JP2699205B2 - Silver halide color photographic materials - Google Patents

Description

Description: BACKGROUND OF THE INVENTION The present invention relates to a silver halide color reversal photographic material having excellent sharpness and granularity.

(Prior Art) A silver halide color photographic light-sensitive material for photographing is required to have high sensitivity and excellent image quality such as sharpness and graininess regardless of negative or reversal.

Generally, in a multilayer silver halide color photographic light-sensitive material having a blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer, light scattering by silver halide grains reduces the sharpness of an underlying emulsion layer. It has been known. On the other hand, U.S. Pat. No. 4,439,520 discloses a multilayer color photographic light-sensitive material having high sensitivity and improved sharpness by using tabular silver halide grains.

However, in the above-mentioned U.S. Pat. No. 5,849,097, when tabular silver halide grains are used in a plurality of layers having different color sensitivities in a multilayer silver halide color photographic light-sensitive material, the tabular halogen used in each layer from the viewpoints of sharpness and graininess. There is no description about more preferable values of the thickness and the aspect ratio of the silver halide grains.

(Problems to be Solved by the Invention) It is an object of the present invention to provide a silver halide color photographic material having improved sharpness and graininess.

(Means for Solving the Problems) The above-mentioned problems are achieved by (1) providing at least one red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer on a support, and a blue-sensitive silver halide emulsion; In a silver halide color photographic material in which a layer is located farthest from a support, at least one layer of a red-sensitive silver halide emulsion layer or a green-sensitive silver halide emulsion layer and at least one layer of a blue-sensitive silver halide emulsion layer 70% or more of the total projected area of the silver halide emulsion contained in the silver halide emulsion layer contained in each silver halide emulsion layer has a thickness of 0.5 μm or less, a diameter of 0.5 μm or more, and an aspect ratio of 3 or more. Yes,
And the ratio of the length of the side having the maximum length to the length of the side having the minimum length is a hexagon that is 2 or less,
And occupied by tabular silver halide having two parallel surfaces as outer surfaces, and further having a monodispersity of 20% or less in the coefficient of variation of the grain size distribution of the hexagonal tabular silver halide grains, And the average thickness of the tabular silver halide grains contained in the red-sensitive silver halide emulsion layer or the green-sensitive silver halide emulsion layer among the tabular silver halide grains contained in the at least two silver halide emulsion layers. Is larger than the average thickness of the tabular silver halide grains contained in the blue-sensitive silver halide emulsion layer, and (2) contained in at least one of the green-sensitive layers. 3. The silver halide color photographic material according to claim 1, wherein the tabular silver halide emulsion has an average thickness of 0.2 μm or more and an average aspect ratio of 8 or less. Solved by light material.

 Hereinafter, the present invention will be described clearly.

The light-sensitive material of the present invention has a silver halide emulsion layer having a different color sensitivity, such as a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer, on a support. These color-sensitive layers are usually composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity and different sensitivities in a photographic material. In the color-sensitive layer, the blue-sensitive layer is located farthest from the support, and the red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer are usually arranged in this order from the support side. However, the above arrangement may be different depending on the purpose, or an arrangement may be adopted in which different color-sensitive layers are sandwiched between the same color-sensitive layers.

Non-light-sensitive layers such as various intermediate layers may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer is described in JP-A-61-43748 and JP-A-59-113438.
No. 59-113440, No. 61-20037, No. 61-20038, couplers, DIR compounds and the like as described in the specification, and may contain a commonly used color mixing inhibitor. Is also good.

As described in West German Patent 1,121,470 or British Patent No. 923,045, a plurality of silver halide emulsion layers constituting each unit light-sensitive layer such as a blue-sensitive layer may be composed of a high-speed emulsion layer and a low-speed emulsion layer. A layer configuration can be preferably used.
Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also, Japanese Patent Application Laid-Open No. 57-11
No. 2751, No. 62-200350, No. 62-206541, No. 62-2065
As described in JP-A-43-43, a low-speed emulsion layer may be provided on the side remote from the support, and a high-speed emulsion layer may be provided on the side near the support.

As specific examples, from the farthest side from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / a high-sensitivity red Sensitivity layer (RH)
/ Low-sensitivity red-sensitive layer (RL) or BH / BL / GL / GH / RH / R
They can be installed in the order of L or in the order of BH / BL / GH / GL / RL / RH.

As described in JP-B-55-34932, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Also, JP-A-56-25738,
As described in JP-A-62-63936, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

As described in JP-B-49-15495, the upper layer is the most sensitive silver halide emulsion layer, the middle layer is the less sensitive silver halide emulsion layer, and the lower layer is more sensitive than the middle layer. A silver halide emulsion layer having a low degree is arranged,
There is an array composed of three layers having different sensitivities in which the sensitivities are sequentially decreased toward the support. Even in the case of three layers having different sensitivities, Japanese Patent Application Laid-Open No.
As described in JP-A-202464, a medium-speed emulsion layer / a high-speed emulsion layer / a low-speed emulsion layer may be arranged in the same color-sensitive layer from the side remote from the support.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer.

The arrangement may be changed as described above even in the case of four or more layers.

No. 4,663,271 to improve color reproduction
No. 4,705,744, 4,707,436, JP-A-62-16
0448, 63-89850, BL, GL, RL
It is preferable to arrange a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layer adjacent to or close to the main photosensitive layer.

As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

Tabular silver halide grains are contained in at least one of the red-sensitive or green-sensitive silver halide emulsion layer and at least one of the blue-sensitive silver halide emulsion layers of the present invention.

In these silver halide emulsion layers, the proportion of tabular silver halide grains in the total projected area is at least 50%, more preferably at least 70%.

Hereinafter, tabular silver halide grains that can be used in each color-sensitive layer will be described.

In the present invention, a tabular silver halide grain (hereinafter, referred to as a "tabular grain") has two opposing parallel main planes and a circle equivalent diameter of the main plane (a circle having the same projected area as the main plane). A particle whose diameter is at least three times larger than the distance between the main planes (ie, the thickness of the particle).

 The aspect ratio is a ratio of particle diameter / particle thickness.

The average aspect ratio is obtained by averaging the aspect ratios of individual tabular grains, but as a simple method, it can be determined as the ratio between the average diameter of all tabular grains and the average thickness of all tabular grains. I can do it.

Tabular silver halide grains contained in the red-sensitive silver halide emulsion layer or the green-sensitive silver halide emulsion layer of the present invention preferably have an average aspect ratio of 3 to 12, and preferably 3 to 8.
Is more preferable.

The diameter (corresponding to a circle) of the tabular grains is 0.5 to 10 μm, preferably 0.5 to 5.0 μm, and more preferably 0.5 to 2.0 μm.

The particle thickness is 0.5 μm or less, preferably 0.1 to 0.5 μm,
More preferably, it is 0.2 to 0.4 μm.

The tabular grains contained in the blue-sensitive silver halide emulsion layer of the present invention preferably have an average aspect ratio of 3 to 12, more preferably 5 to 10.

The diameter (corresponding to a circle) of the tabular grains is 0.5 to 10 μm, preferably 0.5 to 5.0 μm, and more preferably 0.5 to 2.0 μm.

The particle thickness is 0.5 μm or less, preferably 0.05 to 0.5 μm,
More preferably, it is 0.08 to 0.3 μm.

Of the tabular silver halide grains contained in the at least two layers, the tabular silver halide grains contained in the red-sensitive silver halide emulsion layer or the green-sensitive silver halide emulsion layer are contained in the blue-sensitive silver halide emulsion layer. It is necessary that the average thickness is larger than that of the tabular silver halide grains. The difference is preferably at least 0.02 μm, more preferably at least 0.05 μm. Here, the average thickness is preferably an average value of tabular grains having a thickness of 0.5 μm or less, a diameter of 0.5 μm or less, and an aspect ratio of 3 or more, occupying 50% of the projected area of all silver halide grains in each emulsion layer. .

The measurement of the particle diameter and the particle thickness in the present invention can be obtained from an electron micrograph of the particles as in the method described in US Pat. No. 4,434,226.

As a general method for producing tabular grains, U.S. Pat.
No. 4439520, No. 4414310, No. 4399215,
No. 4433048, No. 4386156, No. 400463, No. 44
No. 14306, the method described in No. 4443501, etc.
It can be achieved by combining them.

For example, in an atmosphere having a relatively high pAg value of pBr 1.3 or less, tabular grains form seed crystals in which 40% or more exist by weight, and silver and a halogen solution are added while maintaining the same or higher pBr value. It is obtained by growing a seed crystal.

It is desirable to add a silver and halogen solution so that new crystal nuclei are not generated in the above-described grain growth process.

The size of the tabular grains can be adjusted by controlling the temperature, selecting the type and amount of the solvent, and controlling the addition rate of the silver salt and halide used during grain growth.

The tabular grains that can be used in the present invention are prepared by adding silver halide solution (eg, AgNO ₃ aqueous solution) and halide solution (eg, BKr aqueous solution) at the rate of addition, the amount, and the concentration of the silver salt solution (eg, AgNO ₃ aqueous solution) to be added at the time of its production. The method of raising is preferably used.

Regarding these methods, for example, British Patent No. 1,335,925
No. 3,672,900, U.S. Pat.No. 3,650,757, U.S. Pat.
42,445, JP-A-55-142329, and JP-A-55-158124 can be referred to.

In the present invention, monodisperse hexagonal tabular grains as described in JP-A-63-151618 are used. That is, a silver halide emulsion comprising a dispersion medium and silver halide grains, wherein 70% or more of the total projected area of the silver halide grains has a maximum length with respect to a length of a side having a minimum length. Is occupied by tabular silver halide having a hexagonal shape having a length ratio of 2 or less and having two parallel surfaces as outer surfaces, and further comprising the hexagonal tabular silver halide. It has a monodispersity of 20% or less in the coefficient of variation of the grain size distribution of the grains [the value obtained by dividing the variation (standard deviation) of the grain size represented by the circle-converted diameter of the projected area thereof by the tabular grain size]. .

The tabular grains used in the present invention are silver iodobromide, silver chloroiodobromide or silver bromide having a silver bromide or silver iodide content of 30 mol% or less, and usually have a silver iodide content of 1 mol%. 〜20 mol% of silver iodobromide is used.

The tabular silver halide grains usable in the present invention may have a uniform silver iodide distribution or may have two or more phases having different silver iodide contents.

For example, silver iodobromide tabular grains used in the present invention may have a layered structure composed of a plurality of phases having different iodide contents. JP-A-58-113,927
JP-A-58-113,928, JP-A-59-99,443, JP-A-59-119,344, JP-A-59-119,350, etc., in the composition of the tabular silver halide grains and in the halogen grains. Preferred examples of the distribution are described.

In the tabular grains used in the present invention, silver halides having different compositions may be bonded by epitaxial bonding, or may be bonded to any compound other than silver halide, for example, rhodan silver or lead oxide. These emulsion grains are described in U.S. Pat.Nos. 4,094,684 and 4,142,900.
No. 4,459,353, UK Patent No. 2,038,792, U.S. Pat.Nos. 4,349,622, 4,395,478, 4,433,501, 4,4
63,087, 3,656,962, 3,852,067, JP-A-59-
No. 162540 and the like.

Tabular grains are (111), (100), or (11)
1) It is possible to select one formed from a mixed surface of (100) and (100) surfaces.

The tabular grains that can be used in the present invention are prepared by depositing silver and halogen on the tabular grains at any stage during grain formation while adjusting the pBr value and the temperature in the presence of various additives. The specific surface can be grown in the form of pits on the surface of the tabular grains to increase the surface area. Representative compounds that can be used to grow the specific surface include the following.

Additives for forming pits composed of (211) planes include, for example, compounds (I) to (VI). Examples of additives for forming pits composed of (331) planes include compounds (VII) to (X). It is also possible to select another additive to grow a unique plane including the (100) plane, the (111) plane, the (210) plane, the (321) plane, and the like.

Compound example The tabular grains usable in the present invention may be ordinary surface latent image type silver halide grains or internal latent image type silver halide grains which mainly form a latent image inside.
Further, tabular grains having improved pressure characteristics in which lattice irregularities are caused by the gap of the halogen composition in the grains may be used.

The preferred silver halide contained in other silver halide emulsions used in the present invention is silver bromide or about 30 mol%.
It is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing the following silver iodide. Particularly preferred is about 1 mol%
Silver iodobromide or silver iodochlorobromide containing from 1 to about 20 mol% of silver iodide.

Other silver halide grains of the present invention include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystal forms such as spherical and plate-like, and those having twin planes. Or a combination thereof having crystal defects.

The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion that can be used in the present invention is described in, for example, Research Disclosure (RD) No. 17643 (1978).
December, p. 22-23, "I. Emulsion preparati
on and types) ”and No. 18716 (November 1979),
648 pages, No. 307105 (November 1989), pages 863 to 865, and "The Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (P. Glafkides, Chemie et Photographique, Paul Mo
ntel, 1967), "Digital Photographic Emulsion Chemistry", Focal Press (GFDuffin, Photographic Emulsion Che)
mistry (Focal Press, 1966)), "Production and coating of photographic emulsions" by Zerikuman et al., Focal Press (VLZali)
kmanet al., Making and Coating Photographic Emulsio
n, Focal Press, 1964).

Monodisperse emulsions described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, and may have a layered structure.Also, silver halides having different compositions are joined by an epitaxial junction. And it may be bonded to a compound other than silver halide, such as, for example, silver rhodan or lead oxide. Also, a mixture of particles of various crystal forms may be used.

The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grains, or a type having a latent image on both the surface and the inside. It is necessary to be. Of the internal latent image type,
A core / shell type internal latent image type emulsion described in JP-A-63-264740 may be used. The method for preparing the core / shell type internal latent image type emulsion is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

 The emulsions of the invention are usually spectrally sensitized.

As the spectral sensitizing dye used in the present invention, a methine dye is usually used, which includes a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye,
Holopolar cyanine dyes, hemicyanine dyes, styrine dyes and hemioxonol dyes are included. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc .; Nucleus fused with an aromatic hydrocarbon ring; ie, indolenine nucleus, benzindolenin nucleus, indole nucleus,
A benzoxadol nucleus, a naphthoxadol compound, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

In a merocyanine dye or a complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-
A 5- to 6-membered heterocyclic nucleus such as a 2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied.

The amount of the sensitizing dye added during the preparation of the silver halide emulsion cannot be unambiguously determined depending on the type of the additive or the amount of the silver halide, but it is almost the same as the amount added by the conventional method. Can be used.

That is, the preferable addition amount of the sensitizing dye is 0.001 to 100 mmol per 1 mol of silver halide, and more preferably.
It is 0.01 to 10 mmol.

The sensitizing dye is added after or before chemical ripening. The sensitizing dye is most preferably added to the silver halide emulsion of the present invention during chemical ripening or before chemical ripening (for example, during grain formation or physical ripening).

Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. For example, aminostil compounds substituted with a nitrogen-containing heterocyclic group (for example, those described in U.S. Pat. Nos. 2,933,390 and 3,635,721), aromatic organic acid formaldehyde condensates (for example, those described in U.S. Pat. No. 3,743,510), Cadmium salts, azaindene compounds and the like may be included. US Patent
3,615,613, 3,615,641, 3,617,295, 3,63
The combinations described in 5,721 are particularly useful.

Silver halide emulsions are usually chemically sensitized. For chemical sensitization, for example, H. Frieser,
Die Grundläger del Photography Ischen Protesse Mitt Silberhalogeniden (Die
Grundlagen der Photographishen Prozesse mit Silber
halogeniden) (Academiche Ferragus Gesersacht 1968), pages 675 to 734.

That is, a sulfur sensitization method using a compound containing a sulfur capable of reacting with active gelatin or silver (eg, thiosulfate, thioureas, mercapto compounds, rhodanines); a reducing substance (eg, stannous tin salt, Reduction sensitization using amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, ascorbic acid; noble metal compounds (for example, gold complex salts, and complex salts of Group VIII metals such as Pt, Ir, and Pd) ) Can be used alone or in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro or halogen-substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercapto Benzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketo compounds such as Oxazolinethione; azaindenes such as tetraazaindenes (especially 4-hydroxy-substituted [1,3,3a, 7] tetraazaindenes); benzenethiosulfonic acids; Nsurufin acid; can be added to many compounds known as antifoggants or stabilizers, such as.

The time of addition of these antifoggants or stabilizers is usually
It is carried out after chemical sensitization, but can be more preferably selected during chemical ripening or before chemical ripening. That is, in the course of silver halide emulsion grain formation, even during the addition of the silver salt solution, during the period from the addition to the start of chemical ripening, during chemical ripening (during the chemical ripening time, preferably within 50% from the start, More preferably, up to 20%).

As described above, the silver halide emulsion of the present invention is usually subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such a process are Research Disclosure Nos. 17643, 18716 and 307.
105, and the relevant locations are summarized in the table below.

In the light-sensitive material of the present invention, two or more types of emulsions having at least one characteristic different from each other in the grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used.

The light-sensitive material of the present invention includes silver halide grains having a fogged surface described in U.S. Pat.No. 4,082,553, and halogens having a fogged interior described in U.S. Pat.No. 4,626,498 and JP-A-59-214852. Silver halide grains and colloidal silver can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer. The term "silver halide particles having a fogged inside or surface thereof" means silver halide grains which can be uniformly (non-imagewise) developed regardless of unexposed portions and exposed portions of the photosensitive material. . The method of preparing silver halide grains having the inside or surface of the grains covered is as follows.
It is described in U.S. Pat. No. 4,626,498 and JP-A-59-214852.

The silver halide forming the internal nucleus of the core / shear type silver halide grains whose inside is fogged may have the same halogen composition or different halogen compositions. Any of silver chloride, silver chlorobromide, silver bromoiodide and silver chloroiodobromide can be used as the silver halide having the inside or the surface of the grain fogged. There is no particular limitation on the grain size of these fogged silver halide grains,
0.01 to 0.75 μm as average particle size, especially 0.05 to 0.6
μm is preferred. The grain shape is not particularly limited, and may be regular grains or polydisperse emulsions, but may be monodisperse (at least 95% of the weight or the number of grains of the silver halide emulsion is ± 40% of the average grain size). % Or a particle diameter variation coefficient of 20% or less).

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is not exposed during imagewise exposure to obtain a dye image,
It is preferable that the silver halide fine particles are not substantially developed in the developing process and are not fogged in advance.

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as needed. Preferably 0.5 to 10 mol% of silver iodide
It contains.

The fine grain silver halide preferably has an average grain size (average value of the circle equivalent diameter of the projected area) of 0.01 to 0.5 μm, and 0.02 to 0.2 μm.
μm is more preferred.

Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, before adding this to the coating solution, a triazole-based, azaindene-based,
It is preferable to add a known stabilizer such as a benzothiazolium-based or mercapto-based compound or a zinc compound. Colloidal silver can be preferably contained in the layer containing fine silver halide grains.

Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

Also, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Patent Nos. 4,411,987 and 4,435,503
It is preferable to add a compound capable of being fixed by reacting with formaldehyde described in (1) to the photosensitive material.

U.S. Pat.Nos. 4,740,454 and
No. 4,788,132, JP-A-62-18539 and JP-A-1-283551 preferably contain a mercapto compound.

In the light-sensitive material of the present invention, described in JP-A-1-106052,
A compound capable of releasing a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof, irrespective of the amount of developed silver produced by the development processing can be contained.

In the light-sensitive material of the present invention, a dye or a dye dispersed by the method described in International Publication WO88 / 04794,
EP317,308A, U.S. Pat.No.4,420,555, JP-A-1-25935
The dye described in No. 8 can be preferably contained.

Various color couplers can be used in the present invention, and specific examples thereof are described in the aforementioned Research Disclosure.
No. 17643, VII-CG, and No. 307105, VII-C
-G are described in the patents.

As a yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
No. 1,752, No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, No. 1,476,760, U.S. Pat.
Preferred are those described in 3,968, 4,314,023, 4,511,649, and EP 249,473A.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Patent No. 4,310,
No. 619, No. 4,351,897, European Patent No. 73,636, U.S. Pat. No. 3,061,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-3355
No. 2, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, and JP-A-60-35
No. 730, No. 51-118034, No. 60-185951, U.S. Pat.
Particularly preferred are those described in 4,500,630, 4,540,654, 4,556,630, and WO88 / 04795.

Cyan couplers include phenolic and naphthol couplers, U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200,
No. 2,369,929, No. 2,801,171, No. 2,772,162
No. 2,895,826, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, No. 249,453
A, U.S. Pat.Nos. 3,446,622, 4,333,999,
No. 4,775,616, No. 4,451,559, No. 4,427,767, No. 4,690,889, No. 4,254,212, No. 4,296,199,
Preferred are those described in JP-A-61-42658.

Typical examples of polymerized dye-forming couplers include U.S. Patent Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 4,409,320, No. 4,576,910, UK Patent No. 2,
No. 102,137 and European Patent No. 341,188A.

As a coupler in which the coloring dye has an appropriate diffusivity,
Preferred are those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570, and West German Patent (Published) No. 3,234,533.

Colored couplers for correcting unwanted absorption of coloring dyes are described in Research Disclosure No. 17643 VII.
Section G, Section VII-G of No. 307105, U.S. Pat.
No. 0, Japanese Patent Publication No. 57-39413, U.S. Pat. Nos. 4,004,929 and 4,138,258, and British Patent No. 1,146,368 are preferred. Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.No. 4,744,181 and a dye capable of forming a dye by reacting with a developing agent described in U.S. Pat. It is also preferable to use a coupler having a precursor group as a leaving group.

Compounds that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers releasing a development inhibitor are disclosed in the aforementioned RD17643, Sections VII-F and Nos. 307105 and VII-F.
57-151944, 57-154234, 60-184248, 63
-37346, 63-37350, U.S. Pat.No. 4,248,962,
Those described in JP-A-4,782,012 are preferred.

Examples of couplers that release an image nucleating agent or a development accelerator in the form of an image during development include British Patent Nos. 2,097,140 and 2,1
No. 31,188, JP-A Nos. 59-157638 and 59-170840 are preferred. Also, Japanese Patent Application Laid-Open Nos.
Compounds which release a fogging agent, a development accelerator, a silver halide solvent, etc. by an oxidation-reduction reaction with an oxidized developing agent described in JP-A-252340, JP-A-1-44940 and JP-A-1-45687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat.No. 4,130,427 and the like, multi-equivalent couplers described in U.S. Pat.Nos. 4,283,472, 4,338,393, and 4,310,618. , JP-A-60-1
No. 85950, DIR redox compound releasing couplers described in JP-A-62-24252, etc., DIR coupler releasing couplers, DIR coupler releasing redox compounds or DIR redox releasing redox compounds, European Patent Nos. 173,302A and 313,
No. 308A, couplers releasing dyes that recolor after release, RD Nos. 11449 and 24241, bleaching accelerator releasing couplers described in JP-A-61-201247, U.S. Pat.No. 4,555,477
And the like, and a ligand releasing coupler described in JP-A-63-75747.
US Patent No.
Couplers that release a fluorescent dye described in 4,774,181 are exemplified.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

The color photographic light-sensitive material according to the present invention is described in RD.
Development can be carried out by the usual methods described on pages 28 to 29 of 17643, No. 18716, left column to right column of 651, and No. 307105, pages 880 to 881.

The color developer used in the development of the photosensitive material of the present invention is
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent.
Phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-N-.
β-hydroxyethylaniline-3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-
Examples include methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Among these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferred. These compounds can be used in combination of two or more depending on the purpose.

When the reversal process is performed, color development is usually performed after black and white development. The black-and-white developer includes dihydroxybenzenes such as hydroquinone, 1-phenyl-3-
Known black-and-white developing agents such as 3-pyrazolidones such as pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 or less per square meter of the light-sensitive material. By reducing the bromide ion concentration in the replenishing solution, 500 m
It can be less than l. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air.

The time for the color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of the color developing agent.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further processing in two successive bleach-fix baths,
Fixing processing before bleach-fixing processing or bleaching processing after bleach-fixing processing can be arbitrarily performed according to the purpose.
As a bleaching agent, iron (III) complex salts of aminopolycarboxylate such as iron (III) complex salt of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate are used for rapid treatment and prevention of environmental pollution. Is preferred. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but the processing can be carried out at a lower pH for speeding up the processing.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their prebaths, if necessary.

The silver halide light-sensitive material of the present invention is disclosed in U.S. Pat.
No. 500,626, JP-A-60-133449, JP-A-59-218443, JP-A-6
It is also applicable to the photothermographic materials described in 1-238056, European Patent 210,660A2, and the like.

(Examples) Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Example-1 <Preparation of Monodispersed Cubic Silver Halide Emulsions A to C> A monodispersed cubic silver halide emulsion A was prepared as follows.

50cc of 0.3M silver nitrate aqueous solution and 0.3 ml of 3.0% by weight gelatin aqueous solution containing 0.06M potassium bromide kept at 70 ° C
50 cc of an aqueous potassium bromide solution of M was added over 2 minutes by the double jet method at pAg 7.0. By this 0.24μm
Of silver iodobromide core particles (nucleation step).

Subsequently, at 70 ° C., 250 ml of an aqueous solution containing 1.0 M silver nitrate and 0.95 M potassium bromide and 0.05 M potassium iodide were added at 20 ° C.
Over the course of minutes, it was added at pAg 6.8 by the double jet method (particle growth step I). 1.0M at 70 ° C
250 ml of an aqueous solution containing 250 ml of silver nitrate and 0.95 M potassium bromide and 0.05 M potassium iodide were added by a double jet method at pAg 6.8 over 20 minutes (grain growth stage II).

After that, it is washed with water by a known flocculation method at 35 ° C., 50 g of gelatin is added, and potassium silver chloride and sodium thiosulfate are added at 60 ° C., pH 6.2, and pAg 8.8 to optimize gold-
Sulfur sensitization was applied.

As shown in Table 1, cubic monodisperse emulsions B and C having different average particle sizes were prepared for emulsion A by changing the addition rates of the aqueous silver nitrate solution and the aqueous halogen solution in the nucleation stage.

<Preparation of Monodispersed Tabular Silver Halide Emulsion D-1> Tabular silver halide grains D were prepared by the following method.

While stirring it into a 0.8% by weight gelatin solution 1.7 containing 0.02 mol of potassium bromide, 30 cc of a 2.0 M silver nitrate solution and a 2.0 M potassium bromide aqueous solution are produced by a double jet method.
Add 30 cc in 22 seconds. During this time, the gelatin solution was kept at 30 cc. After the addition, the temperature was raised to 70 cc and 30 g of gelatin was added, followed by aging for 30 minutes.

(Nucleation step) After adjusting the pBr of the emulsion containing the core particles with a silver nitrate solution, accelerate an aqueous solution containing 75 g of silver nitrate and a potassium bromide solution containing 5.0 mol% of potassium iodide in an equimolar amount to silver nitrate in 40 minutes. At the specified flow rate (the flow rate at the end is 10 times the flow rate at the start)
Was added. (Grain growth stage I) Addition of 75 g of silver nitrate and an equimolar potassium bromide aqueous solution at an accelerated flow rate (the flow rate at the end is twice that at the start) in another 20 minutes after the addition after adjusting the pBr to 2 Was done. (Grain growth stage II) Thereafter, the emulsion was cooled to 35 ° C, washed with water by a conventional flocculation method, 60 g of gelatin was added and dissolved at 40 ° C.
PH 6.5 and pAg8.6 were adjusted. Sodium thiosulfate, potassium chloroaurate and potassium thiocyanate were added to this emulsion, and the emulsion was optimally chemically sensitized at 60 ° C. This tabular grain is 75%
Are occupied by hexagonal tabular grains, and the average equivalent circle diameter is 1.
3μm, coefficient of variation of equivalent circle diameter 17%, average thickness 0.18μ
m and monodisperse tabular grains having an average aspect ratio of 7.2.

With respect to Emulsion D, tabular silver halide grains EI having different average diameters, average thicknesses and average aspect ratios were prepared by changing pBr in the grain growth stage. The tabular silver halide emulsions EI were monodisperse tabular silver halide grains having a diameter variation coefficient of 15% to 20%.

Next, each layer having the following composition was coated on an undercoated 127 μm thick cellulose triacetate film support to prepare color reversal photographic light-sensitive materials, Samples 101 to 110. Numbers represent coating amount per m ^2. Fourth of samples 101 to 110
Layer, fifth layer, sixth layer, ninth layer, tenth layer, eleventh layer, fifteenth layer
The silver halide emulsions of the light-sensitive emulsion layers of the layer Nos. 16, 16 and 17 are as shown in Table 3.

First layer: Anti-halation layer Black colloidal silver 0.25 g Gelatin 1.9 g UV absorber U-1 0.04 g UV absorber U-2 0.1 g UV absorber U-3 0.1 g UV absorber U-4 0.1 g UV absorber U-6 0.1 g High-boiling organic solvent Oil-1 0.1 g Second layer: Intermediate layer Gelatin 0.40 g Compound Cad-D 10 mg Dye D-4 0.4 mg High-boiling organic solvent Oil-3 40 mg Third layer: Intermediate layer Fine-grained silver iodobromide emulsion with fogged inside (average particle size 0.06 μm, coefficient of variation 18%,
AgI content mol%) Silver amount 0.05 g Gelatin 0.4 g Fourth layer: low-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 Silver amount 0.4 g Gelatin 0.8 g Coupler C-1 0.15 g Coupler C-2 0.05 g Coupler C-9 0.05 g Compound Cad-D 10 mg High-boiling organic solvent Oil-2 0.10 g Fifth layer: Medium-sensitivity red-sensitive emulsion layer Sensitizing dyes S-1 and S- Silver iodobromide emulsion spectrally sensitized in 2 Silver amount 0.5 g Gelatin 0.8 g Coupler C-1 0.2 g Coupler C-2 0.05 g Coupler C-3 0.2 g High boiling organic solvent Oil-2 0.1 g Sixth layer: High-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1, S-2 and S-7 Silver amount 0.4 g Gelatin 1.1 g Coupler C-3 0.7 g Coupler C-1 0.3 g 7th layer: Intermediate layer Gelatin 0.6 g Color mixing inhibitor Cad-k 2.6 mg UV absorber U-1 0.1 g UV absorber U-6 0.1 g Dye D-1 0.02 g No. 8 Layer: Intermediate layer Surface and inside fogged silver iodobromide emulsion (average grain size
0.06 g Gelatin 1.0 g Color-mixing inhibitor Cad-J 0.1 g Color-mixing inhibitor Cad-A 0.1 g 9th layer: low-sensitivity green-sensitive emulsion layer Sensitizing dye S- Silver iodobromide emulsion spectrally sensitized with 3 and S-4 Silver amount 0.5 g Gelatin 0.5 g Coupler C-4 0.20 g Coupler C-7 0.10 g Coupler C-8 0.10 g Compound Cpd-B 0.03 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g Compound Cpd-H 0.02 g Compound Cpd-D 10 mg High boiling organic solvent Oil-1 0.1 g High boiling organic solvent Oil-2 0.1 g 10th layer: medium green Sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-8 and S-4 Silver amount 0.4 g Gelatin 0.6 g Coupler C-4 0.1 g Coupler C-7 0.1 g Coupler C-8 0.1 g Compound Cpd -B 0.03 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.05 g Compound Cpd-H 0.05 g High-boiling organic solvent Oil-2 0.01 g 11th layer : High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-8 Silver amount 0.5 g Gelatin 1.0 g Coupler C-4 0.4 g Coupler C-7 0.2 g Coupler C-8 0.2 g Compound Cpd-B 0.08 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g Compound Cpd-H 0.02 g High boiling organic solvent Oil-1 0.02 g High boiling organic solvent Oil-2 0.02 g 12th layer: Intermediate layer Gelatin 0.6 g Dye D-1 0.1 g Dye D-3 0.07 g Dye D-2 0.04 g Dye D-2 0.05 g 13th layer: Yellow filter layer Yellow colloidal silver Silver amount 0.1 g Gelatin 1.1 g Color mixing inhibitor Cpd-A 0.01 g High boiling organic solvent Oil-1 0.01 g 14th layer: intermediate layer Gelatin 0.6 g 15th layer: low-sensitivity blue-sensitive emulsion layer Sensitized with sensitizing dyes S-5 and S-6 Silver iodobromide emulsion Silver amount 0.1 g Gelatin 0.8 g Coupler C-5 0.6 g Sixteenth layer: Medium-sensitivity blue-sensitive emulsion layer With sensitizing dyes S-5 and S-6 Felt silver iodobromide emulsion Silver amount 0.4 g Gelatin 0.9 g Coupler C-5 0.3 g Coupler C-6 0.3 g 17th layer: high-sensitivity blue-sensitive emulsion layer Sensitized with sensitizing dyes S-5 and S-6 Silver iodobromide emulsion silver amount 0.4 g gelatin 1.2 g coupler C-6 0.7 g coupler C-6 0.3 g 18th layer: first protective layer gelatin 0.7 g UV absorber U-1 0.04 g UV absorber U- 2 0.01g UV absorber U-3 0.03g UV absorber U-4 0.03g UV absorber U-5 0.05g UV absorber U-6 0.05g High boiling organic solvent Oil-1 0.02g Formalin scavenger Cpd-C 0.2 g Cpd-I 0.4 g Dye D-3 0.05 g 19th layer: 2nd protective layer Colloidal silver Silver amount 0.1 g Fine grain silver iodobromide emulsion (average particle size 0.06 μm, AgI content 1)
Silver content 0.1 g gelatin 0.4 g 20th layer: third protective layer gelatin 0.4 g polymethyl methacrylate (average particle size 1.5 μm) 0.1 g copolymer of methyl methacrylate and acrylic acid (average particle size) 1.5 μm) 0.1 g Silicone oil 0.03 g Surfactant W-1 3.0 mg Surfactant W-2 0.03 mg Additive F-1 was added to each silver halide emulsion layer and intermediate layer.
~ F-8 was added.

In each layer, a gelatin hardener H-
Surfactant No. 1 and surfactants W-3 and W-4 for coating, and surfactant W-5 for emulsification were added.

Further, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, and phenethyl alcohol were added as preservatives and fungicides.

Oil-1 Dibutyl phthalate Oil-2 Tricresyl phosphate For each of the samples 101 to 110, the following processing was performed on a sample exposed to a wedge with a light source at 4800 ° K, a sample exposed through a pattern for MTF measurement, and a sample exposed through a pattern for RMS value measurement.

[Processing step] Processing step Time Temperature Tank capacity Replenishment amount Black and white development 6 minutes 38 ° C 12 2.2 / m ² First water washing 2 minutes 38 ° C 4 7.5 / m ² Inversion 2 minutes 38 ° C 4 1.1 / m ² Color development 6 minutes 38 ° C 12 2.2 / m ² Adjustment 2 minutes 38 ° C 4 1.1 / m ² Bleaching 6 minutes 38 ° C 12 0.22 / m ² Fixed 4 minutes 38 ° C 8 1.1 / m ² Second rinsing 4 minutes 38 ° C 8 7.5 / m ² Stability 1 minute 25 ° C. 2 1.1 / m ² The composition of each treatment solution was as follows.

pH was adjusted with hydrochloric acid or potassium hydroxide.

pH was adjusted with hydrochloric acid or sodium hydroxide.

pH was adjusted with hydrochloric acid or potassium hydroxide.

pH was adjusted with hydrochloric acid or sodium hydroxide.

pH was adjusted with hydrochloric acid or sodium hydroxide.

The pH was adjusted with hydrochloric acid or aqueous ammonia.

After processing, these samples were subjected to normal sensitometry for wedge-exposed samples,
The samples exposed for RMS and RMS measurements were measured with a microdensitometer to determine the MTF value and RMS value and to compare the granularity. The results are shown in Table 4.

<Effects of the Invention> According to Table 4, the samples 106 to 110 of the present invention are comparative samples 101 to 1
It can be seen that both sharpness and granularity are superior to 05.

In particular, in the comparison of Samples 106 and 104 and the comparison of Samples 107 and 105, it is preferable to use tabular silver halide grains having a large thickness for the green-sensitive silver halide emulsion layer and / or the red-sensitive silver halide emulsion layer. Gives good results.

Claims (2)

(57) [Claims] 1. A halogenated silver halide emulsion comprising at least a red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer on a support, wherein the blue-sensitive silver halide emulsion layer is located farthest from the support. In a silver color photographic light-sensitive material, it is contained in at least one of a red-sensitive silver halide emulsion layer or a green-sensitive silver halide emulsion layer and at least one of a blue-sensitive silver halide emulsion layer. 70% or more of the total projected area of the silver halide emulsion to be used has a thickness of 0.5 μm or less, a diameter of 0.5 μm or more, an aspect ratio of 3 or more, and a maximum length with respect to the length of the side having the minimum length. Having a hexagonal shape in which the ratio of the lengths of the sides having a height of 2 or less and occupied by tabular silver halide having two parallel surfaces as outer surfaces, and further comprising the hexagonal tabular halide. Silver Among the tabular silver halide grains contained in the at least two silver halide emulsion layers having a monodispersity having a coefficient of variation of the particle size distribution of the particles of not more than 20%, and a red-sensitive silver halide emulsion. Layer or the average thickness of tabular silver halide grains contained in the green-sensitive silver halide emulsion layer is larger than the average thickness of tabular silver halide grains contained in the blue-sensitive silver halide emulsion layer. A silver halide color photographic light-sensitive material comprising: 2. The method according to claim 1, wherein the average thickness of the tabular silver halide emulsion contained in at least one of the green color-sensitive layers is 0.2 μm or more and the average aspect ratio is 8 or less. The silver halide color photographic light-sensitive material according to 1).