JPH0610753B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

The present invention relates to a silver halide color photographic light-sensitive material, more specifically, a novel halogen having a high maximum color density of a color image and excellent development processing stability. The present invention relates to a silver halide color photographic light-sensitive material.

[Prior art]

In today's photographic light-sensitive materials, substantially polydisperse silver halide grains having a coefficient of variation in particle size distribution of 0.20 or more are often used.In recent years, however, small cameras that are convenient to carry have become popular. However, accompanying the use of small size films, it is necessary to make a great improvement in sharpness and graininess, but the coefficient of variation for particle size distribution is 0.
It is well known that these problems are solved by utilizing substantially monodisperse silver halide grains of 20 or less. However, by using monodisperse silver halide grains, there is a drawback that the exposure area becomes narrower than in the case of using polydisperse silver halide grains, using monodisperse silver halide grains, Moreover, development of a silver halide photographic light-sensitive material having a wide exposure area is desired.

[Object of the Invention]

Therefore, the first object of the present invention is to provide a silver halide color photographic light-sensitive material having improved graininess. A second object of the present invention is to provide a silver halide color photographic light-sensitive material having improved sharpness. A third object of the present invention is to provide a monodisperse silver halide color photographic light-sensitive material excellent in graininess and sharpness and having a wide exposure area.

<Construction of the Invention> An object of the present invention is to have on a support at least one emulsion layer containing 2-equivalent yellow coupler and substantially monodisperse silver halide grains. This is accomplished by a silver halide color photographic light-sensitive material having a light-insensitive colloid layer containing substantially light-insensitive silver halide fine particles on the side closer to the support than the emulsion layer.

The 2-equivalent yellow coupler used in the present invention includes a coupler represented by the following general formula [I].

General formula [I] X ₁ : a halogen atom, an alkoxy group, an alkyl group, a halogen atom: a chlorine atom, etc., an alkoxy group, a methoxy group, an ethoxy group, etc., an alkyl group: a methyl group, an ethyl group Y ₁ : an oxidant of an aromatic primary amine color developing agent It represents a group which is released upon coupling to form a dye (sometimes referred to simply as a leaving component). The following groups are preferred. Aryloxy group, heterocyclic oxy group, Z ₁ is a nitrogen atom, a carbon atom, an oxygen atom, a nitrogen atom,
It represents a group of atoms required for forming a 5- or 6-membered ring by atoms selected from sulfur atoms.

R ₁ : represents a group capable of substituting on the benzene ring, and n is 1 or 2
Represent. When n is 2, R ₁ may be the same or different.

R ₁ is a hydrogen atom, a halogen atom, (for example, fluorine, chlorine, bromine, etc.) R ′ ₁ −, R ′ ₁ O—, R _'1 COO-, R _'1 O-CO-, And so on.

Wherein _{R '1, R "1,} R''' 1 may each hydrogen atom be the same or different, which may have a substituent alkyl group, an aryl group, a heterocyclic group.

R ₂ : represents an alkyl group or an aryl group. Preferred is a tert-butyl group, a phenyl group or an O-methoxyphenyl group.

Next, Y ₁ will be described. The aryl portion of the aryloxy group represented by Y ₁ is preferably phenyl, which may have a substituent. Specific examples of the aryloxy group include a phenoxy group, a 4-carboxyphenyloxy group, and a 4- (4-benzyloxybenzenesulfonyl) phenyloxy group.

Further, as the heterocyclic oxy group, for example, 1-phenyl-5
-Tetrazolyloxy group, isoxazolyloxy group,
4-pyridinyloxy group and the like.

Next, typical examples of the group capable of being eliminated during color development in the general formula [I] will be described below.

(1) (2) (3) (Four) (Five) (6) (7) (8) (9) (Ten) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (twenty one) (twenty two) (twenty three) (twenty four) (twenty five) Next, specific representative examples of the yellow coupler used in the present invention are shown.

Y-1 Y-2 Y-3 Y-4 Y-5 Y-6 Y-7 Y-8 Y-9 Y-10 Y-11 Y-12 Y-13 Y-14 Y-15 Y-16 Y-17 Y-18 Y-19 Y-20 Y-21 Y-22 Y-23 Y-24 Y-25 Y-26 Y-27 Y-28 Y-29 Y-30 Y-31 Y-32 Y-33 Y-34 Y-35 Y-36 Y-37 Y-38 Y-39 Y-40 Y-41 Y-42 Y-43 Y-44 Y-45 Y-46 Y-47 Y-48 Y-49 Y-50 Y-51 Y-52 In the practice of this invention, a 2 equivalent yellow coupler is 1
One type may be used alone, or two or more types may be used in combination. Furthermore, a 4-equivalent yellow coupler may be used in combination.

The addition amount of the 2 equivalent yellow coupler is 2 × 10 ^{−3 to} 5 mol, preferably 1 × 10 ⁻² to 1 mol, per mol of silver halide.
It is 0 mol.

In the present invention, the substantially non-photosensitive silver halide fine particles contained in the non-photosensitive colloidal layer are substantially non-photosensitive ones, that is, those not substantially developed in a developing solution. Although it is possible to use those described above, it is preferable that they are not substantially developed and dissolved in a developing solution.
The silver halide composition is preferably silver bromide, and more preferably silver iodobromide having a silver iodide content of 2 to 10 mol%.

It is also preferable to have an average particle size smaller than 0.3 μ, and further, from the viewpoint of sharpness, the average particle size is 0.02 to 0.2.
It is more preferable that it is μ. The particle size distribution may be wide or narrow, but a narrow distribution is preferable. The amount added is 0.1 to 50 mg / dm ² as silver amount, preferably 1 to 6
It is mg / dm ² .

The non-photosensitive colloidal layer containing the above non-photosensitive fine grain silver halide contains the 2-equivalent yellow coupler of the present invention and is close to the emulsion layer containing substantially monodisperse silver halide grains. Not only when no other layer is included between the emulsion layer and the photosensitive colloid layer, but also when one or two other non-photosensitive colloid layers are included between these layers, preferably 1 The number of layers is equal to or less than that of the layers, and more preferably, nothing is included between them and they are in direct contact. The non-photosensitive colloidal layer is, for example, a protective layer, an intermediate layer, or a well-known layer in the art.
It is a layer having functions such as a filter layer and an antihalation layer. Among the above-mentioned layer configurations, 2 according to the present invention
On the side closer to the support of the emulsion layer containing silver halide grains containing an equivalent amount of yellow coupler and being substantially monodisperse (hereinafter referred to as the emulsion layer of the present invention), the non-photosensitive halide according to the present invention is provided. A layer structure in which the non-photosensitive colloid layer containing silver is in direct contact is preferable.

As will be described later, from the support side, a red light-sensitive silver halide emulsion layer containing a diffusion-resistant cyan coupler, an intermediate layer, a green light-sensitive silver halide emulsion layer containing a diffusion-resistant magenta coupler, a yellow filter layer, and an anti-dispersion dye. In a light-sensitive material comprising a blue-sensitive silver halide emulsion layer containing a photosensitive yellow coupler and a protective layer, a non-photosensitive colloid layer containing a non-photosensitive fine grain silver halide (hereinafter, referred to as It is preferable to separately provide a non-photosensitive colloid layer of the present invention) between the blue-sensitive silver halide emulsion layer and the yellow filter layer in order to obtain the effects of the present invention.

In the present invention, monodisperse silver halide grains (hereinafter referred to as “monodisperse silver halide grains of the present invention”) mean that the weight of silver halide contained within a grain size range of ± 20% around the average grain size. , That which is 60% or more of the total silver halide weight. Here, the average particle size is the frequency n of particles having the particle size ri.
The particle size ri when the product ni × r ⁱ³ of i and r ⁱ³ is maximum
(3 significant digits, minimum digit is rounded to 4).

The term "particle size" used herein means the diameter of spherical silver halide grains, and the diameter of grains having a shape other than spherical when the projected image is converted into a circular image having the same area. The particle diameter can be obtained, for example, by enlarging the particle by an electron microscope from 10,000 times to 50,000 times and photographing it, and measuring the particle diameter on the print or the area of the projected image.
(The number of measured grains shall be 1000 or more indiscriminately.) The above-mentioned "consisting essentially of monodisperse silver halide grains" means that the halogenated grains having different grain sizes do not impair the effect of monodispersity. It is meant that silver emulsions can be mixed and used, for example, those in which the grain size distribution curve has a plurality of modes are also included in the present invention. Including such cases, the grain size distribution of the silver halide grains consisting of substantially monodispersed silver halide grains is defined as above, and the halogen contained within the grain size range of ± 20%. The silver halide grain weight is 60% or more, more preferably 70% or more, and particularly preferably 80%.
That is all.

Further, the monodisperse silver halide grains according to the present invention may be used by arbitrarily mixing two or more kinds of monodisperse silver halide grains having different silver iodide contents as long as they are within the above definition.

The substantially monodisperse silver halide grains according to the present invention are core / shell type silver halide grains,
It is more preferable because the LES value (described later) is improved. In particular, it is desirable that the core and the shell have different silver iodide contents and that the shell has a low content, and a core made of silver halide containing 4 to 30 mol% of silver iodide and an iodide coating the core. It is preferable that the shell is composed of a silver halide having a silver halide content of 0 to 6 mol% from the viewpoint of further enhancing the effect of the present invention.

The thickness of the shell is preferably in the range of 0.01 to 0.1μ.

The distribution state of silver iodide in the above silver halide grains is
It can be detected by various physical measurement methods, for example, by measuring luminescence at low temperature as described in the proceedings of the 56th Annual Conference of the Photographic Society of Japan.

The silver halide grains used in the light-sensitive material of the present invention, including the above core / shell type grains, preferably have a silver halide composition other than silver iodide mainly silver bromide, and a silver chloride content of 10%. It is preferably not more than mol%.

The shape of the silver halide grains according to the present invention may be any of hexahedron, octahedron, tetradecahedron, plate and spheroidal twin, but hexahedron, octahedron and tetradecahedral grains are preferred. .

To produce the substantially monodisperse silver halide grains, grains having a desired size can be obtained by the double jet method while keeping pAg constant. For highly monodisperse silver halide emulsions, the method described in JP-A-54-48521 can be applied. For example, it is produced by a method of adding an aqueous potassium iodobromide-gelatin solution and an aqueous ammoniacal silver nitrate solution to an aqueous gelatin solution containing silver halide seed grains while changing the addition rate as a function of time. At this time, the time function of the addition rate, pH, pAg,
By appropriately selecting the temperature and the like, highly monodisperse silver halide grains can be obtained.

The core / shell type monodisperse silver halide grain can be produced by coating the shell with a monodisperse silver halide grain as a core.

The thickness of the shell that coats the core is a thickness that does not hide the desirable properties of the core, and such a shell is formed by dissolving the soluble halogen compound solution and the soluble silver salt solution in a double jet method to form a monodisperse silver halide grain. It can be formed by being deposited on the core.

The method for producing the above-mentioned core / shell type silver halide grains is described in, for example, West German Patent 1,169,290 and British Patent 1,027,1.
46, JP-A-57-153232 and JP-B-51-1417.

In the present invention, for example, 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 and the like may coexist in the process of producing the silver halide grains according to the present invention.

The present invention can be used as a monochromatic color photosensitive material, but can also be used as a polychromatic color photosensitive material. A multicolor color light-sensitive material usually has a dye image-forming constitutional unit having photosensitivity in each of the three primary color regions of the spectrum, and each constitutional unit is a single-layer emulsion layer or a multi-layer emulsion having photosensitivity to a certain region of the spectrum. The emulsion may be composed of layers (in this case, it is preferable that the respective emulsion layers have different sensitivities), and may have layers such as a filter layer, an intermediate protective layer and an undercoat layer. The layers of the light-sensitive material, including the layers of the image-forming units, can be applied in various orders as known in the art. For example, in a multicolor photosensitive material, the silver halide emulsion containing the 2-equivalent yellow coupler according to the present invention usually has blue sensitivity, but it does not necessarily have to be blue sensitivity. A typical multicolor sensitizer is a cyan dye image-forming unit consisting of at least one red-sensitive silver halide emulsion layer having at least one diffusion-resistant cyan coupler.
Magenta dye image-forming structural unit consisting of at least one green-sensitive silver halide emulsion layer having at least one diffusion-resistant magenta coupler, and at least one blue-sensitive silver halide emulsion layer having at least one diffusion-resistant yellow coupler. And a non-photosensitive layer coated on a support.

The following diffusion-resistant couplers are preferably used.

The diffusion-resistant cyan coupler is preferably a phenol compound or a naphthol compound, for example, US Pat.
No. 2,369,929, No. 2,434,272, No. 2,474,293, No. 2,895,826, No. 3,253,924, No. 3,034,892,
No. 3,311,476, No. 3,386,301, No. 3,419,390
No.3, No.3,458,315, No.3,476,563, No.3,591,38
It can be selected from those described in No. 3 etc., and the synthetic methods of these compounds are also described in the references.

Further, as the colored cyan coupler, there can be mentioned a compound in which the coupling position of the colorless cyan coupler is arylazo-substituted, or a type of colored cyan coupler in which the dye flows out into the processing bath upon reaction with an oxidized product of a color developing agent. .

Examples of the diffusion-resistant magenta coupler include pyrazolone-based pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indazolone-based compounds. As a pyrazolone-based magenta coupler, U.S. Pat.
No. 8, No. 3,062,653, No. 3,127,269, No. 3,311,4
No. 76, No. 3,419,391, No. 3,519,429, No. 3,558,
No. 318, No. 3,684,514, No. 3,888,680, JP-A-49-
29639, 49-111631, 49-129538, 50-13041
Nos. 50-24690, 50-134470, and 50-156327; pyrazolotriazole-based magenta couplers include compounds described in U.S. Pat. No. 1,247,493. As the diffusion-resistant colored magenta coupler, a compound having an arylazo substitution at the coupling position of a colorless magenta coupler is generally used.For example, U.S. Pat.
The compounds described in 2,983,608, 3,005,712, 3,684,514, British Patent 937,621, JP-A-49-123625, and JP-A-49-31448 may be mentioned. Further US patent
Colored magenta couplers of the type in which the dye flows out into the processing bath upon reaction with the oxidized form of the developing agent as described in 3,419,391 can also be used.

As the diffusion resistant yellow coupler, the above general formula [I] is used.
In addition to the 2-equivalent yellow coupler represented by, a benzoylacetanilide type yellow coupler and a pivaloylacetanilide type yellow coupler which are generally widely used can be used.

Examples of these are U.S. Pat.Nos. 2,875,057 and 3,265,506.
Issue No. 3,664,841, Issue No. 3,408,194, Issue No. 3,277,15
No. 5, No. 3,447,928, No. 3,415,652, Japanese Patent Publication No. Sho 49-13
576, JP-A-48-29432, 48-66834, 49-10736
No. 49-122335, No. 50-28834, No. 50-132926, etc., together with the synthetic method.

Further, as color-free couplers that can be used in the present invention, British Patent Nos. 861,138, 914,145, and 1,109,963,
Japanese Examined Patent Publication No. 45-14033, U.S. Pat. No. 3,580,722 and Mid-Taylingen Ausden Forsenings La Poratorie Endea Agfa Revelkusen
Volume 4, pages 352 to 367 (1964) and the like can be selected.

The light-sensitive material of the present invention may further contain a development inhibitor releasing compound (hereinafter referred to as DIR compound). D
Examples of IR compounds include U.S. Pat.Nos. 3,148,062, 3,227,554, British Patent 2,010,818, and Japanese Patent Laid-Open No. 52-696.
No. 24, No. 55-135835, No. 57-44831 to react with the oxidant of the color developing agent to form a dye,
And a compound releasing a development inhibitor, U.S. Pat. No. 3,632,34
No. 5, No. 3,958,993, No. 3,938,996, No. 3,928,0
No. 41, No. 3,961,959, JP-A No. 52-67628, No. 51-6724
Japanese Patent Application No. 50-125202, a compound which releases a development inhibitor by reaction with an oxidant of a color developing agent but does not form a dye, as described in JP-A-54-145135.
Compounds releasing a development inhibitor by an intramolecular nucleophilic substitution reaction as described in U.S. Pat.No. 4,248,962, and a compound releasing by reaction with an oxidized product of a color developing agent, and JP-A-56-114946, As described in JP-A-57-154234, compounds capable of releasing a development inhibitor by electron transfer along a conjugated chain as described may be selected from compounds capable of releasing by reaction with an oxidized product of a color developing agent. it can.

Further, this DIR compound may be used alone or in combination of two or more kinds.

The addition amount of the above-mentioned coupler is generally preferably 2 × 10 ^{−3 to} 5 mol, and more preferably 1 ×, per mol of silver halide.
It is 10 ^{-2 to} 1.0 mol.

The addition amount of the above-mentioned DIR compound is preferably 5 × 10 ^{−5 to} 5 × 10 ⁻² mol, more preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻² mol.

As a dispersion method of the diffusion resistant coupler and the DIR compound,
Various methods such as so-called alkaline aqueous solution dispersion method, solid dispersion method, latex dispersion method, oil-in-water emulsion dispersion method, etc. can be used and can be appropriately selected according to the chemical structure of the diffusion-resistant coupler. .

In the present invention, the latex dispersion method and the oil-in-water type emulsion dispersion method are particularly effective. These dispersion methods are well known in the art, and the latex dispersion method and its effects are described in JP-A-49-74538, 51-59943, 54-32552 and Research Disclosure.
sure), August 1976, No. 14859, pp. 77-79.

Suitable latices are, for example, styrene, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2
-(Methacryloyloxy) ethyltrimethylammonium methosulfate 3- (methacryloyloxy) propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, N- [2- (2-methyl-4-oxopentyl)] acrylamide, 2- Acrylamide-
Homopolymers, copolymers and terpolymers of monomers such as 2-methylpropanesulfonic acid.
As the oil-in-water emulsion dispersion method, a method of dispersing a hydrophobic additive such as a coupler, for example, the method described in US Pat. No. 2,322,027 can be applied. That is, for example, after dissolving in a high boiling point organic solvent having a boiling point of 175 ° C. or higher such as tricresyl phosphate and dibutyl phthalate and / or a low boiling point organic solvent such as ethyl acetate and butyl propionate, alone or in a mixed solvent, a surfactant is used. Or a gelatin aqueous solution containing, and then emulsified and dispersed by a high-speed rotary mixer or a colloid mill, and then directly added to the silver halide emulsion, or
Alternatively, the low boiling point solvent is removed from the emulsified dispersion by a known method, and then this is added to the silver halide emulsion.

In the silver halide color photographic light-sensitive material to which the present invention is applied, the hydrophilic colloid advantageously used for preparing a silver halide emulsion and the hydrophilic colloid used in the non-photosensitive hydrophilic colloid layer are gelatin, phenyl. Derivatives such as carbamylated gelatin, aluminized gelatin, phthalated gelatin, colloidal albumin, agar, gum arabic, hydrolyzed cellulose acetate, carboxymethyl cellulose, hydroxyethyl cellulose, cellulose derivatives such as methyl cellulose, acrylamide, Imidized polyacrylamide, casein, vinyl alcohol polymers containing urethane carboxylic acid groups or cyanoacetyl groups, such as vinyl alcohol-vinyl cyanoacetate copolymers, polyvinyl alcohol, polyvinyl Rupiroridon, hydrolyzed polyvinyl acetates, polymers obtained by polymerization of a monomer having a protein or saturated acylated protein and a vinyl group, and the like.

The silver halide grains used in combination with the substantially monodisperse silver halide grains according to the present invention and the silver halide used in other emulsion layers include silver bromide, silver chloride, silver iodobromide and salts. It includes any of those usually used for silver halide photographic emulsions such as silver bromide and silver chloroiodobromide.

These silver halide grains may be coarse grains or fine grains, and the grain size distribution may be narrow or wide. The crystals of these silver halide grains may be normal crystals or twin crystals, and any ratio of [1.0.0] plane to [1.1.1] plane can be used. The crystal structure of these silver halide grains may be uniform from the inside to the outside or may have a layered structure in which the inside and the outside are different. Further, these silver halides may be of a type that forms a latent image mainly on the surface or may be of a type that is formed inside the grain.

The silver halide emulsion used in the silver halide color photographic light-sensitive material according to the present invention can be manufactured by various methods including commonly used manufacturing methods, for example, the method described in JP-B-46-7772, or U.S. Pat.No. 2,592,250. Described above, i.e., forming an emulsion of silver salt grains consisting of at least a portion of the silver salt, the solubility of which is greater than that of silver bromide, and then at least a portion of the grains is subjected to a silver bromide salt or an iodine odor. It can be prepared by a so-called conversion emulsion production method such as conversion into a silver halide salt or a production method of a Lippmann emulsion comprising fine grain silver halide having an average grain size of 0.1 μ or less.

The above silver halide emulsion can be sensitized with a chemical sensitizer. Chemical sensitizers are roughly classified into four types: precious metal sensitizers, sulfur sensitizers, selenium sensitizers and reduction sensitizers.

The noble metal sensitizer includes compounds such as gold compounds, ruthenium, rhodium, palladium, iridium and platinum. Particularly preferred compounds are chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, potassium chloroaurate and 2-au. Examples include low sulfobenzothiazole methyl chloride, ammonium chloroparadate, potassium chloroplatinate, sodium chloroparatite and sodium chloroiridate. When a gold compound is used, ammonium thiocyanate and sodium thiocyanate can be used together.

In addition to active gelatin, sulfur sensitizers include sulfur compounds, and particularly preferred compounds include sodium thiosulfate, ammonium thiosulfate, thiourea, thioacetamide, allylisothiourea and N-allyl rotanine.

The selenium sensitizer includes active and inactive selenium compounds, and particularly preferred compounds are colloidal selenium, selenoacetophenone, selenoacetamide, selenourea,
N, N-dimethyl selenourea, triphenylphosphine selenide and the like.

Reduction sensitizers include monovalent tin salts, polyamines, bisalkylaminosulfides, silane compounds, iminoaminomethanesulfinic acid, hydrazinium salts, and hydrazine derivatives.

Further, the silver halide emulsion may be subjected to spectral sensitization supersensitization by using cyanine dyes such as cyanine, merocyanine, and carbocyanine alone or in combination, or by using them in combination with styryl dyes, if necessary. You can

The selection can be arbitrarily determined according to the purpose and use of the silver halide color photographic light-sensitive material, such as the wavelength range to be sensitized and the sensitivity.

The above silver halide emulsion contains 1-phenyl-5-mercaptotetrazole and 3-methylbenzo in order to prevent the deterioration of sensitivity and the generation of capri during the manufacturing process, storage or processing of the silver halide color photographic light-sensitive material. Thiazole, 4-
Various compounds such as a heterocyclic compound such as hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, a mercapto compound, and metal salts can be added.

Hardening treatment of the emulsion is carried out according to a conventional method. The hardener used is a conventional photographic hardener, for example, aldehyde compounds such as formaldehyde, glyoxal, glutaraldehyde and their derivative compounds such as acetal or sodium bisulfite adduct, methanesulfonic acid ester compounds, Mucochloric acid or mucohalogenate compounds, epoxy compounds, aziridine compounds,
Active halogen compounds, maleic acid imide compounds, active vinyl compounds, carboximide compounds, isoxazole compounds, N-methylol compounds, isocyanate compounds, or inorganic hardeners such as chromium alum and zirconium sulfate. I can give you.

A surfactant may be added to the above silver halide emulsion alone or as a mixture. Examples of the surfactant include coating aids, emulsifiers, penetrating agents for treating liquids, defoaming agents, antistatic agents, anti-adhesive agents, saponin as a material for improving photographic characteristics or controlling physical properties. Such as natural products, alkylene oxides, glycerin,
Nonionic surfactants such as glycidol-based, higher alkylamines, pyridine, other heterocycles, quaternary nitrogen onium salts, cationic surfactants such as phosphonium or sulfoniums, carboxylic acids, sulfonic acids, phosphoric acid, sulfuric acid Various active agents such as anionic surfactants containing an acidic group such as an ester group and a phosphoric acid ester group, and amphoteric surfactants such as amino acids and aminosulfonic acids can be used.

The silver halide color photographic light-sensitive material according to the present invention comprises a benzotriazole compound, a triazine compound, a benzophenone compound or an acrylonitrile compound as an ultraviolet absorber in its constituent layers (eg, protective layer, intermediate layer, emulsion layer, back layer, etc.). It may contain a compound. Particularly, Tinuvin Ps manufactured by Ciba-Geigy Co., Ltd., 320, 326, 327, 328 and the like are preferably used alone or in combination.

Further, for the purpose of increasing the stability of color photography, the emulsion layer of the silver halide color photographic light-sensitive material of the present invention and /
Alternatively, p-substituted phenols can be contained in the non-photosensitive hydrophilic colloid layer which is the adjacent layer. Particularly preferred p-substituted phenols include alkyl-substituted hydroquinones, bishydroquinones, polymer hydroquinones, p-alkoxyphenols, phenolic compounds and the like. Furthermore, alkoxy or amyloxy derivatives of 6-chromanol or 6,6'-dihydroxy-2,2'-spirochroman can likewise be used.

The silver halide color photographic light-sensitive material according to the present invention is produced by coating on various supports. Examples of this support include films such as cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, polyethylene terephthalate, polyamide, polycarbonate, polystyrene or polyethylene laminated paper, polypropylene synthetic paper, baryta paper, etc., and these supports are respectively It is appropriately selected according to the purpose of use of the silver halide color photographic light-sensitive material.

These supports are generally subbed to enhance adhesion with the silver halide emulsion layers. Typical subbing materials used for subbing processing include vinyl chloride or vinylidene chloride copolymers, vinyl alcohol ester copolymers, unsaturated carboxylic acid-containing copolymers, and diene such as butadiene. Copolymers of acetals, copolymers of unsaturated carboxylic acid anhydrides such as maleic anhydride, particularly vinyl alcohol esters such as vinyl acetate, or copolymers with styrene or water or alkali thereof. , Ring-opened products with alcohols or amines, cellulose derivatives such as nitrocellulose and diacetylcellulose, compounds containing an epoxy group, gelatin or gelatin modified products, and polyolefin copolymers.

Furthermore, gelatin or polyols, monohydric or polyhydric phenols and halogen-substituted products thereof, cross-linking agents (hardeners), metal oxides and the like may be used in combination with these subbing materials to perform subbing processing. it can.

When the support is actually subjected to undercoating, the above-mentioned undercoat materials can be used alone or in combination. Further, these undercoating processes can form the undercoating layer by a single layer or multiple layers, but of course, it may be used in combination with the undercoating material to further overlay. For example, a method in which a gelatin layer is multilayer-coated on a vinylidene chloride copolymer layer, or a layer composed of a vinylidene chloride copolymer, a mixture of gelatin and a vinylidene chloride copolymer, and a gelatin layer are applied in this order in combination such as undercoating. A method of performing multi-layer coating is performed, and arbitrary materials can be used in combination depending on the purpose, and multi-layers can be used in combination.

In addition to the subbing process by the above material processing, the support surface and emulsion are treated by corona discharge, glow discharge, other electron impact flame treatment, ultraviolet irradiation, oxidation treatment, saponification treatment, roughening treatment etc. on the support surface. The layers can also be glued. These treatments can be used alone or in combination, and further sufficient undercoating can be performed by using them in combination with the above-mentioned material processing.

The silver halide color photographic light-sensitive material according to the present invention includes all kinds of silver halide color photographic light-sensitive materials such as a color negative film, a color positive film, a color reversal film and a color paper.

The color developing agent used in the development of the silver halide color photographic light-sensitive material of the present invention is an aromatic primary amine compound, particularly preferably a p-phenylenediamine type developing agent such as 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-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-Β-methoxyethylaniline, 3-β-methanesulfonamidoethyl-4-amino-N, N-diethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-
Hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-
Acetamide-4-amino-N, N-diethylaniline, 4-amino-N, N-dimethylaniline, N-ethyl-N-β- [β- (β-methoxyethoxy) ethoxy] ethyl-3-methyl-4 -Aminoaniline, N-ethyl-N-β- (β-methoxyethoxy) ethyl-3-
Methyl-4-aminoaniline and salts thereof such as sulfate, hydrochloride, sulfite, p-toluenesulfonate and the like.

The photographic additives used in these color developers include alkali agents (eg, alkali metal or ammonium hydroxides, carbonates, phosphates), pH adjusters or buffers (eg, acetic acid, boric acid). Weak acids and weak bases and their salts), development accelerators (eg pyridinium compounds, cationic compounds, potassium nitrate and sodium nitrate, polyethylene glycol condensates and their derivatives, nonionic compounds such as polythioethers, sal Polymer compounds having phytoesters, other pyridines, ethanolamines, organic amines, benzyl alcohol, hydrazines, etc., antifoggants (eg alkali bromide, alkali iodide, nitrobenzimidazoles, mercaptobenzimidazoles, etc. , 5-methylbenzotriazole 1-phenyl-5-mercaptotetrazole, rapid treatment liquid compounds, nitrobenzoic acid,
Benzothiazolium derivatives, phenazine-N-oxides, stain or anti-sludge agents, multi-layer effect accelerators,
There are preservatives (for example, sulfite, acidic sulfite, hydroxylamine hydrochloride, form sulfite, alkanolamine sulfite adduct, etc.).

The silver halide color photographic light-sensitive material which has been color-developed using such a color-developing solution has a conventional photographic processing such as a stopping solution containing an organic acid, fixing of an organic acid and hypo or ammon thiosulfate. Stop fixer containing components, fixer containing fixing components such as hypo or ammonium thiosulfate,
A bleaching solution containing a ferric salt of an aminopolycarboxylic acid and an alkali halide as main components, and a second of the aminopolycarboxylic acid
Each treatment selected from treatments such as a bleach-fixing solution containing an iron salt and a fixing component such as hypo or ammonium thiosulfate, a stabilizing solution, and treatments such as washing and drying may be appropriately combined.

Next, the present invention will be described in detail with reference to Examples, but the embodiments of the present invention are not limited thereto.

[Preparation of polydisperse emulsion]

An aqueous solution of silver nitrate and an aqueous solution of alkali halide were added in advance to an aqueous solution of gelatin and an excess of halide, and they were naturally dropped into a reaction kettle kept at 60 ° C. Then, an aqueous solution of Demol N and magnesium sulfate aqueous solution manufactured by Kao Atlas Co. were added to cause precipitation and removal. Salt was added and gelatin was added to obtain an emulsion with pAg7.8 and pH 6.0.

[Preparation of monodisperse emulsion]

During the grain growth, the ammoniacal silver nitrate aqueous solution and the potassium iodide and potassium bromide aqueous solution were added to the reaction kettle in which the silver halide seed particles and the gelatin aqueous solution had been charged in advance, while controlling the pAg and pH in the reaction kettle. Was added in proportion to the increase in surface area. Then, Kao Atlas Co., Ltd. Demol N aqueous solution and magnesium sulfate aqueous solution were added for precipitation and desalting, and gelatin was added to obtain an emulsion with pAg 7.8 and pH 6.0. Further, the silver iodide mol% was changed by changing the ratio of potassium iodide and potassium bromide, and the particle size was changed by pAg by changing the addition amounts of ammoniacal silver nitrate and potassium halide.

The core / shell emulsion was produced by the method described in JP-A-54-48521.

Example 1 Samples 1 to 10 were prepared by successively coating the following layers on a triacetate base which had been subjected to subbing processing.

Layer-1: The average particle size is 0.03 in the gelatin aqueous solution as shown in Table-1.
Add non-photosensitive fine grain silver iodobromide (μ content of 6 mol
%), Saponin, and 1,2-bis (vinylsulfonyl) ethane as a hardener, and coated so that the silver amount of non-photosensitive fine grain silver iodobromide is 2 mg / m ^{2 and the} dry film thickness is 2 μ. .

Layer-2 ... Blue-sensitive silver halide emulsion layer.

As shown in Table 1, the following emulsions and were used and prepared by a conventional method containing 0.25 mol of silver halide and 40 gr of gelatin per 1 kg of the emulsion. 1 kg of this emulsion was chemically sensitized with gold and sulfur sensitizers, and anhydrous 5,5'-dimethoxy-3,3'-di- (3-sulfopropyl) thiacyanine hydroxide was added as a sensitizing dye. , Then 4-hydroxy-6-
Methyl-1,3,3a, 7-mercaptotetrazole (20.0 mg) was added to prepare a blue-sensitive silver halide emulsion by a conventional method. Further, as shown in Table 1, a yellow coupler was dissolved in a mixture of 50 g of tricresyl phosphate and 10 ml of ethyl acetate by heating and dissolved in 1 mol of silver halide, and the mixture was added to a gelatin aqueous solution containing sodium triisopropylnaphthalenesulfonate. A blue-sensitive silver halide emulsion was prepared by adding the dispersion emulsified and dispersed in a Maloid mill, and the dry film thickness was 4.0.
It was applied so that it would be μ.

Layer-3 ... Protective layer Gelatin 4gr and 1,2-bis (vinylsulfonyl) ethane
100 ml of gelatin aqueous solution containing 0.2 gr was gelatin 1.3 gr / m ²
Was applied to give a dry film thickness of 1.2 μ.

Comparison coupler Emulsion used-Emulsion-monodisperse silver iodobromide emulsion (iodine content 8 mol%,
= 0.49 µ, u value = 75%) Emulsion-polydisperse silver iodobromide emulsion (iodine content 8 mol%,
= 0.49μ, u value = 48%) Here, the u value is the weight% of the weight of silver halide grains with respect to the total weight of silver halide grains, which is included within a grain size range of ± 20% around the average grain size. Represents (The same applies to the following examples.) White light was applied to each of the samples thus obtained through a wedge, and then development processing was performed in the following processing steps. Table 2 shows the yellow color development results obtained for each sample. Table 2 shows the results of sensitivity, RMS and LES.

A linear exposure scale described in The Theory of the Photographic Process, 4th edition, by Te Aina James, pp. 501-502, is used as a measure of the extent of the exposure latitude. , Hereafter referred to as LES). The sensitivity was indicated by the relative value of the reciprocal of the exposure amount that gives the capri density +0.1. The graininess was shown by 1000 times the standard deviation of the variation of the density value produced when a dye image with a dye image density of 1.0 was scanned by a microdensitometer with a circular scanning aperture of 25μ.

For sharpness, the sample has a spatial frequency of 3 lines / mm to 100
Exposure is performed through a wedge changed in the range of up to lines / mm, development processing is performed as shown in the following examples, and MTF (Modulation Transfer Function) of the obtained image is obtained.
The sharpness was evaluated by comparing the MTF values at spatial frequencies of 10 lines / mm and 30 lines / mm.

Processing step (38 ° C) Processing time Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stability 1 minute 30 seconds Composition of processing solution used in each processing step Was as follows:

[Color developer composition] [Bleaching liquid composition] [Fixer composition] [Stabilizing liquid composition] The development processing was performed under the above conditions.

The following is clear from Table 2. Samples 1 to 1 according to the present invention
4 and Comparative Sample 5, the sensitivity is lower than that of the sample according to the present invention unless the coupler according to the present invention is used.
The ES value will also be low. By comparing the sample 1 of the present invention with the comparative sample 6, it is easily understood that the LES is not increased unless the non-photosensitive colloid layer containing fine grain silver halide is provided in the first layer. Further, in the comparison between Sample 1 of the present invention and Comparative Samples 6 and 8, the monodisperse emulsion and the coupler according to the present invention were used in the second layer, and the non-photosensitive silver halide containing fine grain silver halide was used as the first layer. It can be seen that by providing the layers, the narrowness of the exposure area, which is a problem of the monodisperse emulsion, is successfully solved without impairing the sensitivity and graininess which are the advantages of the monodisperse emulsion.

Example-2 Sample Nos. 11 to 16 were prepared in the same manner as in Sample 1 of Example 1 using the emulsions shown in Table 3.

The emulsion of No. 14 was prepared by mixing emulsions with each other at a mixing ratio of 8: 2.

The above samples were processed in the same manner as in Example 1 to obtain the results shown in Table-3.

From these results, the monodisperse silver halide grains of the present invention in which the silver iodide content of the core of sample 11 is 10 mol% and the silver iodide content of the shell part is 3 mol% are good for LES. You can see that you get the results. Furthermore, the LES value of the core / shell type silver halide grains, NO.11, is superior to that of NO.12. Further, as can be seen from the sample of NO.14, the effect of the present invention can be obtained even when mixed with the polydisperse emulsion.

Example 3 Sample Nos. 17 to 19 were prepared by sequentially coating the following layers on a triacetate base which had been subjected to an undercoating process. Sample No. 17: Layer-1 ... Red photosensitive emulsion layer Silver iodobromide emulsion containing 6 mol% of silver iodide (average grain size
0.6μ, 0.25 mol silver halide / kg emulsion, 2 gelatin
2 gr) was prepared by a method for preparing a polydisperse emulsion, 1 kg of this emulsion was chemically sensitized with gold and sulfur sensitizers, and anhydrous 9-ethyl-3,3'-as a red-sensitizing sensitizing dye. The- (3
-Sulfopropyl) -4,5,4, ', 5'-dibenzothiacarbocyanine hydroxide, anhydrous 5,5'-dichloro-9
-Ethyl-3,3'-di- (3-sulfopropyl) thiacarbocyanine hydroxide, anhydrous 5,5'-dichloro-
3, '9-Diethyl-3- (4-sulfophtyl) oxythiacarbocyanine hydroxide was added, followed by 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.2
5 g was added. Further, 262 ml of the following cyan coupler dispersion was added to 1 kg of this emulsion to prepare a red-sensitive silver halide emulsion, which was coated so as to have a dry film thickness of 4.0 µ.

(Cyan coupler dispersion) 1-hydroxy-N- [δ- (2,4-di-t-aluminphenoxy) butyl] -2-naphthamide 45.0 g and 1
-Hydroxy-4- [4- (1-hydroxy-8-acetamido-3,6-disulfo-2-naphthylazo) phenoxy] -N- [δ- (2,4-di-t-aminophenoxy) butyl]- 2-naphthamide disodium salt 4.7
25 g of tricresyl phosphate, 167 ml of ethyl acetate
Of 5% gelatin aqueous solution containing 2.1 g of sodium triisopropylnaphthalene sulfonate dissolved in a mixture of
In addition to ml, it was emulsified and dispersed by a colloid mill to prepare 1000 ml.

Layer-2: Gelatin layer 4 g / 100 ml of 1,2-bissulfonylethane per 100 ml of gelatin layer.
An aqueous gelatin solution containing 2 g was applied at a rate of 1.3 g / m ² of gelatin so that the dry film thickness would be 1.2 μm.

Layer-3 ... Green light-sensitive silver halide emulsion layer.

A silver iodobromide emulsion containing 7 mol% of silver iodide (average flow size:
6μ, 0.25 mol of silver halide, 3 gelatin per kg of emulsion
7 gr) was prepared by the method for preparing a polydisperse emulsion, 1 kg of this emulsion was chemically sensitized with gold and sulfur sensitizers, and further anhydrous 5,5'-dichloro-9-as a green-sensitizing sensitizing dye. Ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine hydroxide; anhydrous 5,5'-diphenyl-9-ethyl-3,3'-di- (3-sulfopropyl) -5,6 ,Five,',
6'-Di-benzooxacarbocyanine hydroxide was added, followed by 4-hydroxy-6-methyl-1,3,3a, 7.
-0.25 g of tetrazaindene was added. Then, to 1 kg of this emulsion was added 350 ml of the following magenta coupler dispersion,
A green light-sensitive silver halide emulsion was prepared and coated so as to have a dry film thickness of 4.0 μm.

(Magenta coupler dispersion) 1- (2,4,6-trichlorophenyl) -3- [3- (2,4
35 g of (di-t-amylphenoxyacetamido) benzamido] -5-pyrazolone and 1- (2,4,6-trichlorophenyl) -4- (1-naphthylazo) -3- (2-
Chloro-5-octadecenylsuccinimide anilino)
-5-pyrazolone 8 g tricresyl phosphate 43
g, and 143 ml of ethyl acetate and dissolved in a mixture of 720 ml of 5% gelatin aqueous solution containing 4.0 gr of sodium triisopropylnaphthalenesulfonate.

Layer-4: Yellow filter layer.

Dry yellow filter layer consisting of yellow colloidal silver 1.
It was applied to have a thickness of 2μ.

Layer-5 ... Non-photosensitive colloid layer.

Same as Layer-1 of Sample No.-1 of Example-1.

Layer-6 ... Blue-sensitive silver halide emulsion layer Same as Layer-2 of Sample No.-1 of Example-1.

Layer-7 ... Protective layer Same as Layer-3 of Sample No.-1 of Example-1.

Sample No.18 Layer-1 to Layer-3 are the same as Sample No.17.

Layer-4 ... Non-photosensitive colloid layer Same as Layer-5 of Sample No.17.

Layer-5: Yellow filter layer Same as Layer-4 of Sample No.17.

Layer-6 ... Blue-sensitive silver halide layer Same as Layer-6 of Sample No.17.

Layer-7 ... Protective layer Same as Layer-7 of sample NO.17.

Sample No.19 Layer-1 to Layer-4 are the same as Sample No.17.

Layer-5 ... Blue-sensitive silver halide layer.

Same as Layer-6 of Sample No.17.

Layer-6 ... Protective layer Same as Layer-7 of sample NO.17.

Sample No.20 Layer-1 to Layer-5 are the same as Sample No.17.

Layer-6 ... Blue-sensitive silver halide layer.

Same as Layer-2 of Sample No.8.

Layer-7 ... Protective layer Same as Sample No. 17 and Layer-7.

Each sample thus obtained was treated in the same manner as in Example 1. The results obtained for each sample are shown in Tables 3 and 4.

As a comparison of each sample, the effect of the present invention is increased when the fine grain silver halide layer according to the present invention is provided as close to the blue-sensitive silver halide layer as possible and closer to the support side. Things will be easily understood. Further, when a non-photosensitive colloid layer is provided close to the green-sensitive silver halide emulsion layer, a large increase in Dmm of the green-sensitive silver halide layer occurs as shown in Table-3. Table 4 shows that the sample No. 17 according to the present invention has a better MTF value in the green photosensitive layer than the sample No. 20 in which the emulsion of the blue-sensitive silver halide layer is changed to a polydisperse emulsion. I understand.

Example-4 Non-photosensitive fine grain silver halide in Layer-5 of Sample No. 17 of Example-3 was used as non-photosensitive silver iodobromide having an average grain size of 0.35 µ (iodine content 6 mol%). Sample No. 21 was prepared in the same manner as Sample No. 17, except that

Samples NO.17 and NO21 were treated simultaneously as in Example-1,
When comparing the MTF values of the green photosensitive layer, sample NO21 is MT than NO.17.
The F value was small and inferior.

Sample No. 22 was prepared in the same manner as Sample No. 17 except that the amount of fine grain silver halide in Layer-5 of Sample No. 17 was changed from 2 mg / dm ² to 4 mg / dm ² and 10 mg / dm ^2. , No23 was created. When NO.17, No22, and No23 were treated at the same time as in Example-1, the LES value of the blue-sensitive layer was 2.3 for sample NO.17 while 2.3 for LES of the blue-sensitive layer. However, the MTF value of the green photosensitive layer of Sample No. 23 was Sample No. 1.
7, inferior to No22.

Example-5 Sample 24 Layers 6 to 6 were coated in the same manner as in Sample No. 17.

Layer-7: Blue-sensitive high-sensitivity silver halide emulsion layer Silver iodobromide emulsion (average grain size 1.2 μ, silver iodide 7 mol%
Of a polydisperse emulsion, chemically sensitized with gold and a sulfur sensitizer, and anhydrous 5,5'-dimethoxy-3,3'-di- Add (3-sulfopropyl) thiacyanine hydroxide, then 4-
Hydroxy-6-methyl-1,3,3a, 7 tetrazaindene
A blue-sensitive high-sensitivity silver halide emulsion was prepared by adding 1.0 g and 10.0 mg of 1-phenyl-5-mercaptotetrazole. Further, α-bivaloyl-α- (1-benzyl-2-phenyl-3.5-dioxo-1,2,4-triazolidin-4-yl) -2'-chloro-5'-as a yellow coupler per mol of silver halide. [Α- (dodecyloxycarbonyl) pentoxycarbonyl] acetanilide 80 g
A mixture of 40 g of dibutyl phthalate and 240 ml of ethyl acetate is dissolved by heating and added to an aqueous gelatin solution containing sodium triisopropylnaphthalene sulfonate, and the dispersion is emulsified and dispersed by a colloid mill to add a blue-sensitive high-sensitivity silver halide. An emulsion was prepared and coated so that the dry film thickness was 2.0 μm.

Layer-8 ... Protective layer Same as layer 7 of sample NO17.

The samples 24 and 17 thus obtained were treated in the same manner as in Example 1 and compared with each other. As a result, it was found that the effects of the present invention were sufficiently exhibited even if the blue-sensitive layer had a two-layer structure. It was From this fact, it can be predicted that the effects of the present invention are exhibited even when the blue-sensitive layer has a multilayer structure of three or more layers.

(Effect of the Invention) The silver halide color photographic light-sensitive material of the present invention has a wide latitude and is improved in graininess and sharpness.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-50-23228 (JP, A) JP-A-56-14236 (JP, A) JP-A-50-34232 (JP, A) JP-A-51- 53825 (JP, A) Japanese Patent Publication 4-17410 (JP, B2) Japanese Patent Publication 4-10055 (JP, B2)

Claims (1)

[Claims] 1. At least one layer on a support, adjacent to an emulsion layer containing silver halide grains containing a 2-equivalent yellow coupler and being substantially monodisperse, on the near side of the support, A silver halide color photographic light-sensitive material comprising a non-light-sensitive colloid layer containing substantially non-light-sensitive fine silver halide grains.