is 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 if 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 distance between the cyan dyes produced by color development is close and it is easy to form intermolecular hydrogen bonds. . Therefore, the coupler solvent/coupler ratio is 1.0 or less, preferably 0.7 or less, more preferably 0.5 or less. The phosphate coupler solvent used in the present invention generally has very good solubility for ureido couplers, but if the coupler is insufficiently dissolved due to the small coupler solvent/coupler ratio, For example, other coupler solvents such as phthalate coupler solvents can be used in combination. In addition, in the invention, before dissolving the coupler in the coupler solvent, the boiling point is about 30 to 150°C.
It may be dissolved in an organic solvent such as lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, or the like. Even when a coupler dissolved in a coupler solvent is introduced into a silver halide emulsion layer by these methods, for example, the method described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-Open No. 51-59943, A dispersion method using a polymer can also be used. 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 coloring coupler, a known open-chain ketomethylene coupler can be used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. A specific example of a yellow coupler that can be used is a US patent.
No. 2875057, No. 3265506, No. 3408194, No.
No. 3551155, No. 3582322, No. 3725072, No.
No. 3891445, West German Patent No. 1547868, West German Application Publication
No. 2219917, No. 2261361, No. 2414006, British Patent No. 1425020, Japanese Patent Publication No. 10783, No. 1978, Japanese Patent Publication No. 1977-
No. 26133, No. 48-73147, No. 51-102636, No. 50
-6341, 50-123342, 50-130442, 50-123342, 50-130442,
No. 51-21827, No. 50-87650, No. 52-82424,
This is described in No. 52-115219, etc. As the magenta coloring coupler, pyrazolone compounds, indazolone compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are particularly advantageous. Specific examples of magenta coloring couplers that can be used include U.S. Pat. No. 2,600,788;
No. 2983608, No. 3062653, No. 3127269, No. 3127269, No.
No. 3311476, No. 3419391, No. 3519429, No.
No. 3558319, No. 3582322, No. 3615506, No.
No. 3834908, No. 3891445, West German Patent No. 1810464,
West German patent application (OLS) No. 2408665, OLS No. 2417945,
No. 2418959, No. 2424467, Special Publication No. 40-6031,
JP-A No. 51-20826, No. 52-58922, No. 49-
No. 129538, No. 49-74027, No. 50-159336, No.
No. 52-42121, No. 49-74028, No. 50-60233,
This is described in No. 51-26541, No. 53-55122, etc. As the cyan coloring coupler, phenol compounds, naphthol compounds, etc. can be used. Specific examples include U.S. Patent No. 2369929 and
No. 2434272, No. 2474293, No. 2521908, No.
No. 2895826, No. 3034892, No. 3311476, No. 3311476, No.
No. 3458315, No. 3476563, No. 3583971, No.
No. 3591383, No. 3767411, No. 4004929, West German patent application (OLS) No. 2414830, No. 2454329, Japanese Patent Application Publication No. 48-59838, No. 51-26034, No. 48-5055,
These are those described in No. 51-146828, No. 52-69624, and No. 52-90932. For colored couplers, for example, the US patent
No. 3476560, No. 2521908, No. 3034892, Tokko Akira
No. 44-2016, No. 38-22335, No. 42-11304, No. 42-11304, No.
No. 44-32461, JP-A No. 51-26034, No. 52-
Specification No. 42121, West German Patent Application (OLS) 2418959
You can use those listed in the issue. As a DIR coupler, for example, the US patent
No. 3227554, No. 3617291, No. 3701783, No.
No. 3790384, No. 3632345, West German patent application (OLS)
No. 2414006, No. 2454301, No. 2454329, British Patent No. 953454, Japanese Patent Application Publication No. 1983-69624, No. 49-122335
Those described in Japanese Patent Publication No. 51-16141 can be used. In addition to the DIR coupler, the light-sensitive material may also contain a compound that releases a development inhibitor during development; for example, U.S. Pat.
West German Patent Application (OLS) No. 2417914, Japanese Unexamined Patent Publication No. 1983-
Those described in No. 15271 and No. 53-9116 can be used. 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 are generally added in an amount of 2x10 ^-3 to 5x10 ^-1 mol, preferably 1x10 ^-2 to 5x10 ^-1 mol, per mole of silver in the emulsion layer. The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (such as those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (such as those described in U.S. Pat.
3314794 and 3352681), benzophenone compounds (for example, those described in JP-A-46-2784), cinnamic acid ester compounds (for example, those described in U.S. Pat. No. 3705805 and 3707375), butadiene Compounds such as those described in US Pat. No. 4,045,229 or benzoxide compounds (such as those described in US Pat. No. 3,700,455) can be used. Furthermore, U.S. Patent No. 3,499,762,
The material described in 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. Glafkides
Written by Chimie et Physique Photographique (Paul
Montel Publishing, 1967), GFDuffin
Photographic Emulsion Chemistry (The Focal
Press, 1966), VLZelikman et al.
MaKing and Coating Photographic Emulsion
(The Focal Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the methods for reacting the soluble silver salt and soluble halogen salt include one-sided mixing method, 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, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled double jet method can also be used. According to this method, a silver halide emulsion with a regular crystal shape and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be mixed and used. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present. 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 sulfates; sugar derivatives such as sodium alginate and starch 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. In addition to lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Phot.Japan, No. 16,
Enzyme-treated gelatin as described in P30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. Gelatin derivatives include gelatin with acid halides,
Those obtained by reacting various compounds such as acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinylsulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds can be used. Specific examples include US Patent Nos. 2,614,928, 3,132,945, and US Pat.
3186846, 3312553, British Patent No. 861414,
It is described in No. 1033189, No. 1005784, and Japanese Patent Publication No. 42-26845. The gelatin graft polymer is a gelatin grafted with a single (homo) or copolymer of vinyl monomers such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile, styrene, etc. can be used. In particular, polymers with some degree of compatibility with gelatin, such as acrylic acid,
Graft polymers with polymers such as methacrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylate are preferred. Examples of these are U.S. Pat.
It is described in issues such as No. 2956884. Typical synthetic hydrophilic polymer substances include, for example, West German Patent Application (OLS) No. 2312708, U.S. Patent Application No.
These are those described in No. 3620751, No. 3879205, and Japanese Patent Publication No. 43-7561. 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. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; Zaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,
3a, 7) tetraazaindenes), pentaazaindenes, etc.; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfonic acid, benzenesulfonic acid amide, etc. can be added. For example, U.S. Patent No. 3954474, U.S. Patent No. 3982947,
-28660 can be used. The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholins, and quaternary ammonium salts for the purpose of increasing sensitivity, increasing contrast, or accelerating development. compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. For example, US Patent No. 2400532,
Same No. 2423549, No. 2716062, No. 3617280, Same No.
Those described in No. 3772021, No. 3808003, British Patent No. 1488991, etc. can be used. The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments,
Included are 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 of Imidazole nuclei, quinoline nuclei, etc. can be applied.
These nuclei may be substituted on carbon atoms. Merocyanine dyes or complex merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, a thiazolidine-2,4-dione nucleus, and a thiazolidine-2,4-dione nucleus with a ketomethylene structure. A 5- to 6-membered heteroartic ring nucleus such as a barbiturate nucleus can be applied. Useful sensitizing dyes include, for example, the German patent
929080, U.S. Patent No. 2231658, U.S. Patent No. 2493748, U.S. Patent No.
No. 2503776, No. 2519001, No. 2912329, No. 2519001, No. 2912329, No.
No. 3656959, No. 3672897, No. 3694217, No.
No. 4025349, No. 4046572, British Patent No. 1242588,
Examples include those described in Japanese Patent Publication Nos. 44-14030 and 52-24844. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.
Typical examples are U.S. Patent No. 2688545, U.S. Patent No. 2977229,
3397060, 3522052, 3527641, 3527641, 3522052, 3527641,
No. 3617293, No. 3628964, No. 3666480, No.
No. 3672898, No. 3679428, No. 3703377, No. 3672898, No. 3679428, No. 3703377, No.
No. 3769301, No. 3814609, No. 3837862, No. 3837862, No. 3814609, No. 3837862, No.
4026707, British Patent No. 1344281, British Patent No. 1507803,
Special Publication No. 43-4936, No. 53-12375, Japanese Patent Publication No. 52-
It is described in No. 110618, No. 52-109925, etc. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostyl compounds substituted with nitrogen-containing heterocyclic groups (e.g.,
2933390 and 3635721), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3743510), cadmium salts, azaindene compounds, and the like. US patent
No. 3615613, No. 3615641, No. 3617295, No. 3615613, No. 3615641, No. 3617295, No.
The combination described in No. 3635721 is particularly useful. The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include
Included are oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used include British Patent No. 584609, British Patent No. 1177429, Japanese Patent Application Laid-Open No. 1985-85130,
No. 49-99620, No. 49-114420, No. 52-108115
No., U.S. Patent No. 2274782, U.S. Patent No. 2533472, U.S. Patent No.
No. 2956879, No. 3148187, No. 3177078, No. 3177078, No. 3148187, No. 3177078, No.
No. 3247127, No. 3540887, No. 3575704, No.
No. 3653905, No. 3718472, No. 4071312, No. 3653905, No. 3718472, No. 4071312, No.
It is described in No. 4070352. In the photographic material produced using the present invention, the photographic emulsion layer and other hydrophilic colloid layers may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener. These brighteners may be water-soluble, or water-insoluble brighteners may be used in the form of a dispersion. Specific examples of fluorescent brighteners are given in U.S. Pat. No. 2,632,701;
3169840, 3359102, British Patent No. 852075,
It is described in issues such as No. 1319763. In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known anti-fading agents include, for example, U.S. Pat.
No. 2675314, No. 2701197, No. 2704713, No. 2728659
No. 2732300, No. 2735765, No. 2710801,
Hydroquinone derivatives described in U.S. Patent No. 2816028, British Patent No. 1363921, etc.;
Gallic acid derivatives described in US Pat. No. 3069262, etc., US Pat. No. 2735765, US Pat.
p-alkoxyphenols described in No. 52-6623, US Pat. No. 3,432,300, US Pat.
No. 3574627, No. 3764337, JP-A-52-35633,
p described in No. 52-147434 and No. 52-152225
-Oxyphenol derivatives, such as bisphenols described in US Pat. No. 3,700,455. The photosensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifogging agent, and specific examples thereof include:
U.S. Patent No. 2360290, U.S. Patent No. 2336327, U.S. Patent No. 2403721,
Same No. 2418613, No. 2675314, No. 2701197, Same No.
No. 2704713, No. 2728659, No. 2732300, No.
No. 2735765, Japanese Patent Application Publication No. 50-92988, No. 50-92989,
No. 50-93928, No. 50-110337, No. 52-146235
No., and the specification of Japanese Patent Publication No. 50-23813. The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. A multilayer natural color photographic material usually has at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. For photographic processing of the light-sensitive material of the present invention, any known method can be used, and known processing solutions can be used. Further, the treatment temperature is usually selected between 18°C and 50°C, but it may be lower than 18°C or higher than 50°C.
Depending on the purpose, either a development process that forms a silver image (black and white photographic process) or a color photographic process that consists of a development process that forms a dye image can be applied. Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylene diamines (for example, 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino- N-Ethyl-N-
β-hydroxyethylaniline, 3-methyl-4
-Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamide ethylaniline, 4-amino-3-methyl-N-ethyl-N ―
β-methoxyethylaniline, etc.) can be used. Other Photography by LFAMason
Processing Chemistry (Focal Press, 1966)
P226-229, U.S. Patent No. 2193015, U.S. Patent No. 2592364
JP-A No. 48-64933, etc. may be used. Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants. can include. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, Fogging agents such as sodium boron hydride, auxiliary developers such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, US patents
The polycarboxylic acid chelating agent described in No. 4083723,
It may also contain antioxidants such as those described in OLS 2622950. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As a bleach,
For example, iron (), cobalt (), chromium (),
Compounds of polyvalent metals such as copper, peracids, quinones, nitroso compounds, etc. are used. for example,
Ferricyanide, dichromate, organic complex salts of iron () or cobalt (), aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or citric acid, tartaric acid, Complex salts of organic acids such as malic acid; persulfates, permanganates; nitrosophenols, etc. can be used. Of these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate, and ammonium ferric ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron() complex salts are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. Furthermore, bleaching solutions or bleach-fixing solutions are disclosed in US Pat. No. 3,042,520, US Pat.
In addition to the bleach accelerators described in Japanese Patent Publication No. 8506-8506 and Japanese Patent Publication No. 45-8836, the thiol compounds described in Japanese Patent Application Laid-open No. 65732-1983, various additives can also be added. <<Effects of the Invention>> According to the present invention, a ureido cyan coupler can be dissolved in a very small amount of a coupler solvent having high dissolution performance and introduced into a photographic emulsion layer. The dispersion stability of the coupler can be improved. 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. Color reproduction is also good. Furthermore, when a coupler of the general formula [] or [] is used, the above effects can be further improved, and even when processed with a bleaching solution with weak oxidizing power or a bleaching solution with fatigue, A sufficiently high image density can be obtained. Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited thereby. Example 1 As shown in Table 1 below, a coupler (example coupler No. 1) and a coupler solvent were mixed together with 10 ml of ethyl acetate and 0.25 g of sodium dodecylbenzenesulfonate at 60°C.
It was completely dissolved by heating to ℃. This solution was mixed with a 10% aqueous solution of Alkanol B (alkylnaphthalene sulfonate manufactured by DuPont).
A coupler dispersion was prepared by mixing 3.5 ml with 1 ml of 10% citric acid and 100 ml of a 10% aqueous gelatin solution, and emulsifying the mixture using a colloid mill. This dispersion was then mixed into a negative red-sensitive silver iodobromide emulsion (silver iodide;
5 mol %, average particle size: 0.5 μ), the coupler was added in an amount of 0.08 mol per mol of silver, and coated on a cellulose triacetate film base at a coating silver amount of 2.0 g/m ² . Obtained sample
Images 101 to 104 were wedge exposed to white light and subjected to the following development process at 38°C. 1 Color development... 3 minutes 15 seconds 2 Bleaching... 6 minutes 30 seconds 3 Washing... 3 minutes 15 seconds 4 Fixing... 6 minutes 30 seconds 5 Washing... 3 minutes 15 seconds 6 Stabilization... 3 minutes 15 seconds These The composition of the treatment liquid used in each step 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 Add 4.5g water 1 Bleach solution Ammonium bromide 160.0g Ammonia water (28%) 25.0ml Ethylenediamine-tetraacetic acid sodium iron salt
130.0g Glacial acetic acid 14.0ml Add water 1 Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0ml Sodium bisulfite 4.6g Add water 1 Stabilizer formalin 8.0ml Add water 1 After each of these processes, the maximum image density (Dmax)
Table 1 shows the results of measuring the spectral absorption characteristics of the area close to
It was shown to. Table 1 shows that the maximum absorption wavelength (λmax) of the photographic light-sensitive materials 101 to 103 of the present invention is a preferable spectral absorption wavelength equivalent to that of the conventionally used naphthol type coupler 104, and the photographic light-sensitive materials of the present invention Although it is a photographic light-sensitive material containing a cyan coupler having a ureido group, a photograph containing a conventional naphthol type cyan coupler [Table]

Claims (1)

[Scope of Claims] 1. Any coupler solvent represented by the following general formula [] whose water content is 1% by weight or more or a mixed coupler solvent thereof, (coupler solvent/coupler ) is dissolved in an amount such that the weight ratio of Color photographic material. General formula [] In the formula, R ¹ , R ² and R ³ are each a substituted or unsubstituted alkyl group having 4 to 18 carbon atoms, which can be optionally substituted with aryl, alkoxycarbonyl or alkyloxy, or alkyl , a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, which can be optionally substituted with alkoxycarbonyl or alkyloxy. 2. The silver halide according to claim 1, wherein the phenol cyan coupler substituted with an acylamino group at the 5th position and a ureido group at the 2nd position is represented by the following general formula [] Color photographic material. General formula [] In the formula, 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 an optionally substituted alkyl group, phenyl group or heterocyclic group. 3. The silver halide color photographic light-sensitive material according to claim 2, wherein the general formula [] is particularly a phenol cyan coupler represented by the following general formula []. General formula [] R and X in the formula are the same as R and X in the general formula []. R ⁴ is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy 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, or a nitro group. represent. n is 1~
When an integer of 5 is represented and multiple numbers are substituted, they may be the same or different. 4 In the general formula [], R ⁴ is a halogen atom, a sulfonyl group, a sulfonamide group, a sulfamoyl group, a polyfluoroalkyl group, an acyl group, an alkoxycarbonyl group, particularly substituted at the m or p position,
The silver halide color photographic material according to claim 3, wherein the silver halide color photographic material is a cyano group, and n is 1 or 2.