JPH0614178B2 - Silver halide color reversal light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide color reversal light-sensitive material, more specifically, a light-sensitive material having excellent image sharpness and graininess and being stored. The present invention relates to a silver halide color reversal light-sensitive material having a small photographic variation.

(Prior Art) U.S. Pat. No. 4,439,520 discloses that at least one of a green-sensitive emulsion layer and a red-sensitive emulsion layer has a thickness of less than 0.3 micron, a diameter of at least 0.6 micron, and a diameter / thickness of at least 0.6 micron. A color photographic light-sensitive material is disclosed which has improved sharpness, sensitivity and graininess by using tabular silver halide emulsion grains having a ratio of 8: 1 or more.

The method of using such tabular silver halide grains in a color photographic light-sensitive material is excellent in improving sharpness, sensitivity and graininess. Using was not always a satisfactory method.

Normally, the processing of a color reversal light-sensitive material is performed in the steps of black and white development (first development) → washing → reversal → color development → adjustment → bleaching → fixing → washing → stabilization → drying. First of this process
The developing solution contains a silver halide solvent such as KSCN in order to impart a development accelerating action by dissolution physical development. Therefore, in the first development processing step, dissolution of unexposed grains proceeds simultaneously with development of exposed silver halide grains, and dissolution physical development occurs with developed silver or colloidal silver in the yellow filter layer as nuclei. become.

The silver halide grains remaining without being dissolved in the first development are
It is fogged in the reversal bath and contributes to color development.
Therefore, when the solubility of silver halide grains is high,
The contribution to color development is reduced, and the color density is lowered in some cases. Further, the size of silver halide grains usually has a certain distribution, but when the solubility of silver halide grains is high, grains of relatively small size disappear due to dissolution. Therefore, in this case, only large-sized particles contribute to color development, and the graininess is deteriorated.

Since the tabular silver halide emulsion grains are tabular in shape, they have the property of higher solubility than spherical silver halide grains. Therefore, the use of tabular silver halide grains in a color reversal light-sensitive material has been extremely inconvenient for practical use due to the above reasons.

The inventors of the present invention previously invented a technique for providing a color reversal light-sensitive material having improved sharpness without deteriorating graininess by using tabular silver halide emulsion grains and a specific compound. Wish sho 59-195408).

Although sharpness was greatly improved by the present invention, research for minimizing photographic variation (especially, decrease in maximum density) of the light-sensitive material during storage was insufficient.

Although it is impossible to completely eliminate the variation in photographic performance over time, it is desirable to make it as small as possible, and many studies have been conducted for that purpose.

As a method for preventing the fluctuation of photographic performance, especially the occurrence of fog, which occurs during storage with time or during development processing, for example
-Phenyl-5-mercaptotetrazoles (Belgian Patent 671,402, U.S. Patent 3,295,97)
No. 6, No. 3,376,310, No. 3,615,6
16, No. 3,071,465, No. 3,420,
No. 664, No. 2,403,927, JP-A-50-3.
7436); benzotriazoles (British Patent Nos. 919,061, 768,438, U.S. Pat. Nos. 3,157,509, 3,082,088, and German Patent No. 617,712). Etc.); Benzimidazoles (US Pat. Nos. 3,137,578 and 3,14)
8,066, 3,511,663, British Patents 271,475, 1,344,548, 3,148,066, 3,511,663, United Kingdom Patent Nos. 271,475 and 1,344,548
, German Patents 708,424 and 635,76
No. 9, No. 2,205,539); and indazoles (U.S. Pat. Nos. 3,106,467, 3,420,670, 1,763,990, and 2,). No. 271,229) etc. are known to be added to a light-sensitive material or a processing solution. However, these compounds have drawbacks such that they are not sufficiently effective in suppressing the decrease in the maximum density of the color reversal light-sensitive material due to the occurrence of fog during storage with time, or lead to a decrease in sensitivity.

(Object of the Invention) Accordingly, an object of the present invention is to use tabular silver halide emulsion grains to contain a compound which has improved sharpness and can reduce fluctuation in photographic properties during storage without causing sensitivity deterioration. To provide a color reversal light-sensitive material.

(Structure of the Invention) An object of the present invention is to provide a silver halide color reversal light-sensitive material having at least one red-sensitive, green-sensitive, and blue-sensitive emulsion layer. An emulsion containing tabular silver halide grains having a silver iodide content of 5 times or more and having a silver iodide content of 5 mol% or less, and (2) a compound having a repeating unit represented by the following general formula (I), and general A silver halide color containing at least one compound represented by the formula (II), wherein the grains represent at least 50% of the total projected area of silver halide grains present in the same layer. Achieved with a reversal photographic material.

Hereinafter, the present invention will be described in detail.

General formula (I) Here, R ₁ is -OR, -SR, And R and R ′ each represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group, a sulfoalkyl (or salt thereof) group, a carboxyalkyl (or salt thereof) group, an aralkyl group, or a sulfo group. (Or a salt thereof)-, a carboxyl (or a salt thereof)-, an alkyl having 1 to 4 carbons, and an alkoxy having 1 to 4 carbons.
Or, represents an aryl group having a carbon number of 6 to 12 with or without a halogen-substituent, or a cycloalkyl group, or R and R ′ together form an alkylene ring or an alkylene ring containing —O—. Alternatively, R ₂ , R ₃ , R ₄ and R ₅ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Y ₁ , Y ₂ , Y ₃ and Y ₄ each have a carbon number. 2-12
Or a polymethylene group having 2 to 12 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, sulfo (or a salt thereof)-, carboxyl (or a salt thereof)-, an alkyl group having 1 to 4 carbon atoms, or halogen - if having substituents or having no arylene group or represents a cycloalkylene group,, Z is -O -, - SO ₂ - or -CH ₂ - represents, and m represents 0 or 1.

Next, typical compounds having a repeating unit of the general formula (I) used in the present invention are shown, but the compounds used in the present invention are not limited thereto.

(I-1) (I-2) (I-3) (I-4) (I-5) (I-6) (I-7) (I-8) (I-9) (I-10) (I-11) (I-12) (I-13) (I-14) (I-15) (I-16) (I-17) (I-18) (I-19) (I-20) (I-21) (I-22) (I-23) (I-24) (I-25) (I-26) (I-27) (I-28) (I-29) (I-30) (I-31) General formula (II) In the formula, M represents a hydrogen atom, a cation or a protecting group for a mercapto group which is cleaved by an alkali, and Z represents an atomic group necessary for forming a 5-membered or 6-membered heterocycle. This heterocycle may have a substituent or may be condensed. R ₁₁ and R ₁₂ represent a hydrogen atom, an unsubstituted or substituted aliphatic group or an unsubstituted or substituted aromatic group, and R ₁₁ and R ₁₂ may be the same or different, and They may combine to form a ring. More specifically, M is a hydrogen atom, a cation (eg, sodium ion, potassium ion, ammonium ion, etc.) or an alkali-cleavable mercapto group protecting group (eg, —COR ″, —COOR ″, —CH ₂ CH ₂ CO _2).
R ″, —CH ₂ CH ₂ CN, etc., provided that R ″ is a hydrogen atom,
Represents an alkyl group, aralkyl group, aryl group, etc.)
Represents

Z represents an atomic group necessary for forming a 5-membered to 6-membered heterocycle. This heterocycle may be fused,
Further, it may have a substituent on the heterocycle or the condensed ring.

Examples of Z include tetrazole, triazole, imidazole, benzimidazole, and the like.

Particularly preferred as Z is tetrazole.

The aliphatic group of R ¹ and R ² is preferably an alkyl group or an alkenyl group having up to 18 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a t-butyl group, an n-group.
-Pentyl group, n-hexyl group, cyclohexyl group, n
-Octyl group, n-dodecyl group, n-octadecyl group,
There are allyl groups.

The aromatic group of R ₁₁ and R ₁₂ is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

The ring formed by R ₁₁ and R ₁₂ is a ring having 2 to 10 carbon atoms and may contain O, N or S in the ring member. For example _{-CH 2 CH 2 OCH 2 CH 2} -, and so on.

Substituents for R ₁₁ and R ₁₂ include an alkoxy group (eg, methoxy group, ethoxy group) halogen (eg, chloro, bromo, etc.), alkyl group (eg, methyl group, ethyl group, etc.) phenyl group, alkoxycarbonyl group (eg, ethoxy group). Carbonyl group), acyl group (eg acetyl group),
Examples thereof include an acyloxy group (eg acetyloxy group), a cyano group, a nitro group, an alkylthio group (eg methylthio group), an amide group (eg acetamide group) and a sulfonamide group (eg methanesulfonamide group).

Particularly preferred R ₁₁ and R ₁₂ are an alkyl group having 1 to 6 carbon atoms and a phenyl group, more preferably a methyl group,
An ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group.

Specific examples of the compound of the general formula (II) used in the present invention are shown below, but the invention is not limited thereto.

(II-1) (II-2) (II-3) (II-4) (II-5) (II-6) (II-7) (II-8) (II-9) (II-10) (II-11) (II-12) (II-13) (II-14) (II-15) (II-16) (II-17) (II-18) (II-19) (II-20) (II-21) (II-22) (II-23) (II-24) (II-25) (II-26) (II-27) (II-28) (II-29) (II-30) (II-31) (II-32) (II-33) (II-34) (II-35) The compound having a repeating unit represented by the general formula (I) of the present invention is a known compound, and is disclosed in JP-B-46-15471.
It can be easily synthesized by the method described in the publication.

The compound represented by the general formula (II) of the present invention can be easily synthesized by the method described in JP-A-58-95728.

The addition amount of the compound having the repeating unit of the general formula (I) is
There is no particular limitation, but when used in the silver halide emulsion layer, 0.01 to 50 g / mol Ag is preferable, and when used in the protective layer or the intermediate layer, 0.05 to 250 g / kg gelatin is preferable.

The amount of the compound of general formula (II) added is not particularly limited,
When used in a silver halide emulsion layer, 10 ^-6 to 10 ^-2 mol / mol Ag, and when used in a protective layer or an intermediate layer, 1
Gelatin of 0 ^-5 to 10 ^-1 mol / kg is preferred.

The compound represented by formula (I) or (II) of the present invention is preferably used in the same layer as the tabular silver halide emulsion of the present invention, and may be used alone or in combination. Good.

A compound having a repeating unit of the general formula (I),
The compound represented by I) can be incorporated in the photographic emulsion by a conventional method. Usually, it is dissolved in a solvent such as methanol, ethanol, water, or a ketone soluble in water and added to the emulsion. The time of addition may be any stage in the emulsion production process, but it is generally preferable that the chemical ripening is completed.

Next, the tabular silver halide grains used in the present invention will be described.

The tabular silver halide grains used in the present invention have a diameter / thickness ratio of 5 times or more.

Here, the diameter of a silver halide grain means the diameter of a circle having an area equal to the projected area of the grain. In the present invention, the tabular silver halide grains have a diameter of 0.4 to 5.0 µ, preferably 0.6 to 4.0 µ.

In general, tabular silver halide grains are tabular having two parallel planes, and therefore "thickness" in the present invention means a distance between two parallel planes constituting the tabular silver halide grain. Represented.

The halogen composition of the tabular silver halide grains may be any of silver bromide, silver iodide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, and silver chloride. And silver iodobromide, and particularly preferably silver iodobromide having a silver iodide content of 0 to 30 mol%.

The tabular silver halide grain of the present invention has a silver iodide content on the grain surface of 5 mol% or less, more preferably 3 mol% or less. The silver iodide content on the surface of the grain is XPS (Xray
Photoelectron Spectroscopy
It can be measured by the opay method. For the XPS analysis method, see M.K. Gardner & M.A. Photo by Lay
-Emission in Solids (I) Spr
It was described in detail in inger-Verlag 1978.

Next, a method for producing tabular silver halide grains will be described.

Tabular grains are described by Katoff, Photographic Science and Engineering (Gutoff, Pho
toographic Science and Eng
ineering), Vol. 14, pp. 248-257 (1
970); U.S. Pat. Nos. 4,434,226, 4,
No. 414, 310, No. 4,433, 048, No. 4, 4
It can be easily prepared by the method described in 39,520 and British Patent 2,112,157.
When the tabular grains are used, there are advantages such as an increase in covering power and an increase in color sensitizing efficiency by the sensitizing dye, which are described in detail in the above-cited US Pat. No. 4,434,226. .

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. These emulsion grains are described in British Patent 1,027,1
46, U.S. Pat. Nos. 3,505,068 and 4,44
No. 4,877 and Japanese Patent Application No. 58-248469. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver halide such as silver rhodanide and lead oxide. These emulsion grains are described in U.S. Pat. Nos. 4,094,684, 4,142,900,
No. 4,459,353, British Patent No. 2,038,79.
No. 2, U.S. Pat. Nos. 4,349,622 and 4,39.
5,478, 4,433,501, 4,46
No. 3,087, No. 3,656,962, No. 3,85
2,067, JP-A-59-162540 and the like.

The tabular silver halide grain of the present invention can be chemically sensitized if necessary.

As the chemical sensitization method, a gold sensitization method using a so-called gold compound (for example, US Pat. Nos. 2,448,060 and 3,32) is used.
No. 0,069) or a sensitization method using a metal such as iridium, platinum, rhodium or palladium (for example, US Pat. No. 2,4,4).
48,060, 2,566,245, 2,56
No. 6,263) or a sulfur sensitizing method using a sulfur-containing compound (for example, US Pat. No. 2,222,264), or a reduction sensitizing method with tin salts, polyamines and the like (for example, US Pat. No. 2,487,850). No. 2,518,698, No. 2,521,925), or a combination of two or more thereof.

From the viewpoint of sensitization, the tabular silver halide grain of the present invention is preferably gold-sensitized or sulfur-sensitized, or a combination thereof.

In the layer containing the tabular silver halide grains of the present invention,
It is necessary that tabular grains having a diameter / thickness ratio of 5 or more are contained in 50% or more of the total projected area of silver halide grains present in the layer, and tabular grains having a diameter / thickness ratio of 5 to 30. It is preferred that the lamellar grains account for 50% or more of the total projected area of the silver halide grains present in the layer.

The thickness of the layer containing tabular silver halide grains is 0.3-
It is preferably 6.0 μ, and particularly preferably 0.5 to 4.0 μ.

The coating amount of tabular silver halide grains is 0.1 to 6 g /
It is preferably m ² , particularly 0.3 to 3 g / m ² .

The silver halide color reversal light-sensitive material of the present invention has at least one red-sensitive, green-sensitive, and blue-sensitive emulsion layer, but the order of these light-sensitive layers is not particularly limited and may be depending on the purpose. Determined.

Further, as described later, a dye-forming coupler is used in the silver halide color reversal light-sensitive material of the present invention. Usually, a cyan dye-forming coupler is used in the red-sensitive layer and a magenta dye-forming coupler is used in the green-sensitive layer. Although a yellow dye-forming coupler is used in the blue-sensitive layer, different combinations may be used depending on the purpose.

The tabular silver halide emulsion used in the present invention may be used in any of the above red-sensitive, green-sensitive and blue-sensitive layers.
When these color-sensitive layers are composed of two or more photosensitive layers, they may be used in any of the layers, but particularly preferably, they are used in the layer farthest from the support. Also,
It is preferable that the layer has the highest sensitivity among the same color-sensitive layers.

The effect of the present invention is maximized when a tabular silver halide emulsion is added to a blue-sensitive layer (especially when it is composed of two or more layers, the layer on the side farther from the support). , When it is at the farthest position with respect to the support than the other color-sensitive layers.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, in addition to tabular silver halide grains, any of ordinary silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride can be used. You may use the silver halide of. However, the silver halide emulsion used in the present invention is a negative type. A preferred silver halide is silver iodobromide or silver iodochlorobromide containing about 30 mol% or less of silver iodide. Particularly preferred is about 10 mol%
It is a silver iodobromide containing up to silver iodide.

The silver halide grains in the photographic emulsion may be so-called regular grains having regular crystal bodies such as cubes, octahedra and tetradecahedrons, and those having an irregular crystal shape such as spheres, It may have a crystal defect such as a twin plane or a composite form thereof. Also, a mixture of particles having various crystal forms may be used.

The grain size of the silver halide may be fine grains of about 0.1 micron or less, or large grains with a projected area diameter of up to about 10 microns, a monodisperse emulsion having a narrow distribution, or a polydisperse grain having a wide distribution. It may be an emulsion.

The silver halide photographic emulsion which can be used in the present invention can be produced by a known method, for example, Research Disclosure,
Volume 176, No.17643 (December 1978), 22
Pp. 23, "I. Emulsion Pre
partition and Types) ”and the same,
Volume 187, No.18716 (November 1979), 64
The method described on page 8 can be followed.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Graphide, published by Paul Montel (P. Glafki).
des, Chimie et Physique Ph
otographique paul Montel,
1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photogra.
phic Emulsion Chemistry (F
Ocal Press, / 966), "Production and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (VL Zelikman et al, Makin).
g and Coating Photographi
c Emulsion, Focal Press, 19
64) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method or a combination thereof. Good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Known silver halide solvents (for example, ammonia, rhodancal or U.S. Pat. No. 3,271,157, JP-A-51-12360, JP-A-53-82408, JP-A-53-144319, JP-A-53-144319, JP-A-53-144319, SHO 54-100717
Physical aging in the presence of thioethers and thione compounds described in JP-A No. 54-155828. Also by this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size distribution can be obtained.

The silver halide emulsion composed of the regular grains can be obtained by controlling the pAg and pH during grain formation.
For details, see, for example, Photographic Science and Engineering (Photographic S
science and Engineering) No. 6
Volume 159-165 (1962); Journal of Photographic Science (Journal o
f Photographic Science), 1
Volume 2, Pages 242-251 (1964), U.S. Pat. No. 3,
655,394 and British Patent 1,413,748.
No.

The monodisperse emulsion comprises silver halide grains having an average grain diameter of greater than about 0.1 micron, at least 9
Emulsions such that 5% by weight are within ± 40% of the average grain diameter are typical. The average grain diameter is 0.25 to 2 microns and at least 95% by weight or (number of grains) at least 95% of the silver halide grains have an average grain diameter of ± 2.
Emulsions such as within 0% can be used in the present invention.
A method for producing such an emulsion is described in US Pat. No. 3,574,6.
28, 3,655,394 and British Patent 1,413,748. In addition, JP-A-4
8-8600, 51-39027, 51-83
097, 53-137133, and 54-4852.
1, No. 54-99419, No. 58-37635,
Monodisperse emulsions such as those described in JP-A-58-49938 can also be preferably used in the present invention. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof,
A rhodium salt or a complex salt thereof, an iron salt, an iron complex salt, or the like may coexist.

These various emulsions may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which is formed inside the grain, or a type which forms a latent image both on the surface and inside.

The surface-fogged silver halide grains described in U.S. Pat. No. 4,082,553, or U.S. Pat. Nos. 2,996,382 and 3,178,282.
The silver halide grains having a fog nucleus inside can be used in the present invention described in JP-A-59-214852.

In order to remove the soluble silver salt from the emulsion before and after physical ripening, Nudel water washing, flocculation sedimentation method or ultrafiltration method is used.

The emulsion used in the present invention is usually one that has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process include Research Disclosure No. 17643 (December 1978) and No. 1 mentioned above.
8716 (November 1979), and the relevant parts are summarized in the table below.

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

Various color couplers can be used in the present invention, specific examples of which are mentioned above in Research Disclosure.
No. 17643, VII-C to G. As the dye-forming coupler, a coupler that gives the three primary colors (that is, yellow, magenta, and cyan) of the subtractive color method by color development is important, and specific examples of the diffusion-resistant hydrophobic 4-equivalent or 2-equivalent coupler are described above. Research Disclosure No.17643, VII-C
In addition to the couplers described in the patents described in paragraphs D and D, the following can be preferably used in the present invention.

A typical example of the yellow coupler that can be used in the present invention is a hydrophobic acylacetamide coupler having a ballast group. A specific example is US Pat. No. 2,
No. 407,210, No. 2,875,057 and No. 3,265,506. In the present invention, it is preferable to use a two-equivalent yellow coupler, and US Pat. Nos. 3,408,194 and 3,447,928 are preferred.
No. 3,933,501 and No. 4,022.
No. 620 and other yellow couplers of oxygen atom elimination type or Japanese Patent Publication No. 58-10739, U.S. Pat. Nos. 4,401,752, 4,326,024, R
D18053 (April 1979), British Patent No. 1,42
No. 5,020, West German Application Publication No. 2,219,917,
Typical examples thereof include nitrogen atom releasing yellow couplers described in Nos. 2,261,361, 2,329,587 and 2,433,812. The α-pivaloyl acetanilide type coupler is excellent in the fastness of the color forming dye, especially the light fastness, while
The benzoylacetanilide coupler provides high color density.

Examples of magenta couplers that can be used in the present invention include hydrophobic indazolone or cyanoacetyl, preferably 5-pyrazolone and pyrazoloazole couplers having a ballast group. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and a typical example thereof is US Pat.
311,082, 2,343,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896 and No. 3,936,015.
As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897 is particularly preferable. European Patent No. 7
The 5-pyrazolone-based coupler having a ballast group described in JP-A No. 3,636 provides high color density. As a pyrazoloazole coupler, US Pat. No. 3,061,43
2 pyrazolobenzimidazoles, preferably pyrazolo [5,1-c] [1,2,4] triazoles described in US Pat. No. 3,725,067, Research Disclosure No. 24220 ( 1984 6
And the disclosure of pyrazolotetrazole and research disclosure described in JP-A-60-33552.
No. 24230 (June 1984) and JP-A-60-
The pyrazolopyrazoles described in 43659 are mentioned. The imidazo [1,2-b] pyrazoles described in U.S. Pat. No. 4,500,630 are preferable in view of low yellow sub-absorption of a coloring dye and light fastness, and described in European Patent 119,860A. Pyrazolo [1,5-b]
[1,2,4] triazole is particularly preferred.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant naphthol-based and phenol-based couplers. The naphthol-based couplers described in U.S. Pat. No. 2,474,293, preferably U.S. Pat. 052
No. 212, No. 4,146, 396, No. 4,22
Typical examples are the oxygen atom desorption type two-equivalent naphthol couplers described in JP-A-8,233 and JP-A-4,296,200. Further, specific examples of the phenol-based coupler are described in US Pat. Nos. 2,369,929 and 2,8.
01,171, 2,772,162, 2,
No. 895,826.

A cyan coupler which is fast against humidity and temperature is preferably used in the present invention, and typical examples thereof include an alkyl group having an ethyl group or more at the meta position of the phenol nucleus described in US Pat. No. 3,772,002. A phenolic cyan coupler having U.S. Pat. No. 2,772,162,
No. 3,758,308, No. 4,126,396
No. 4,334,011, No. 4,327,17
3, 2,5-diacylamino-substituted phenol-based couplers described in West German Patent Publication No. 3,329,729 and European Patent 121,365, and US Pat. Nos. 3,446,622 and 4 , 333, 999, 4,451, 559 and 4,427, 767.
JP-A No. 1994-237, which has a phenylureido group at the 2-position and an acylamino group at the 5-position.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such couplers are
Examples of magenta couplers are described in U.S. Pat. No. 2,125,570, and examples of yellow, magenta or cyan couplers are described in European Patent No. 96,570 and West German Patent Publication No. 3,234,533. ing.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are found in US Pat. No. 3,451,82.
0 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and US Patent No. 4,367,
282.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. As the DIR coupler releasing a development inhibitor, the couplers of the patents described in the above-mentioned Research Disclosure No. 17643, VII to F are useful.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods, for example, a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, more preferably an oil-in-water dispersion method, etc. are typical examples. be able to. In the oil-in-water dispersion method, after dissolving in either a single liquid of a high boiling organic solvent having a boiling point of 175 ° C. or higher and a so-called auxiliary solvent having a low boiling point or a mixed liquid of both, water or gelatin is added in the presence of a surfactant. Finely dispersed in an aqueous medium such as an aqueous solution. Examples of high boiling organic solvents are US Pat. No. 2,32
2, 027 and the like. The dispersion method may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, washing with noodles or ultrafiltration, and then used for coating.

The steps of latex dispersion method, effects, and specific examples of latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230. It is described in.

The light-sensitive material produced by using the present invention, as a color fog-preventing agent or color-mixing preventing agent, a hydroloquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler, a sulfone. It may contain an amidophenol derivative or the like.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Hydroquinones as organic anti-fading agents,
6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols,
Typical are hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl groups of these compounds. Take as an example. Further, a metal complex represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

The light-sensitive material according to the present invention, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, antihalation layer,
It is preferable to appropriately provide an auxiliary layer such as a back layer.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as a plastic film, paper or cloth usually used for a photographic light-sensitive material or a rigid support such as glass, pottery or metal. To be done. Useful as flexible supports are cellulose derivatives (cellulose nitrate,
Films made of cellulose acetate, cellulose acetate butyrate, etc.), synthetic polymers (polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc.), baryta layers or α-olefin polymers (eg polyethylene, polypropylene, ethylene / butene copolymers), etc. It is a paper or the like coated or laminated with. The support may be colored with a dye or pigment. It may be black for the purpose of shading. The surface of these supports is generally
It is subjected to a subbing treatment to improve the adhesion with the photographic emulsion layer and the like. The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment or the like before or after the undercoat treatment.

For coating the photographic emulsion layer and the hydrophilic colloid layer thereafter, for example, dip coating method, roller coating method, curtain coating method,
Various known coating methods such as extrusion coating method can be used. US Pat. No. 2,681,294 as required
No. 2761791, No. 3526528, No. 3508947, and the like, the multilayers may be simultaneously coated by the coating method.

For the processing of the color reversal light-sensitive material of the present invention, as described above, black and white development (first development) → stop → washing → reversal → washing → color development → stop → washing → adjusting bath → washing → bleaching → Washing with water → Fixing →
The steps of washing with water, stabilizing, and drying are used. In this step, a pre-bath, a pre-hardening bath, a neutralizing bath and the like may be further provided. Also, stop, flip,
Washing with water after color development, conditioning bath or bleaching may be omitted. The reversal may be carried out in a fogging bath or re-exposure. It can also be omitted by adding a fogging agent to the color developing bath. Furthermore, the conditioning bath can be omitted.

Known developing agents can be used in the first developing solution used in the present invention. Examples of developing agents include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p-).
Aminophenol), 1-phenyl-3-pyrazolines, ascorbic acid, and U.S. Pat. No. 4,067,872.
A heterocyclic compound such as 1,2,3,4-tetrahydroquinoline ring and an indole ring described in No.
They can be used alone or in combination.

In the black and white developer used in the present invention, other preservatives (eg, sulfite, bisulfite, etc.), buffers (eg, carbonate, boric acid, borate, alkanolamine), alkaline agents (eg, Hydroxides, carbonates,), solubilizers (eg polyethylene glycols, their esters), pH adjusters (eg organic acids such as acetic acid), sensitizers (eg quaternary ammonium salts), A development accelerator, a surfactant, a toning agent, a defoaming agent, a film hardening agent, a viscosity imparting agent and the like can be contained.

The first developing solution used in the present invention needs to contain a compound which acts as a silver halide solvent, and the sulfite salt added as the preservative usually plays the role. Specific examples of the sulfite and other silver halide solvents that can be used include KSCN, NaSCN, K ₂ SO ₃ and Na.
₂ SO ₃ , K ₂ S ₂ O ₅ , Na ₂ S ₂ O ₅ , K ₂ S ₂ O ₃ , Na ₂ S
₂ O _{3 and the} like can be mentioned.

Further, a development accelerator is used for imparting a development accelerating action. Particularly, a compound represented by the following general formula (VII) described in JP-A-57-63580 is used alone or in combination of two or more kinds. May be used in combination with the above silver halide solvent.

General formula (VII) If the amount of these silver halide solvents used is too small, the progress of development is slowed, and if the amount is too large, fogging occurs in the silver halide emulsion, and therefore, there is a preferable amount used by itself. Can be easily done by those skilled in the art.

For example, SCN ⁻ is 0.005 to 0.0 per developer.
It is preferably 2 mol, particularly 0.01 to 0.015 mol, and SO ₃ ²⁻ is 0.05 to 1 mol, particularly 0.1 to 3.
It is preferably 0.5 mol.

When the compound of the general formula [VII] is used by adding it to the black and white developer of the present invention, the addition amount is preferably 5 × 10 ⁻⁶ mol to 5 × 10 ⁻¹ mol, and more preferably ¹ × 10 ⁻⁶ mol. 1
It is from x10 ^-4 mol to 2 x 10 ^-1 mol.

The pH value of the developer thus adjusted is selected to an extent sufficient to give the desired density and contrast, but is preferably in the range of about 8.5 to about 11.5.

To perform a sensitization process using such a first developing solution,
The time may be extended up to about 3 times the standard processing.
At this time, if the processing temperature is raised, the extension time for the sensitization processing can be shortened.

The fogging bath used in the present invention may contain a known fogging agent. That is, stannous ion-organic phosphoric acid vinegar (US Pat. No. 3,617,282), stannous ion organic phosphonocarboxylic acid vinegar (Japanese Patent Publication No. 56-56).
-32616), stannous ion-aminopolycarboxylic acid complex salts (British Patent No. 1,209,050) and other stannous ion borohydride compounds (US Pat. No. 2,984,567). ), A boron compound such as a heterocyclic amine borane compound (British Patent No. 1,011,000), and the like. The fogging bath (inversion bath) has a wide pH range from the acidic side to the alkaline side and has a pH of 2 to 12, preferably 2.5 to 1.
The range is 0, particularly preferably 3 to 9.

The color developer used in the present invention has a composition of a general color developer containing an aromatic primary amine developing agent. Preferred examples of aromatic primary amine color developing agents are the following p-phenylenediamine derivatives. N, N-diethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, 2-amino-5- (N-ethyl-
N-laurylamino) toluene, 4- [N-ethyl-N
-(Β-Hydroxyethyl) amino] aniline, 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline, N-ethyl-N- (β-methanesulfoamidoethyl) -3 -Methyl-4-aminoaniline, N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide, N, N-dimethyl-p-
Phenylenediamine, 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline and 4-amino-3-methyl-N-ethyl-described in U.S. Pat. Nos. 3,656,950 and 3,698,525. N-β-ethoxyethylaniline and 4-amino-3-methyl-
N-ethyl-N-β-butoxyethylaniline and salts thereof (for example, sulfate, hydrochloride, sulfite, p-toluenesulfonate, etc.) are preferred representative examples.

The color developer may contain other known developer component compounds. For example, caustic soda, caustic potash, sodium carbonate, potash carbonate, and the like can be used as the alkaline agent and the buffer.
Tertiary sodium phosphate or potassium, potassium metaphoric acid, borax, etc. may be used alone or in combination.

A sulfite salt (for example, sodium sulfite, potassium sulfite, potassium bisulfite, sodium bisulfite) or hydroxylamine which is usually used as a preservative can be added to the color developer.

If necessary, an optional development accelerator may be added to the color developing solution. For example, various pyridinium compounds represented by U.S. Pat. No. 2,648,604, Japanese Patent Publication No. 44-9503, U.S. Pat. No. 3,671,247 and other cationic compounds, cationic dyes such as phenosafranine, thallium nitrate and potassium nitrate. Such neutral salts, JP-B-44-9504, US Pat. No. 2,533,990, US Pat. No. 2531832, US Pat.
No. 970, No. 2577127, polyethylene glycol and its derivatives, nonionic compounds such as polythioethers, organic solvents, organic amines, ethanolamines described in JP-B-44-9509 and Belgian Patent 682862. Ethylenediamine, diethanolamine, etc. F. A. Photographic processing C by Mason
chemistry P40-43 (Focal Pre
The promoters described in ss-London-1966) can be used.

Further, the color developer may contain an aminopolycarboxylic acid represented by ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid as a water softener. .

Competing couplers and compensating developers can also be added to the color developer.

Citrazinic acid, J acid, H acid and the like are useful as competitive couplers.

As the compensating developer, p-aminophenol, N-benzyl-p-aminophenol, 1-phenyl-3-pyrazolidone, etc. can be used.

The pH of the color developing solution is preferably in the range of about 8-13. The temperature of the color developing solution is selected in the range of 20 ° C to 70 ° C, preferably 30 ° C to 60 ° C.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process, or may be performed individually. As the bleaching agent, compounds of polyvalent metals such as iron (III), cobalt (IV), chromium (VI) and copper (II), peracids, quinones and nitrone compounds are used. For example, ferricyanide, dichromate, iron (II
Organic complex salts of I) or cobalt (III), for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or complex salts of organic acids such as citric acid, tartaric acid, malic acid Persulfates, permanganates, nitrosophenols and the like can be used. Of these, potassium ferricyanide, sodium iron (III) diamine tetradiamine tetraacetate and ammonium iron (III) triamine diamine tetraacetate are particularly useful. Aminopolycarboxylic acid iron (III)
The complex salts are useful in either a stand-alone bleaching solution or a one-bath bleach-fixing solution.

As the bleaching or bleach-fixing solution, U.S. Pat. Nos. 3,042,520 and 3,241,966, JP-B-45-85.
In addition to the bleaching accelerators described in JP-B No. 06, JP-B-45-8836, etc., various additives can be added.

In the fixing bath of the present invention, as a fixing agent, ammonium salts, sodium salts and potassium salts of thiosulfate are 30 g /
It is used in an amount of up to about 200 g / s. In addition, stabilizers such as sulfites and isomeric bisulfites, hardeners such as potassium alum, acetates, borates, phosphates, carbonates, etc.
A pH buffer or the like can be included. The pH of the fixer is 3-10
And more preferably 5 to 9.

Other constitutions of the layer containing the tabular silver halide grains of the present invention, for example, binder, curing agent, antifoggant, silver halide stabilizer, surfactant, spectral sensitizing dye, dye, ultraviolet absorber There is no particular limitation on the chemical sensitizer, etc., for example, Research Disclosure.
e 176, pages 22 to 28 (December 1978) can be referred to.

(Example) Next, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.

Example-1 A tabular silver halide emulsion was prepared by the following method.

Add 30 g of gelatin and 10.3 g of potassium bromide to water 1 and in a container (pAg 9.1, pH 6.0) kept at 60 ° C., stir the solution I and II of Table 1 over 60 minutes and double jet. Method was added simultaneously.

In the resulting tabular silver halide grains, grains having a diameter / thickness number average of 7.0 accounted for 50% of the projected area of all grains, and silver iodide was 2.5 mol%. . This emulsion was chemically sensitized by using gold and sulfur together. The tabular silver halide emulsion thus obtained is hereinafter referred to as Emulsion A.

For comparison with Emulsion A, spherical grains of silver iodobromide (silver iodide 2.5 mol%) were prepared by the double jet method. The average grain size of the obtained emulsion grains was 0.7 μm. Chemical sensitization was performed by using gold and sulfur together. The emulsion thus obtained is hereinafter referred to as Emulsion B.

Emulsions other than Emulsion A and Emulsion B were monodisperse silver iodobromide emulsions (variation coefficient of average grain size <20%) prepared by keeping the pAg at 7.8 by the double jet method. These monodisperse silver iodobromide emulsions were prepared so that the grain size and iodine content would be suitable for the emulsion layers to be coated.

Next, a multi-layer color light-sensitive material having the following compositions was formed on a triacetate film base to prepare a sample 101.

First layer; antihalation layer Black colloidal silver 0.25 g / m ² UV absorber U-1 0.04 g / m ² UV absorber U-2 0.1 g / m ² UV absorber U-3 0.1 g / m ² High-boiling point organic solvent Gelatin layer containing 0.1 cc / m ² (dry film thickness 2 μ) Second layer; Intermediate layer Compound H-1 0.05 g / m ² High-boiling point organic solvent O-2 0.05 cc / m Gelatin layer containing ² (dry film thickness 1 μm) Third layer: first red-sensitive emulsion layer Silver iodobromide monodisperse emulsion spectrally sensitized with sensitizing dye S-1 and sensitizing dye S-2 ... Silver amount ... 0.5 g / m ² Coupler C-1 0.2 g / m ² High boiling point organic solvent O-2 0.12 cc / m ² gelatin layer containing 0.12 cc / m ² (dry film thickness 1 μ) 4th layer; 2nd red-sensitive emulsion layer Sensitizing dye S-1 Silver iodobromide monodisperse emulsion spectrally sensitized with the dye S-2: Silver amount: 0.8 g / m ² Coupler C-1 0.6 g / m ² Gelatin layer containing high boiling organic solvent O-2 0.33 cc / m ² (dry film thickness 2.5 μm) Fifth layer; Intermediate layer Compound H-1 0.1 g / m ² High boiling organic solvent O-2 Gelatin layer containing 0.1 cc / m ² (dry film thickness 1 μ) 6th layer; 1st green sensitive emulsion layer Sensitizing dye S-3 Spectral sensitizing with sensitizing dye S-4 Silver iodobromide monodispersed emulsion ... Silver amount ... 0.7 g / m ² Coupler C-2 0.35 g / m ² High boiling point organic solvent O-2 Gelatin layer containing 0.26 g / m ² (dry film thickness 1 μm) 7th layer; 2nd green sensitive emulsion layer Sensitizing dye S-3 enhanced Silver iodobromide monodisperse emulsion spectrally sensitized with dye S-4: Silver amount: 0.7 g / m ² Coupler C-4 0.25 g / m ² high boiling point organic solvent O-2 0.05 cc / m ² Compound A-1 gelatin layer containing 0.5 mg / m ² (dry film thickness 2.5 μm) Eighth layer; intermediate Layer Compound H-1 0.05 g / m ² High boiling point organic solvent O-2 Gelatin layer containing 0.1 g / m ² (dry film thickness 1 μm) 9th layer; Yellow filter layer Yellow colloidal silver 0.1 g / m ² Compound H-1 0.02 g / m ² Compound H-2 0.03 g / m ² Gelatin layer containing high boiling point organic solvent O-2 0.04 cc / m ² (dry film thickness 1 μm) 10th layer; 1st blue Emulsion-sensitive layer Silver iodobromide monodisperse emulsion spectrally sensitized with sensitizing dye S-5: Silver amount: 0.6 g / m ² Silver bromide monodisperse core-shell type grains having fog nuclei inside ... Silver amount ... 0.03 g / m ² (average particle size 0.2 μ, (core part having fog nuclei = 0.15, shell thickness = 0) .025 μ)) Coupler C-5 gelatin layer containing 0.5 g / m ² high boiling point organic solvent O-2 0.1 cc / m ² (dry film thickness 1.5 μ) Eleventh layer; second blue-sensitive emulsion layer Silver iodobromide emulsion B spectrally sensitized with dye S-5: Silver amount: 1.1 g / m ² Coupler C-5 1.2 g / m ² High boiling point organic solvent O-2 0.23 cc / m ² Compound A-1 Gelatin layer containing 0.5 mg / m ² (dry film thickness 3 μm) 12th layer; first protection Layer UV absorber U-1 0.10 g / m ² UV absorber U-4 0.29 g / m ² High boiling point organic solvent O-1 Gelatin layer containing 0.28 cc / m ² (dry film thickness 2 μm) 13th layer; fine silver iodobromide fogged second protective layer surface emulsion ...... silver ............ 0.1g / m ² Gelatin layer containing polymethylmethacrylate particles (average particle size 1.5 μm) (dry film thickness 0.8 μm) In addition to the above composition, a gelatin hardening agent H-3 and a surfactant were added to each layer.

The compounds used to make the samples are shown below.

C-1 C-2 C-3 C-4 C-5 U-1 U-2 U-3 U-4 H-1 H-2 H-3 O-1 O-2 S-1 S-2 S-3 S-4 S-5 A-1 Then, instead of the spherical emulsion B, the tabular emulsion A was
Layer; Sample 102 was prepared in the same manner as Sample 101 except that it was coated on the second blue-sensitive emulsion layer.

Next, Sample 1 was prepared except that the compound of the present invention shown in Table 2 was coated on the 11th layer; the second blue-sensitive emulsion layer together with the emulsion A.
Samples 103 to 124 were manufactured by the same method as 02.

The obtained sample was exposed to a light source of 4800 ° K at an exposure surface illuminance of 10
It was exposed to white light through a pattern for sharpness measurement at 00 lux, and then subjected to the development processing described later to obtain a color image.

The processing steps and processing solutions used here are as follows.

Treatment process Time Temperature First development 6 minutes 38 ° C Water wash 2 minutes 〃 Inversion 2 minutes 〃 Color development 6 minutes 〃 Adjustment 2 minutes 〃 Bleach 6 minutes 〃 Soaking 4 minutes 〃 Water washing 4 minutes 〃 Safety 1 The composition of the normal temperature dry solution is as follows.

First developer water 700
m Nitrilo-N, N, N-trimethylene phosphonic acid pentasodium salt 2
g Sodium sulfite 20
g Hydroquinone monosulfo 30
g Nate Sodium carbonate (monohydrate) 30
g 1-phenyl-4 methyl-4-hydroxymethyl-3 pyrazolidone 2
g potassium bromide 2.5
g potassium thiocyanate 1.2
g Potassium iodide (0.1% solution) 2
m Add water 1000
Inversion liquid water 700
m Nitrilo-N, N, N-trimethylene phosphonic acid pentasodium salt 3
g stannous chloride (dihydrate) 1
g p-aminophenol 0.1
g Sodium hydroxide 0.1
g glacial acetic acid 15
m Add water 1000
m color developer water 700
m Nitrilo-N, N, N-trimethylene phosphonic acid pentasodium salt 3
g Sodium sulfite 7
g Tribasic sodium phosphate (12-hydrate) 36
g potassium bromide 1
g Potassium iodide (0.1% solution) 90
m sodium hydroxide 3
g Citrazine acid 1.5
g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / sulfate 11
g 3,6-dithiaoctane-1,8-diol 1
g Add water 1000
m adjustment liquid water 700
m Sodium sulfite 12
g Ethylenediaminetetraacetic acid sodium (dihydrate) 8
g thioglycerin 0.4
m glacial acetic acid 3
m Add water 1000
m bleaching water 800
g Ethylenediaminetetraacetic acid sodium salt (dihydrate) 2
g Ethylenediaminetetraacetic acid iron (III) ammonium (dihydrate) 120
g potassium bromide 100
g Add water 1000
m fixer water 800
m Sodium thiosulfate 80.0
g Sodium sulfite 5.0
g Sodium bisulfite 5.0
g Add water 1000
m Stabilized water 800
m Formalin (37% by weight) 5.0
m Fuji Drywell (Fuji Film Co., Ltd. surfactant) 5.0
m Add water 1000
m The sharpness of magenta and cyan images of these treated samples was measured.

The sharpness was judged by the MTF value.

Table 2 shows the MTF values at 25 frequencies per mm.

Also, the optical density of the yellow image of a sample which was subjected to the same exposure and development processing except that a sensitometric wedge was used instead of the sharpness measurement pattern, was measured through a blue filter to obtain a constant density (D = 1. The sensitivity was expressed by the reciprocal of the exposure amount required to obtain the yellow density of 0).

After aging at 60 ° C. × 60% RH for 2 days, the same exposure, treatment, and optical density measurement were performed.

The obtained results are shown in Table-2.

From Table 2, as compared with the sample (Sample No. 101) in which the spherical emulsion B was applied to the second blue-sensitive layer, the sharpness was observed in the sample (Sample No. 102) in which the tabular emulsion A was applied to the second blue-sensitive layer. It can be seen that the degree is significantly improved. However, the decrease in the maximum concentration of this sample after high temperature aging is increased as compared with the comparative sample 101.

On the other hand, the samples in which the tabular emulsion A and the compound of the present invention were used in combination to coat the second blue-sensitive layer (Sample Nos. 103 to 12)
In 4), the sharpness is improved without lowering the maximum density after aging.

The above results show that the compound of the present invention has the effect of preventing the decrease in the maximum density over time that occurs when the tabular emulsion is used in a color reversal light-sensitive material. When used in color reversal photosensitive materials,
It shows that the sharpness can be significantly improved without deteriorating the photographic performance of the light-sensitive material during storage.

Example 2 Sample 201 was prepared in the same manner as Sample 102 of Example 1 except that the emulsion B of Example 1 was applied to the seventh layer; the second green-sensitive emulsion layer.
Was produced.

Next, instead of the emulsion B used in the second green-sensitive layer of Sample 201, the emulsion A of Example 1 was used as the second green-sensitive layer, and instead of the coupler C-2, C-3 was used as the first green-sensitive layer. Sample 202 was prepared in the same manner as sample 201 except that it was applied to the layer. (C
-3 coating amount 0.25 g / m ² ) Next, Samples 203 to 224 were prepared in the same manner as Sample 202 except that the compound of the present invention shown in Table 3 was coated on the second green-sensitive layer together with the emulsion A. It was made.

Among the color images obtained by exposing and processing these samples in the same manner as in Example 1, the sensitivity was measured for the magenta image and the sharpness was measured for the cyan image.

The results obtained are shown in Table 3.

From Table 3, as compared with the sample 201 in which the spherical emulsion B is applied to the second green-sensitive layer, the sample 202 in which the tabular emulsion A is applied to the second green-sensitive layer has significantly improved sharpness, and It can be seen that the sensitivity is also high. However, the decrease in the maximum concentration of this sample after high temperature aging is larger than that of the comparative sample 201.

On the other hand, a sample in which the tabular emulsion A and the compound of the present invention were used in combination to coat the second green-sensitive layer (Sample Nos. 203 to 224)
Indicates that the sharpness and sensitivity are improved without a decrease in the maximum density after aging.

Example 3 Tabular silver halide emulsions C to E were prepared in the same manner as in the emulsion A of Example 1 except that the reaction temperature was changed.

The diameter / thickness ratio of the obtained emulsion (the value when the total projected area of grains having a diameter / thickness ratio not less than this value occupies 50% of the total projected area of all grains) is shown in Table 4. As shown in.

Next, a comparative spherical emulsion F and tabular emulsions C to E prepared in the same manner as in the emulsion B of Example 1 were used instead of the emulsion A of Example 1 in the 11th layer: the second blue-sensitive emulsion. Sample 3 was prepared in the same manner as Sample 102 of Example 1 except that it was applied in layers.
01-304 were produced.

Next, except that the amounts of the compounds (I-1) and (II-2) of the present invention shown in Table 4 were applied together with the tabular emulsions C to E to the 11th layer: the second blue-sensitive emulsion layer, respectively. Sample 302
Samples 305 to 308 were manufactured by the same method as that of ˜304.

The obtained sample was exposed and processed in the same manner as in Example 1 to obtain a color image. The maximum density and sensitivity of the yellow image and the sharpness of the magenta and cyan images of these processed samples were measured by the same method as in Example 1.

The results obtained are shown in Table 4.

From Table 4, as compared with the sample 301 in which the spherical emulsion H is applied to the high blue-sensitive layer, the sharpness of the samples 302 to 304 in which the tabular emulsions C to E are applied to the second blue-sensitive layer are all sharp. It can be seen that is significantly improved. However, the decrease in the maximum concentration of these samples after high temperature aging is worse than that of the comparative sample.

On the other hand, it can be seen that Samples 305 to 308 in which the tabular emulsion and the compound of the present invention are used in combination to coat the second blue-sensitive layer have an effect of preventing a decrease in maximum density.

Here, the sharpness is improved as the “diameter / thickness ratio” is increased. However, in contrast to the comparative sample 301, the degree of maximum concentration decrease after high temperature aging of the samples (sample numbers 305 and 306) having a relatively low “diameter / thickness ratio” is as good as that of the “diameter / thickness ratio”. Sample with high ratio (Sample No. 30
In 7), it can be seen that the degree of improvement in the decrease in maximum concentration after aging at a high temperature is slightly small. However, even with respect to such particles having a relatively high “diameter / thickness ratio” (in other words, having a large surface area per unit weight), it is slightly increased by increasing the addition amount of the compound of the present invention as in Sample 308. It can be seen that the sensitivity decreases, but the decrease in the maximum concentration after aging at high temperature is repeated as in the comparative sample.

Example 4 A tabular silver halide emulsion was prepared in the same manner as in Emulsion A of Example 1 except that the amounts of KBr and KI contained in the liquid II of Table 1 of Example 1 were changed as shown in Table 5. I was prepared.

The diameter / thickness ratio of the obtained emulsion (value when the total projected area of grains having a diameter / thickness ratio of this value or more occupies 50% of the total projected area of all grains) is 5 or more. Met.

Next, a sample 402 was prepared in the same manner as the sample 102 of the example 1 except that the tabular emulsion I was coated on the 11th layer: the second blue-sensitive emulsion layer instead of the emulsion A of the example 1. Table 6 shows the results of the surface silver iodide contents of emulsions A and I obtained by the XPS method.

Next, the compounds (I-1) and (II-2) of the present invention were added together with the tabular emulsions A and I in the 11th layer: the 2nd layer.
Samples 305 to 3 of Example 3 except that it was coated on the blue-sensitive emulsion layer.
Samples 403 and 405 were produced in the same manner as in 07. The details are shown in Table 6.

The obtained sample was exposed and processed in the same manner as in Example 1 to obtain a color image. The maximum density and sensitivity of the yellow image and the sharpness of the magenta and cyan images of these processed samples were measured by the same method as in Example 1.

The results obtained are shown in Table 6.

From Table 6, it is shown that the tabular emulsion I having a high surface silver iodide content was applied to the sample 402 in which the second blue-sensitive layer was coated with the compound (I) of the present invention.
Compared with the degree of reduction of the decrease in the maximum density of Sample 405 using Samples (II) and (II) after high temperature aging, Sample 102 in which tabular emulsion A having a low surface silver iodide content was applied to the second blue sensitive layer Sample 403 using the compounds (I) and (II) of the present invention for
The degree of reduction in the decrease in maximum concentration after aging at high temperature is remarkable,
The improvement effect is great. Therefore, it is shown that the present invention is effective for tabular grains having a low surface silver iodide content.

Claims (1)

[Claims] 1. A silver halide color reversal light-sensitive material comprising at least one red-sensitive, green-sensitive and blue-sensitive emulsion layer, each of which (1) has a grain size of 5 times or more the grain thickness. An emulsion containing tabular silver halide grains having a silver iodide content of 5 mol% or less on the grain surface, and (2) a triazine polymer compound of the following general formula (I) and a general formula (II) At least 50% of the total projected area of silver halide grains containing at least one kind of mercaptotetrazole compound and in which the grains are present in the same layer.
Silver halide color reversal light-sensitive material. General formula (I) Here, R ₁ is -OR, -SR, And R and R ′ each represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group, a sulfoalkyl (or salt thereof) group, a carboxyalkyl (or salt thereof) group, an aralkyl group, or a sulfo group. (Or a salt thereof)-, a carboxyl (or a salt thereof)-, an alkyl having 1 to 4 carbons, and an alkoxy having 1 to 4 carbons.
Or, represents an aryl group having a carbon number of 6 to 12 with or without a halogen-substituent, or a cycloalkyl group, or R and R ′ together form an alkylene ring or an alkylene ring containing —O—. Alternatively, R ₂ , R ₃ , R ₄ and R ₅ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Y ₁ , Y ₂ , Y ₃ and Y ₄ each have a carbon number. 2-12
Or a polymethylene group having 2 to 12 carbon atoms substituted with an alkyl group having 1 to 4 carbon atoms, sulfo (or a salt thereof)-, carboxyl (or a salt thereof)-, an alkyl group having 1 to 4 carbon atoms, or halogen - if having substituents or having no arylene group or represents a cycloalkylene group,, Z is -O -, - SO ₂ - or -CH ₂ - represents, and m represents 0 or 1. General formula (II) In the formula, M represents a hydrogen atom, a cation or a protecting group for a mercapto group which is cleaved by an alkali, and Z represents an atomic group necessary for forming a 5-membered or 6-membered heterocycle. This heterocycle may have a substituent or may be condensed. R ₁₁ and R ₁₂ represent a hydrogen atom, an unsubstituted or substituted aliphatic group or an unsubstituted or substituted aromatic group, and R ₁₁ and R ₁₂ may be the same or different, and They may combine to form a ring.