JP2566393B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having high image quality and excellent stability over time.

[Conventional technology]

In recent years, two major trends can be seen in the photographic material for photographing due to the great increase in photographing opportunities due to the spread of compact cameras and the diversification of user needs.
One is the high sensitivity represented by 150-1000 and 1600,
The other is the demand for high image quality for the small format. On the other hand, with the spread of compact laboratories, short-time finishing, etc., demands for higher sensitivity, higher image quality, and more stable quality are increasing.

In order to meet such demands, research on silver halide emulsions has been actively conducted in recent years.

One of the flows is JP-A-55-142329 and JP-A-58-95337.
No. 58, No. 58-108526, No. 58-113927, No. 59-55426.
No. 58-127921, and the like, are tabular silver halide emulsion technology.

Tabular silver halide emulsions are ordinary hexahedron, octahedron, 14
It has the same amount of silver and a larger grain surface area than grains such as a face piece, which is advantageous for higher sensitivity. Further, by adsorbing more sensitizing dye, higher sensitivity and improved graininess, especially in a color sensitizing system. Is expected. Further, it is expected that light scattering can be prevented by improving the sharpness by reducing the thickness of the particles.

Such excellent features are expected, but on the other hand, increased fog on heat and sensitivity to humidity. Increased gamma reduction,
Many problems remain to be overcome for practical use, such as increase in latent image fluctuation after exposure and increase in fog due to pressure, and the solution is desired.

[Purpose of the present invention]

A first object of the present invention is to provide a silver halide photographic light-sensitive material which has high sensitivity, is excellent in graininess and sharpness, and has an improved variation in its ability to change with heat and humidity.

A second object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity, excellent graininess and sharpness, and having improved latent image fluctuation after exposure.

A third object of the present invention is to provide a silver halide photographic light-sensitive material which has high sensitivity, is excellent in graininess and sharpness, and has improved fog increase with respect to pressure.

[Structure of Invention]

The object of the present invention is to provide a silver halide photographic light-sensitive material comprising a support and a plurality of light-sensitive silver halide emulsion layers coated thereon. At least one of the emulsion layers has a solubility in water of 10% by weight or less. Hydrophobic photographic additives and the following general formulas [I] to [II
I] containing at least one kind of cyclic ether compound represented by I) as oil droplets, and the layer containing the cyclic ether compound contains a tabular silver halide emulsion having an average aspect ratio of 5: 1 or more. Was achieved by a silver halide photographic light-sensitive material.

General formula [I] In the formula, R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, a halogen atom,
Represents an unsubstituted or substituted linear or branched alkyl group, cycloalkyl group, aryl group, alkoxycarbonyl group, carbamoyl group, acyl group, cyano group, R ₁
And R ₂ and / or R ₁ and R ₄ may combine to form a ring.

General formula (II) In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ have the same meanings as R _{1 to} R _{4 in} the general formula [I], and R ₁ and R ₂ , R ₇ and R ₈ and / or R ₁ and R ₄ may combine to form a ring.

General formula (III) In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each R _{1 of the} general formula [I].
To R ₄ in the above formula, R ₁ and R ₂ may form a ring.

The silver halide emulsion of the present invention has an average aspect ratio of 5:
One or more tabular silver halide grains are contained. Aspect ratio refers to the ratio of diameter to thickness of a particle.
The diameter of a silver halide grain refers to the diameter of a circle having an area equal to the projected area of the grain. The preferred aspect ratio of the silver halide emulsion of the present invention is 6: 1 or more and 100 or less, more preferably 7: 1 or more and 50 or less, and particularly preferably 8: 1 or more and 20 or less.

The average thickness of the silver halide grains contained in the tabular silver halide emulsion of the present invention is preferably from 0.5 to 0.01 μm, particularly preferably from 0.3 to 0.05 μm.

The average grain size of the silver halide grains contained in the tabular silver halide emulsion of the present invention is preferably 0.5 to 30 µm, more preferably 1.0 to 20 µm.

The tabular silver halide emulsion of the present invention is preferably silver iodobromide or silver chloroiodobromide.

Tabular silver halide emulsions are disclosed in JP-A-52-153428 and JP-A-54-153428.
Nos. 155827, 54-118823, 58-127921, and 58-113928.

The silver halide emulsion of the present invention has a form in which the silver iodide content in the central portion of the tabular grains is lower than the silver iodide content in the disk-shaped outer week portion surrounding it, that is, silver iodide is the central portion. It is preferably composed of particles localized in.

The content of the high iodine content phase at the center is preferably 80% or less of the total volume of the grains, particularly preferably 60% to 10%.

The silver iodide content in the central portion is preferably 5 to 40 mol%, particularly preferably 10 to 30 mol%.

The low iodide content phase (peripheral portion) surrounding the central high iodide content phase has a silver iodide content of 0 to 10 mol%, more preferably 0.
It is preferably composed of 1 to 6.0 mol% silver iodobromide.

A tabular silver halide emulsion in which silver iodide is localized at the center can be obtained by a known method disclosed in JP-A-59-99433.

The average silver iodide content of the tabular silver halide emulsion of the present invention is preferably 3 to 20 mol%, more preferably 4 to 20 mol%.
To 15 mol%, particularly preferably 6 to 12 mol%.

In the tabular silver halide emulsion of the present invention, the ratio of the silver iodide content to the peripheral portion of the central portion is preferably 4 times or more, particularly preferably 5 times or more.

The halogen composition at the boundary between the central portion and the peripheral portion may change continuously or may have a clear boundary.

In the layer containing the tabular silver halide emulsion of the present invention, the tabular grains are preferably present in a weight ratio of at least 40%, especially at least 60%, based on all silver halide grains of the layer.

As a method for confirming the halogen composition structure in the grains of the silver halide grains of the present invention, JI Goldstein (goldatei) is used.
n) and DB Williams “X-ray analysis in TEM / ATEM”, Scanning Electron.
Microscopy (1977), Volume 1, IIT Research Institute, March 1977, p.651. The particles to be examined were placed on a grid and cooled to the temperature of liquid nitrogen. A focused beam of electrons is directed at a 0.2 micrometer spot on each particle to be examined. 7
Inspect the sample at a 5 kilovolt accelerating voltage. By measuring the intensity and energy of the X-rays generated by the electron beam, the ratio of iodide to bromide in the particles at the spot where the electrons hit can be determined.

The compound represented by the general formula [I] of the present invention will be described.

General formula [I] Wherein R ₁ , R ₂ , R ₃ and R ₄ are selected from:

: Hydrogen atom: Halogen atom (for example, chlorine, bromine, fluorine, etc.): Linear or branched alkyl group (preferably having 1 carbon atom)
-40, for example, methyl, ethyl, i-propyl, 2-ethylhexyl, lauryl, stearyl, etc.) and may further have a substituent. Examples of the substituent include the above-mentioned halogen atom, alkoxy group (eg methoxy, butoxy, stearyloxy etc.), aryloxy group (eg phenoxy etc.), aryl group (eg phenyl group etc.),
Arylthio groups (eg phenylthio etc.), aralkylthio groups (eg benzylthio etc.), amino groups (eg piperidino, dimethylamino etc.), acyloxy groups (eg acetoxy, benzoyloxy, furanoyloxy,
Cyclohexanoyloxy etc.), alkoxycarbonyl group (eg butoxycarbonyl, 2-ethylhexyloxycarbonyl etc.), cycloalkoxycarbonyl group (eg cyclohexyloxycarbonyl group), aryloxycarbonyl group (eg phenoxycarbonyl etc.), oxalyloxy group ( For example, ethoxyoxalyloxy etc.), carbamoyloxy group (eg hexylcarbamoyloxy etc.), sulfonyloxy group (eg phenylsulfonyloxy etc.), amide group (eg benzoylamino group etc.), ureido group (eg phenylureido etc.), aminosulfur Famoyl group (eg, dimethylaminosulfamoyl etc.) and the like.

: A cycloalkyl group (preferably having a carbon number of 3 to 6, for example, cyclopropyl, cyclohexyl and the like), and may further have a substituent, and examples thereof include the examples of the substituent for the above-mentioned alkyl group.

: An aryl group (for example, phenyl or the like) may have the same substituent as in the case of an alkyl group.

: Alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, etc.) or an alkyl group may have the same substituent.

: Carbamoyl group (eg phenylcarbamoyl etc.): Acyl group (eg acetyl, p-methoxybenzoyl etc.): Cyano group Further, R ₁ and ₂ and / or R ₁ and R ₄ may combine to form a ring. .

The following are exemplary compounds, but the present invention is not limited thereto.

Next, the compound represented by the general formula [II] of the present invention will be described.

General formula (II) In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are selected from the following.

: Hydrogen atom: Halogen atom (eg chlorine, bromine, fluorine etc.): Linear or branched alkyl group (preferably having 1 carbon atom)
-40, for example, methyl, ethyl, i-propyl, 2-ethylhexyl, lauryl, stearyl, etc.) and may further have a substituent. Examples of the substituent include the above-mentioned halogen atom and alkoxy group (for example, methoxy, butoxy,
Stearyloxy etc.), aryloxy group (eg phenoxy etc.), aryl group (eg phenyl group etc.), arylthio group (eg phenylthio etc.), aralkylthio (eg benzylthio etc.), amino group (eg piperidino, dimethylamino etc.), Acyloxy group (eg acetoxy, benzoyloxy, furanoyloxy, cyclohexanoyloxy etc.), alkoxycarbonyl group (eg butoxycarbonyl, 2-ethylexyloxycarbonyl etc.), cycloalkoxycarbonyl group (eg cyclohexyloxycarbonyl etc.), Aryloxycarbonyl group (eg phenoxycarbonyl etc.), oxalyloxy group (eg ethoxyoxalyloxy etc.), carbamoyloxy group (eg hexylcarbamoyloxy etc.), sulphate Niruokishi group (e.g. phenylsulfonyloxy, etc.), an amido group (e.g., benzoylamino group, etc.), a ureido group (e.g., phenylureido, etc.), amino sulfamoyl group (e.g., dimethylamino sulfamoyl, etc.) and the like.

: A cycloalkyl group (preferably having a carbon number of 3 to 6, for example, cyclopropyl, cyclohexyl and the like), and may further have a substituent, and examples thereof include the examples of the substituent for the alkyl group described above.

: An aryl group (eg, phenyl) may have the same substituent as in the case of an alkyl group.

: Alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, etc.) or an alkyl group may have the same substituent.

: Carbamoyl group (eg phenylcarbamoyl etc.): Acyl group (eg acetyl, p-methoxybenzoyl etc.): Cyano group Further, R ₁ and R ₂ , R ₇ and R ₈ and / or R ₁ and R ₄ are bonded to each other. You may form a ring.

The following are exemplary compounds, but the present invention is not limited thereto.

Next, the compound represented by the general formula [III] of the present invention will be described.

General formula (III) In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are selected from the following.

: Hydrogen atom: Halogen atom (eg chlorine, bromine, fluorine etc.): Linear or branched alkyl group (preferably having 1 carbon atom)
-40, for example, methyl, ethyl, i-propyl, 2-ethylhexyl, lauryl, stearyl, etc.) and may further have a substituent. Examples of the substituent include the above-mentioned halogen atom, alkoxy group (eg, methoxy, butoxy, stearyloxy, etc.), aryloxy group (eg, phenoxy, etc.), aryl group (eg, phenyl group, etc.),
Arylthio groups (eg phenylthio etc.), aralkylthio groups (eg benzylthio etc.), amino groups (eg piperidino, dimethylamino etc.), acyloxy groups (eg acetoxy, benzoyloxy, furanoyloxy,
Cyclohexanoyloxy etc.), an alkoxycarbonyl group (eg butoxycarbonyl, 2-ethylhexyloxycarbonyl etc.), a cycloalkoxycarbonyl group (eg cyclohexyloxycarbonyl etc.), an aryloxycarbonyl group (eg phenoxycarbonyl etc.), an oxalyloxy group ( For example, ethoxyoxalyloxy etc.), carbamoyloxy group (eg hexylcarbamoyloxy etc.), sulfonyloxy group (eg phenylsulfonyloxy etc.), amide group (eg benzoylamino group etc.), ureido group (eg phenylureido etc.), aminosulfur Famoyl group (eg, dimethylaminosulfamoyl etc.) and the like.

: A cycloalkyl group (preferably having a carbon number of 3 to 6, for example, cyclopropyl, cyclohexyl and the like), and may further have a substituent, and examples thereof include the examples of the substituent for the alkyl group described above.

: An aryl group (eg, phenyl) may have the same substituent as in the case of an alkyl group.

: An alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, etc.) or an alkyl group may have the same substituent.

: Carbamoyl group (eg phenylcarbamoyl etc.): Acyl group (eg acetyl, p-methoxybenzoyl etc.): Cyano group Further, R ₁ and R ₂ may be bonded to form a ring.

The following are exemplary compounds, but the present invention is not limited thereto.

Among the cyclic ether compounds described above, preferred 1
The group comprises at least one ether linkage, ester linkage (eg, −SO ₂ −, Amide bond (for example, -CON, -SO ₂ N) or a ureido bond (e.g. Further, it is preferable that at least one hydrogen atom is bonded to the carbon atom directly connected to the oxygen atom in the ring.

The cyclic ether compound may be purchased as a commercial product.
It can also be obtained by previously synthesizing a corresponding compound having a double bond and then oxidizing the double bond with an oxidizing agent (for example, hydrogen peroxide). In addition, the above-mentioned 6-membered cyclic ether compound is, for example, JCO Vol.36p.1176 (1971), Macrolecul
According to the method described in es1980.p.252, the 5-membered one is described in, for example, British Patent No. 867918 and Ann 623 p.191 (1959), and the four-membered one is described in German Patent No. 1021858. Can be synthesized by the method of.

In the present invention, the object of the present invention is achieved if the amount of the cyclic ether compound added to the light-sensitive material is 0.001 part by weight or more based on 1 part by weight of the binder in the layer containing the cyclic ether compound.

The cyclic ether compound of the present invention must be contained as oil droplets. It is essential that the oil droplets contain a hydrophobic photographic additive. The addition amount of the cyclic ether compound of the present invention is a weight ratio to the hydrophobic photographic additive, preferably 0.1 to 10, and more preferably 0.2 to
It is 5.

As a hydrophobic photographic additive, its solubility in water is 10
It is not particularly limited as long as it is a photographic additive in an amount of not more than 10% by weight, but it may be a dye-forming coupler, a colored coupler, a DIR coupler, a DIR compound, an image stabilizer, an antifoggant, an ultraviolet absorber and a fluorescent whitening agent. preferable. It is particularly preferably a dye-forming coupler.

In order to incorporate the cyclic ether compound in the present invention as oil droplets in the light-sensitive material, it is preferable to use the oil-in-water type emulsion dispersion method described later.

The cyclic ether compound is a liquid at room temperature (20 ℃),
When it has a boiling point of 150 ° C or higher (for example, Exemplified Compounds 15 and 2
4, 26, 28, 44, 46, 89, 98, 102 and the like) can be contained as oil droplets in the photosensitive material by using as a high boiling point organic solvent.

Further, when the cyclic ether compound is a solid at room temperature, it can be contained as an oil drop in the light-sensitive material by dissolving the cyclic ether compound in a high boiling point organic solvent.

The present invention can be preferably applied to color negative films, color reversal films and the like.

The color negative film and the color reversal film are generally composed of a blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer and a non-photosensitive colloid layer, and the present invention is not limited to the arrangement of these layers on the support. is not.

The layer structure capable of particularly exhibiting the effect of the present invention is, from the support, a colloidal silver antihalation layer (intermediate layer), a red-sensitive layer (intermediate layer), a green-sensitive layer (intermediate layer), a colloidal silver-yellow filter layer, and a blue-sensitive layer (intermediate layer). Layer) A protective layer is applied, and further from the support Colloidal silver antihalation layer (intermediate layer) Red-sensitive layer (intermediate layer) Green-sensitive layer (intermediate layer) Blue-sensitive layer (intermediate layer) Red-sensitive layer (intermediate layer) ) A layer structure in which a green-sensitive layer (colloidal silver-yellow filter layer) and a blue-sensitive layer (intermediate layer) protective layer are applied.

The layers in parentheses may be omitted. The red-sensitive layer, the green-sensitive layer and the blue-sensitive layer may be divided into low-sensitivity and high-sensitivity layers. Further, a layer structure in which at least one of a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer as shown in JP-B-49-15495 is divided into three partial layers, a high-sensitivity emulsion as shown in JP-A-51-49027. Layer structure in which a layer unit and a low-sensitivity emulsion layer unit are separated and West German publication Nos. 2,622,922, 2,622,923, 2,622,
No. 924, No. 2,704,826 and No. 2,704,797 include the layer structure.

The silver halide grains used in the silver halide emulsion in the present invention may be those obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after forming seed grains. Even though the method of making seed particles and the method of growing them are the same,
May be different.

In the present invention, in the silver halide emulsion, halide ions and silver ions may be mixed at the same time, or the other may be mixed in a liquid containing either one. Alternatively, it may be produced by sequentially adding halide ions and silver ions simultaneously while controlling the pH and pAg in the mixing vessel while considering the critical growth rate of silver halide crystals. By this method, silver halide grains having a regular crystal form and a substantially uniform grain size can be obtained. The halogen composition of the grains may be changed using a conversion method in any step of the formation of AgX.

In the present invention, a known silver halide solvent such as ammonia, thioether or thiourea can be present during the growth of the silver halide emulsion.

In the present invention, the silver halide emulsion includes a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt (including a complex salt), in the step of forming grains and / or the step of growing the grains.
A metal ion is added using at least one selected from rhodium salts (including complex salts) and iron salts (including complex salts),
These metal elements can be contained inside the grain and / or on the surface of the grain, and reduction sensitization nuclei can be imparted to the inside and / or the surface of the grain by placing in a suitable reducing atmosphere.

In the present invention, the silver halide emulsion may have unnecessary soluble salts removed after the growth of the silver halide grains is completed, or may be contained therein. When removing the salts, Research Disclosure (Research D
isclosure (hereinafter abbreviated as RD)) can be performed based on the method described in Item 17643, Item II.

In the present invention, other silver halide grains are cubic,
It may have a regular crystal form such as an octahedron or a tetradecahedron, or may have an irregular crystal form such as a sphere or a plate. In these particles, {100} planes and {11}
Any ratio of 1} faces can be used. Further, those having a composite form of these crystal forms may be used, and particles of various crystal forms may be mixed. The size of silver halide grains may be 0.05 to 30 μm, preferably 0.1 to 20 μm.

In the present invention, the silver halide emulsion may have any grain size distribution. An emulsion having a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion having a narrow grain size distribution (referred to as a monodisperse emulsion).
The monodisperse emulsion referred to herein is one having a value of 0.20 or less when the standard deviation of the grain size distribution is divided by the average grain size. Here, the grain size indicates the diameter in the case of spherical silver halide, and in the case of grains having a shape other than spherical, the projected image thereof is converted into a circular image of the same area. ) May be used alone or in combination of several kinds. Further, a polydisperse emulsion and a monodisperse emulsion may be used in combination.

The silver halide emulsion of the present invention may be used as a mixture of two or more kinds of silver halide emulsions formed separately.

The silver halide emulsion of the present invention can be chemically sensitized by a conventional method. That is, the sulfur sensitizing method, the selenium sensitizing method, the reduction sensitizing method, the noble metal sensitizing method using gold and other noble metal compounds can be used alone or in combination.

The silver halide emulsion of the present invention can be optically sensitized in a desired wavelength range by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. A dye that does not have a spectral sensitizing action by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, and that contains a supersensitizer that enhances the sensitizing action of the sensitizing dye in the emulsion. Good.

As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a steryl dye and a hemioxanol dye are used.

Particularly useful dyes are cyanine dyes, merocyanine dyes, and complex merocyanine dyes.

The silver halide emulsion includes chemical ripening, chemical ripening at the end of chemical ripening, and / or chemical ripening for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage, or photographic processing, or maintaining stable photographic performance. After the completion of ripening, a compound known as an antifoggant or a stabilizer in the photographic art can be added by the time of coating the silver halide emulsion.

Silver halide emulsion binder (or protective colloid)
It is advantageous to use gelatin, but a gelatin derivative, a graft polymer of gelatin and another polymer,
Other hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic high molecular substances such as homopolymers and copolymers can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material using the silver halide emulsion of the present invention may comprise one or more hardeners for increasing the film strength by crosslinking the binder (or protective colloid) molecules. By using it, it can be hardened. The hardener can be added in an amount such that the photosensitive material can be hardened to the extent that it is not necessary to add the hardener to the processing liquid, but it is also possible to add the hardener to the processing liquid.

For example, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives, (2,3-dihydroxyoxane, etc.), active vinyl compounds (1,3 , 5, -Triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc., active halogen compounds (2.4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid) , Mucophenoxic acid, etc.) or the like can be used alone or in combination.

A plasticizer can be added to the silver halide emulsion layer and / or another hydrophilic colloid layer of the light-sensitive material for the purpose of enhancing flexibility. Preferred plasticizers are the compounds described in A of RD17643, section XII.

A photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material may contain a dispersion (latex) of a water-insoluble or hardly-soluble synthetic polymer for the purpose of improving dimensional stability and the like.

For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or these and acrylic acid, A polymer having a monomer component of a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid and the like can be used.

In the color developing process, the emulsion layer of the photosensitive material undergoes a coupling reaction with an oxidized aromatic primary amine developer (for example, a p-phenylenediamine derivative or an aminophenol derivative) to form a dye. Couplers are used. The dye-forming couplers are usually selected such that for each emulsion layer a dye is formed that absorbs the light in the sensitive spectrum of the emulsion layer, with the blue-sensitive emulsion layer containing a yellow dye-forming coupler and a green dye-forming coupler. A magenta dye-forming coupler is used in the light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, a silver halide color photographic light-sensitive material may be prepared by a method different from the above combination depending on the purpose.

It is desirable that these dye-forming couplers have a group having a carbon number of 8 or more, which makes a coupler called a plast group non-diffuse in the molecule. Also, these dye-forming couplers need only reduce two molecules of silver ions, even if they are four-equivalent, in which four molecules of silver ions need to be reduced in order to form one molecule of dye. Either of two equivalents may be used. The dye-forming coupler has a color-correcting effect and is coupled with a colored coupler and an oxidation product of a developing agent to develop a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent. , Hardeners, antifoggants, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizing compounds that release photographically useful fragments. Among these, a coupler which releases a development inhibitor with development and improves the sharpness of images and the graininess of images is called a DIR coupler. Instead of the DIR coupler, a DIR compound which releases a development inhibitor at the same time as producing a colorless compound by coupling reaction with an oxidized product of a developing agent may be used.

The DIR coupler and the DIR compound used include those in which an inhibitor is directly bonded to the coupling position, and those in which the inhibitor is bonded to the coupling position via a divalent group, and within the group which is released by the coupling reaction. (A timing DIR coupler and a timing DIR compound) in which an inhibitor is released by an intramolecular nucleophilic reaction, an intramolecular electron transfer reaction, or the like. Further, as the inhibitor, those having a diffusibility after release and those having a low diffusivity can be used alone or in combination depending on the use. A colorless coupler (also referred to as a competing coupler) that undergoes a coupling reaction with an oxidized product of an aromatic primary amine developer but does not form a dye can also be used in combination with the dye-forming coupler.

As the yellow dye-forming coupler, a known acylacetanilide type coupler can be preferably used. Among these, benzoylacetanilide compounds and bivaloylacetanilide compounds are advantageous. Specific examples of yellow color couplers that can be used include, for example, U.S. Pat.
No. 5,057, No. 3,265,506, No. 3,408,194, No. 3,5
No. 51,155, No. 3,582,322, No. 3,725,072, No. 3,
891,445, West German Patent 1,547,868, West German Application Publication 2,219,
No. 917, No. 2,261,361, No. 2,414,006, UK Patent No. 1,4
No. 25,020, No. 51-10783, JP-A No. 47-26133,
48-73147, 50-6341, 50-87650, 50-12
No. 3342, No. 50-130442, No. 51-21827, No. 51-10263
No. 6, No. 52-82424, No. 52-115219, No. 58-95346 and the like. As the magenta dye-forming coupler, known 5-pyrazolone-based couplers, pyrazolobenzimidazole-based couplers, pyrazolotriazole-based couplers, open-chain acylacetonitrile-based couplers, indazolone-based couplers and the like can be used. Specific examples of magenta color couplers that can be used are described in, for example, US Pat.
No. 2,600,788, No. 2,983,608, No. 3,062,653, No. 3,127,269, No. 3,311,476, No. 3,419,391,
No. 3,519,429, No. 3,558,319, No. 3,582,322
No. 3,615,506, 3,834,908, 3,891,44
5, West German patent 1,810,464, West German patent application (OLS) 2,40
8,665, 2,417,945, 2,418,959, 2,424,467
No. 4, Japanese Patent Publication No. 40-6031, Japanese Unexamined Patent Publication No. 49-74027, No. 49-740.
No. 28, No. 49-129538, No. 50-60233, No. 50-159336
No. 51-20826, No. 51-26541, No. 52-42121,
JP-A-52-58922, JP-A-53-55122, and Japanese Patent Application No. 55-110943.

As the cyan dye-forming coupler, a phenol or naphthol coupler is generally used. Specific examples of cyan coloring couplers that can be used include, for example, U.S. Pat.
No. 730, No. 2,474,293, No. 2,801,171, No. 2,89
5,826, 3,476,563, 3,737,326, 3,7
58,308, 3,893,044, JP-A-47-37425
No. 50, No. 50-10135, No. 50-25228, No. 50-112038,
The couplers described in JP-A Nos. 50-117422 and 50-130441 and the couplers described in JP-A-58-98731 are preferable.

Of the dye-forming couplers, colored couplers, DIR couplers, DIR compounds, image stabilizers, antifoggants, UV absorbers, optical brighteners, etc. that do not need to be adsorbed on the surface of silver halide crystals, hydrophobic compounds are solid dispersions. Method, latex dispersion method, oil-in-water emulsion dispersion method and the like, which can be appropriately selected according to the chemical structure of the hydrophobic compound such as the coupler. The oil-in-water type emulsification dispersion method can be applied by a conventionally known method of dispersing a hydrophobic additive such as a coupler, and usually, a low boiling point organic solvent having a boiling point of about 150 ° C. or higher, if necessary, having a low boiling point, and / or an aqueous solution. Dissolve in combination with a hydrophilic organic solvent, using a dispersing means such as a stirrer using a surfactant in a hydrophilic binder such as an aqueous gelatin solution, a homogenizer, a colloid mill, a flow mixer, an ultrasonic device, After emulsification and dispersion, it may be added to the target hydrophilic colloid solution. A step of removing the low boiling point organic solvent may be added at the same time as the dispersion or dispersion.

Organic solvents having a boiling point of 150 ° C or higher such as phenol derivatives, alkyl phthalates, phosphates, citrates, benzoates, alkylamides, fatty acid esters and trimesic acid esters which do not react with the oxidized form of the developing agent as high boiling solvents A solvent is used.

A low boiling or water-soluble organic solvent can be used with or instead of a high boiling solvent. Examples of the organic solvent having a low boiling point and substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane and benzene.

When the dye-forming coupler, DIR coupler, colored coupler, DIR compound, image stabilizer, color fogging inhibitor, ultraviolet absorber, fluorescent whitening agent, etc. have an acid group such as carboxylic acid and sulfonic acid, they are used as an alkaline aqueous solution. It can also be introduced into a hydrophilic colloid. Dissolving a hydrophobic compound in a solvent having a low boiling point solvent alone or in combination with a high boiling point solvent, as a dispersion aid when dispersed in water using mechanical or ultrasonic waves, an anionic surfactant, a nonionic surfactant, Cationic and amphoteric surfactants can be used.

Between the emulsion layers of the light-sensitive material (same color-sensitive layers and / or different color-sensitive layers), the oxidant of the developing agent or the electron transfer agent migrates to cause color turbidity or deterioration of sharpness, An antifoggant can be used to prevent the graininess from being noticeable.

The color antifoggant may be contained in the emulsion layer itself, or may be contained in the intermediate layer by providing an intermediate layer between adjacent emulsion layers.

An image stabilizer that prevents deterioration of a dye image can be used in the light-sensitive material. Compounds that can be preferably used are those described in RD17643, item VII J.

The hydrophilic colloid layers such as the protective layer and the intermediate layer of the light-sensitive material may contain an ultraviolet absorber in order to prevent fogging due to discharge caused by charging of the material due to friction and the like and to prevent deterioration of the image by ultraviolet rays. .

In order to prevent deterioration of the magenta dye-forming coupler and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used for the light-sensitive material. When the hydrophilic colloid layer of the light-sensitive material contains a dye or an ultraviolet absorber, it may be mordanted with a mordant such as a cationic polymer. To the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material, a compound such as a development accelerator or a development retarder which changes the developability and a bleaching accelerator can be added. The compound that can be preferably used as the development accelerator is the compound described in the RD17643 item XXI, B to D, and the development retarder is the compound described in the 17643 item XXI, E. A black-and-white developing agent and / or a precursor thereof may be used for development promotion and other purposes.

The emulsion layer of the photographic light-sensitive material comprises a polyalkylene oxide or a derivative thereof such as an ether, ester or amine, a thioether compound, a thiomorpholine compound, a quaternary ammonium compound or a urethane derivative for the purpose of increasing sensitivity, increasing contrast or promoting development. It may include a urea derivative, an imidazole derivative and the like.

A fluorescent brightening agent can be used in the light-sensitive material for the purpose of emphasizing the whiteness of the white background and making the coloring of the white background inconspicuous. Compounds which can be preferably used as the optical brightening agent are described in RD17643, item V.

The photosensitive material includes a filter layer, an antihalation layer,
An auxiliary layer such as an irradiation prevention layer can be provided. In these layers and / or in the emulsion layers, dyes which are bleached or bleached from the light-sensitive material during the development processing may be contained. Examples of such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes.

A matting agent can be added to the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material for the purpose of reducing the gloss of the light-sensitive material, improving writing properties, and preventing sticking of the light-sensitive materials to each other. As the matting agent, any can be used. For example, silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate,
Examples include polymers of calcium carbonate, acrylic acid and methacrylic acid and their esters, polyvinyl resins, polycarbonates, and polymers of styrene and their copolymers. The matting agent preferably has a particle size of 0.05 μ to 10 μ. The amount to be added is preferably 1 to 300 mg / m ² .

A lubricant can be added to the light-sensitive material to reduce sliding friction.

An antistatic agent for the purpose of antistatic can be added to the light-sensitive material. The antistatic agent may be used in the antistatic layer on the side of the support where the emulsion is not laminated, and a protective colloid layer other than the emulsion layer and / or the emulsion layer on the side where the emulsion layer is laminated on the support. May be used. Antistatic agents preferably used are compounds described in RD17643 XIII.

For the photographic emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material, coating property improvement, antistatic property, slipperiness improvement, emulsion dispersion, adhesion prevention, photographic properties (development acceleration, hardening agent, sensitization, etc.)
Various surfactants can be used for the purpose of improvement and the like.

The support used in the light-sensitive material of the present invention includes a flexible reflective support such as paper or synthetic paper laminated with α-olphine polymer (for example, polyethylene, polypropylene, ethylene / butene copolymer), acetic acid. Films made of semi-synthetic or synthetic polymers such as cellulose, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, and flexible supports provided with a reflective layer on these films, glass, metal, Includes pottery.

The photosensitive material is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support as required, and then directly or on the surface of the support, antistatic property, dimensional stability, abrasion resistance, hardness, It may be applied via one or more subbing layers to improve antihalation properties, friction properties, and / or other properties.

When coating the photosensitive material, a thickener may be used to improve the coating property. In addition, for example, for a hardener such as a hardener, which causes gelation before coating when added to a coating solution in advance due to its high reactivity, it is recommended to mix it immediately before coating using a static mixer or the like. preferable.

As an application method, extrusion coating and curtain coating, which can simultaneously apply two or more layers, are particularly useful, but bucket coating is also used depending on the purpose. Further, the coating speed can be arbitrarily selected.

The surfactant is not particularly limited, for example, natural surfactants such as saponin, alkylene oxide-based, glycerin-based, nonionic surfactants such as glycidol-based,
Higher alkylamines, quaternary ammonium salts, pyridine and other compound rings, cation surfactants such as phosphonium or sulfonium, and acidic groups such as carboxylic acid, sulfonic acid, phosphoric acid, sulfuric acid ester, phosphoric acid ester, etc. Anionic surfactants including, amphoteric surfactants such as amino acids, aminosulfonic acids, sulfuric acid or phosphoric acid esters of amino alcohols may be added. For the same purpose, it is also possible to use a fluorine-based surfactant.

To obtain a dye image using the light-sensitive material of the present invention, color photographic processing is performed after exposure. The color processing includes a color development processing step, a bleaching step, a fixing step, a washing step, and a stabilizing step as required. Instead of the bleaching step and the fixing step, In addition, a bleach-fixing process can be performed using a one-bath bleach-fixing solution, or a monobath processing process using a one-bath developing bleach-fixing solution capable of performing color development, bleaching, and fixing in one bath. Can also be performed.

In combination with these treatment steps, the pre-hardening treatment step, the neutralizing step thereof, the stop fixing treatment step, and the post-hardening treatment step may be performed. In these processes, instead of the color developing process, an activator process in which a color developing agent or a precursor thereof is contained in the material and the developing process is performed with an activator solution may be performed, or the activator may be used in the mono bath process. Processing can be applied. Among these processes, a typical process is shown below. (These steps include any one of a washing step, a washing step, and a stabilizing step as the final step.) ・ Color development processing step-bleach-fixing processing step-fixing processing step-color development processing step-bleach-fixing step Processing step-Interlayer hardening processing step-Color development processing step-Stop fixing processing step-Water washing processing step-Bleach processing step-Fixing processing step-Water washing processing step-Post-hardening processing step-Color development processing step-Water washing processing step- Supplementary color development processing step-stop processing step-bleaching processing step-fixing processing step-activator processing step-bleach fixing processing step-activator processing step-bleaching processing step-fixing processing step-monobath processing step The processing temperature is usually 10 ℃ ~ 65 ℃ is selected, but 65
The temperature may exceed ℃. The treatment is preferably performed at 25 ° C to 45 ° C.

The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. The color-developing agent is an aromatic primary amine color-developing agent and includes aminophenol-based and p-phenyleneamine-based derivatives. These color developing agents can be used as salts of organic acids and inorganic acids, for example, salt acid, sulfate, p-toluenesulfonate, sulfite, oxalate, benzenesulfonate, etc. it can.

These compounds are generally about 0.
It is used at a concentration of 1 to 30 g, more preferably at a concentration of about 1 to 15 g per color developing solution 1. If the amount is less than 0.1 g, a sufficient color density cannot be obtained.

Examples of the aminophenol-based developer include o-
Aminophenol, p-aminophenol, 5-amino-2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene and the like are included.

Particularly useful primary aromatic amine color developing agents are N, N-
A dialkyl-p-phenylenediamine compound,
Alkyl and phenyl groups may be substituted or unsubstituted. Among them, particularly useful compound examples are NN-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N, N-dimethyl-p-phenylenediamine hydrochloride,
2-amino-5- (N-ethyl-N-dodecylamino)
-Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N
-Ethyl-N-β-hydroxyethylaminoaniline,
4-amino-3-methyl-N, N-diethylaniline, 4
-Amino-N- (2-methoxyethyl) -N-ethyl-
Examples thereof include 3-methylaniline-p-toluenesulfonate.

The color developing agents may be used alone or in combination of two or more kinds. Further, the color developing agent may be incorporated in a color photographic material. In this case, the silver halide color photographic light-sensitive material can be processed with an alkali solution (activator solution) instead of the color developing solution, and bleach-fix processing is performed immediately after the alkali solution processing.

The color developing solution used in the present invention may contain an alkaline agent usually used in the developing solution such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate or borax. And further contains various additives such as benzine alcohol, alkali metal halides such as potassium bromide or potassium chloride, or development modifiers such as citrazinic acid, and preservatives such as hydroxylamine or sulfite. May be. Furthermore, various antifoaming agents and surfactants, and organic solvents such as methanol, dimethylformamide and dimethylsulfoxide can be appropriately contained.

The pH of the color developer used in the present invention is usually 7 or higher,
It is preferably about 9 to 13.

In the color developing solution used in the present invention, if necessary, diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, an aromatic secondary alcohol, hydroxamic acid, bentose or an antioxidant is used. Exose, pyrogallol-1,
3-dimethyl ether and the like may be contained.

In the color developing solution used in the present invention, various chelating agents can be used in combination as a sequestering agent. For example, as the chelating agent, ethylenediaminetetraacetic acid, amine polycarboxylic acid such as diethylenetriaminopentaacetic acid,
Organic phosphonic acid such as 1-hydroxyethylidene-1,1'-diphosphonic acid, aminopolyphosphonic acid such as aminotri (methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acid such as citric acid or gluconic acid, 2-phosphonobutane 1 Examples thereof include phosphonocarboxylic acid such as 2,2,4-tricarboxylic acid, polyphosphoric acid such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compound.

The bleaching step may be performed simultaneously with the fixing step as described above, or may be performed individually. As the bleaching agent, a metal complex salt of an organic acid is used, and for example, an organic acid such as polycarboxylic acid, aminopolycarboxylic acid or oxalic acid or citric acid, which is coordinated with a metal ion such as iron, cobalt, or copper is used. . The most preferred organic acids among the above organic acids include polycarboxylic acids and aminopolycarboxylic acids. Specific examples of these include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β-oxyethyl) -N, N ′,
N'-triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine citric acid (or tartaric acid), ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine tetrapropionic acid, Examples thereof include phenylenediamine tetraacetic acid. These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. These bleaches are used at 5-450 g /, more preferably at 20-250 g /.

As the bleaching liquid, a liquid having a composition containing a sulfite as a preservative, if necessary, is applied in addition to the bleaching agent as described above.
Further, a bleaching solution containing an ethylenediaminetetraacetate iron (III) complex bleach and having a composition in which a large amount of a halide such as ammonium bromide is added may be used. As the halide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may be used in addition to ammonium bromide. it can.

The bleaching solution used in the present invention includes JP-A-48-280,
Japanese Patent Publication Nos. 45-8506 and 46-556, Belgian Patent No. 770,9
No. 10, JP-B-45-8836, JP-B-53-9854, JP-A-54-71
Various bleaching accelerators described in JP-A Nos. 634 and 49-42349 can be added.

The bleaching solution is used at a pH of 2.0 or higher, but generally 4.0-
It is used at 9.5, preferably at 4.5-8.0, most preferably at 5.0-7.0.

A fixing solution having a commonly used composition can be used. As a fixing agent, a compound capable of forming a water-soluble complex salt by reacting with silver halide used in a usual fixing process, for example, thiosulfates such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, and potassium thiocyanate And thiocyanates such as sodium thiocyanate and ammonium thiocyanate, thiourea, thioether and the like. These fixatives
5g / or more, used in an amount that can be dissolved, but generally 7
Use at 0-250g /. A part of the fixing agent can be contained in the bleaching tank, and conversely, a part of the bleaching agent can be contained in the fixing tank.

The bleaching solution and / or the fixing solution are various pH buffers such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide. The agents can be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents or surfactants may be contained. In addition, preservatives such as bisulfite adducts of hydroxylamine, hydrazine and aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohol and collecting salts, and hardening agents such as water-soluble aluminum salts. ,methanol,
An organic solvent such as dimethylsulfonamide and dimethylsulfoxide can be appropriately contained.

The fixer is used at a pH of 3.0 or higher, but generally 4.5-
10 is used, preferably 5 to 9.5, most preferably 6 to 9.

Examples of the bleaching agent used in the bleach-fixing solution include the metal complex salts of organic acids described in the above-mentioned bleaching step, and preferred compounds and the concentrations in the processing solution are the same as those in the above-mentioned bleaching step.

As the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the above-mentioned bleaching agent and, if necessary, a sulfite as a preservative is applied. Further, a bleach-fixing solution having a composition in which a small amount of a halogenide such as ammonium bromide other than the above-mentioned silver halide fixing agent and an ethylenediaminetetraacetic acid iron (III) complex bleaching agent is added, or conversely, a halide such as ammonium bromide Use a bleach-fixing solution containing a large amount of added, and a special bleach-fixing solution containing a combination of ethylenediaminetetraacetic acid iron (III) complex salt bleaching agent and a large amount of a halide such as ammonium bromide. You can Examples of the halide include hydrochloric acid, hydrobromic acid, in addition to ammonium bromide,
Lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide and the like can be used.

Examples of the silver halide fixing agent that can be contained in the bleach-fixing solution include the fixing agents described in the above fixing processing step. The concentration of the fixing agent and the pH buffer and other additives that can be contained in the bleach-fixing solution are the same as those in the above-mentioned fixing process.

The bleach-fix solution is used at a pH of 4.0 or higher, but generally
It is used at 5.0 to 9.5, preferably 6.0 to 8.5, and most preferably 6.5 to 8.5.

[Example-1] Specific examples of the present invention will be described below, but embodiments of the present invention are not limited thereto.

In all of the following examples, the addition amount in the silver halide photographic light-sensitive material is based on 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver.

A multilayer color photographic element sample 1 was prepared by sequentially forming each layer having the composition shown below from the support side on a triacetyl cellulose film support.

Sample-1 (Comparison) First layer: Antihalation layer (HC-1) Gelatin layer containing black colloidal silver.

Second layer: intermediate layer (IL) A gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Third layer: low-sensitivity red-sensitive silver halide emulsion layer (RL-1) Emulsion composed of AgBr I containing average grain size of 0.65 μm and Ag I 6 mol% (Emulsion I) ... Silver coating amount 1.8 g / m ² sensitization Dye I: 6 × 10 ⁻⁵ mol per mol of silver Sensitizing dye II: 1.0 × 10 ⁻⁵ mol per mol of silver Cyan coupler (C-1): 0.06 per mol of silver Molar color cyan coupler (CC-1): 0.003 mol for 1 mol of silver DIR compound (D-1): 0.0015 mol for 1 mol of silver DIR compound (D-2): for 1 mol of silver 0.002 mol Oil drop additive Comparative compound-1 …… Same weight as coupler C-1 4th layer; High-sensitivity red-sensitive silver halide emulsion layer (RH-1) Average particle size 1.02 μm, Ag I 6.0 mol% Emulsion consisting of AgBr I containing (Emulsion II): Silver coating amount 1.3 g / m ² Sensitizing dye I: 3 × 10 ⁻⁵ mol per mol of silver Sensitizing dye II: against 1 mol of silver 1.0 × 10 ^-5 mol cyan cap Lar (C-1): 0.02 mol per mol of silver Colored cyan coupler (CC-1): 0.0015 mol per mol of silver DIR compound (D-2): 0.001 mol per mol of silver Mol Oil Droplet Additive Comparative Compound-1: Same weight as coupler M-1 5th layer; Intermediate layer (IL) Same as 2nd layer, gelatin layer.

Sixth layer: low-sensitivity green-sensitive silver halide emulsion layer (GL-1) Emulsion-1 ... Coating amount of silver 1.5 g / m ² Sensitizing dye III: 2.5 × 10 ^-5 mol increase per mol of silver Dye IV: 01.2 × 10 ^-5 mol / mol silver Magenta coupler (M-1): 0.05 / mol silver
0 mol Colored magenta coupler (CM-1) ... 0.009 mol to 1 mol of silver DIR compound (D-1) ... 0.0010 mol to 1 mol of silver DIR compound (D-3) ... to 1 mol of silver On the other hand, 0.0030 mol Oil drop additive Comparative compound-1 Same amount as coupler M-1 7th layer; High-sensitivity green-sensitive silver halide emulsion layer (GH-1) Emulsion-II ... coating silver amount 1.4 g / m ² Sensitizing dye III: 1.5 × 10 ^-5 mol per mol of silver Sensitizing dye IV: 1.0 × 10 ^-5 mol per mol of silver Magenta coupler (M-1): Per mol of silver 0.02
0 mol Colored magenta coupler (CM-1) ... 0.002 mol per mol of silver DIR compound (D-3) ... 0.0010 mol per mol of silver Oil drop additive Comparative compound-1 ... Coupler M- Eighth layer having the same weight as 1; Yellow filter layer (YC-1) A gelatin layer containing yellow colloidal silver and an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Ninth layer: Low-sensitivity blue-sensitive silver halide emulsion layer (BL-1) Emulsion composed of AgBr I containing 0.75 μm average grain size and 8 mol% AgI (Emulsion III): Silver coating amount 0.9 g / m ² sensitization Dye V: 1.3 × 10 ^-5 moles per mole of silver Yellow coupler (Y-1): 0.29 per mole of silver
Molar 10th layer: High-sensitivity blue-sensitive emulsion layer (BH-1) Emulsion composed of AgBr I containing 1.10 μm average grain size and 10 mol% Ag I (Emulsion IV) ... Silver coating amount 0.5 g / m ² sensitizing dye V: 1.0 × 10 ^-5 mol per mol of silver Yellow coupler (Y-1): 0.08 per mol of silver
Mol DIR compound (D-2): 0.0015 mol per mol of silver 11th layer; 1st protective layer (Pro-1) Silver iodobromide (Ag I 1 mol% average particle size 0.07 μm) Silver coating amount 0.5
g / m ² Gelatin layer containing UV absorbers UV-1, UV-2 12th layer; 2nd protective layer (Pro-2) Polymethylmethacrylate particles (diameter 1.5 μm) and formalin scavenger (HS-1) Gelatin layer In addition to the above composition, a gelatin hardening agent (H-1) is used in each layer.
And a surfactant were added.

Comparative compound-1 Comparative compound-2 The oil drop additive of the present invention and the comparative oil drop additive were weighed in the same amount as the couplers of the respective layers, dissolved in ethyl acetate together with the coupler, the colored coupler and the DIR compound, and added to a 5% aqueous gelatin solution containing sodium dodecylbenzenesulfonate. After the addition, the dispersion liquid obtained by dispersing with a homogenizer was added to the emulsion.

 The compounds contained in each layer of Sample 1 are as follows.

Sensitizing dye I; anhydro 5,5'-dichloro-9-ethyl 3,
3'-Di- (3-sulfopropyl) thiacarbocyanine hydroxide Sensitizing dye II; Anhydro 9-ethyl 3,3'-di (3-sulfopropyl) -4,5,4 ', 5'-dibenzothia Carbocyanine hydroxide Sensitizing dye III; Anhydro 5,5'-diphenyl-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine hydroxide Sensitizing dye IV; Anhydro 9-ethyl-3 , 3'-di- (3-
Sulfopropyl) 5,6,5 ', 6'-dibenzooxacarbocyanine hydroxide Sensitizing dye V; Anhydro 3,3'-di- (3-sulfopropyl) -4,5-benzo-5'-methoxythia Cyanine Next, in Sample 1, Samples 1 to 16 were prepared by changing the silver halide emulsions and the oil drop additives of the third, fourth, sixth and seventh layers as shown in Table-1.

Each of the samples 1 to 16 thus prepared was exposed to a wedge with white light and then subjected to the following development processing.

Treatment process (38 ℃) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying The composition of the treatment solution used in each processing step is as follows. It is as follows.

[Color developer]

4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) -aniline ・ sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine ・ 1/2 sulfate 2.0 g anhydrous sodium carbonate 37.5 g sodium bromide 1.3 g Nitrilotriacetic acid / 3 sodium salt (monohydrate) 2.5 g Potassium hydroxide 10.0 g Add water to make 1.

[Bleaching solution]

Ethylenediaminetetraacetic acid iron ammonium salt 100. g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Add water to make 1 and pH = 6.0 using ammonia water.
Adjust to.

[Fixer]

Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to make 1 and adjust to pH = 6.0 with acetic acid.

[Stabilizer]

 Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konishi Roku Photo Industry Co., Ltd.) 7.5 ml Add water to make 1

The relative sensitivity (S) and sharpness MTF) and RMS of each of the obtained samples were measured using red light and green light. The results are shown in Table 2.

The relative sensitivity (S) is the relative value of the reciprocal of the exposure amount that gives the fog density +0.1, and is shown as a value with the W sensitivity of Sample No. 1 being 100. The effect of improving the sharpness is the MTF (M
odulation transfer function), MT at 10 lines / mm
The relative value of F (sample No. 1 is 100) is shown.

The RMS value is the minimum density +1.2 when the aperture scanning area is 250 μm ²
The standard deviation of the variation of the concentration value generated when the sample was scanned with the microdecitometer was 1000 times.

As can be seen from Table-2, the silver halide photographic emulsion containing the cyclic ether compound of the present invention and the tabular silver halide emulsion was found to have the remarkable effect of improving the sensitivity, graininess and sharpness.

Further, it has been found that the effect of the present invention is particularly great when the silver halide emulsion is composed of grains in which silver iodide is localized in the central portion.

Further, it has been found that the effect of the present invention is greater when the silver iodide is contained in the outer peripheral portion of the silver halide emulsion than when pure silver bromide is used.

Further, the frequency of pressure fog generation in the developed sample at this time was examined. As shown in the right column of Table 2, the frequency of pressure fog generation was found in the sample containing the cyclic ether compound of the present invention and the tabular silver halide emulsion. Significant improvement was observed (+ low frequency-high frequency).

Example 2 Samples 1 to 16 of Example 1 were subjected to the following strength deterioration treatment, and then subjected to the same development treatment and sensitometric evaluation as in Example 1 to evaluate the aging of the silver halide photographic light-sensitive material. Stability was evaluated.

Strength degradation treatment A Strength degradation treatment B Temperature 65 ° C 40 ° C Relative humidity 20% 80% Number of treatment days 1 day 7 days In addition, using other sample Nos. 1 to 16 of Example 1, latent image stability after exposure In order to test the above, the sample was exposed for 2 months at room temperature / normal temperature, and then subjected to the same development processing and sensitometry as in Example 1.

The results are shown in Table-3. Table 3 shows the fluctuation range or fluctuation rate based on the sensitometric characteristics of each sample of Example 1.

As can be seen from Table-3, the silver halide photographic emulsion containing the cyclic ether compound and the tabular silver halide emulsion of the present invention is remarkably improved in fog increase at high temperature and density decrease under high humidity condition, It can be seen that the latent image stability is also improved. It was also found that the effect of the present invention is greater when a silver halide emulsion composed of silver halide grains in which silver iodide is localized in the central portion is used.

Further, it has been found that the effect of the present invention is greater when silver iodide is contained in the outer peripheral portion of the silver halide emulsion than when pure silver bromide is used.

 ─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-52-51938 (JP, A) JP-A-54-104339 (JP, A) JP-A-59-99433 (JP, A) JP-A-59- 215378 (JP, A) JP 53-99928 (JP, A) JP 54-94319 (JP, A) JP 59-149348 (JP, A) JP 60-220338 (JP, A)

Claims (1)

(57) [Claims] 1. A silver halide photographic light-sensitive material comprising a support and a plurality of light-sensitive silver halide emulsion layers coated on the support.
At least one of the emulsion layers has a solubility in water.
An emulsion layer containing 10% by weight or less of a hydrophobic photographic additive and at least one cyclic ether compound represented by the following general formulas [I] to [III] as oil droplets, and containing the cyclic ether compound. , Containing a tabular silver halide emulsion having an average aspect ratio of 5: 1 or more. General formula [I] In the formula, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen atom, halogen atom, unsubstituted or substituted linear or branched alkyl group, cycloalkyl group, aryl group, alkoxycarbonyl group,
Represents a carbamoyl group, an acyl group, and a cyano group, but R ₁ and R ₂
And / or R ₁ and R ₄ may combine to form a ring. General formula (II) In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ have the same meanings as R _{1 to} R _{4 in} the general formula [I], and R ₁ and R ₂ , R ₇ and R ₈ and / or R ₁ and R ₄ may combine to form a ring. General formula (III) In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each represented by R ₁ to R ₁ of the general formula [I].
It has the same meaning as R ₄ , and R ₁ and R ₂ may combine to form a ring.