JP2001005129A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide color photographic sensitive material having superior developability and a wide latitude and containing an emulsion constitution excellent in production stability by incorporating a cubic grain emulsion and a (100) flat platy grain emulsion into an emulsion layer. SOLUTION: The silver halide color photographic sensitive material contains a cubic grain emulsion and a (100) flat platy grain emulsion in at least one of emulsion layers. The number average aspect ratio of the (100) flat platy grains is preferably 1.2-100, further preferably 2.1-70, most preferably 2.5-20. The number average thickness of the (100) flat platy grains is preferably 0.04-0.25 μm, further preferably 0.08-0.20 μm. The coefficient of variation of equivalent circular diameter of the (100) flat platy grains is preferably 1-25%, further preferably 1-20%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material excellent in latitude, development processing property and production stability.

[0002]

2. Description of the Related Art In recent years, technical trends in silver halide photographic light-sensitive materials include high-sensitivity light-sensitive materials represented by ISO 1600 photographic light-sensitive materials, and small-size formats such as APS, 110 size systems and disk size systems. Satisfactory photographic performance with photosensitive materials used in photography with computerized cameras, and photosensitive materials used in filming with lenses, such as "Sharun Run Hi" and "Sharun Run Panoramic" Granularity, pressure resistance,
Sharpness, color reproducibility, latitude, rapid processing, etc.)
There is a demand for a higher level of performance for each type of photosensitive material. Among them, a photographic photosensitive material with a wide latitude that can cope with excellent development processability and a wide exposure area has been desired.

[0003] To meet such demands, tabular silver halide grains having various features due to their shapes have been used, but most of them have parallel twin planes and have a size of # 11.
1} Tabular grains having a crystal plane as a main plane (hereinafter {111})
Flat plate).

In addition, in recent years, particularly in recent years, research on tabular grains having no twin planes and having parallel {100} crystal planes as main planes (hereinafter referred to as {100} tabular grains) has been energetically conducted. It is becoming possible to proceed.

To obtain a photographic light-sensitive material having a wide latitude, it is necessary to use a low-sensitivity emulsion excellent in latitude. Recent silver halide color photographic materials are {111}
Most of the tabular grain emulsions are prepared with a multilayer structure, but it is known that it is difficult to prepare small-sized grains for use in a low-sensitivity region with {111} tabular grains.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material having an emulsion constitution which has excellent development processability, a wide latitude and excellent production stability. .

[0007]

Means for Solving the Problems As a result of intensive studies on the above-mentioned prior art, it has been clarified that the use of cubic particles having a small size can ensure the latitude of a high concentration portion. However, when {111} tabular grains and cubes are used together in the same layer, depending on the grain size range used, the photographic performance of the emulsion mixed in each layer may be reduced by the actual coating after the emulsion mixing starts during production. The change occurred before the test was performed, which proved to be undesirable.

The object of the present invention has been attained by the following items.

(1) In a silver halide color photographic material having at least one silver halide emulsion layer on a support, at least one of the emulsion layers contains a cubic grain emulsion and a {100} tabular grain emulsion. A silver halide color photographic light-sensitive material, characterized in that:

(2) The silver halide color photographic material as described in (1), wherein the number average grain thickness of the {100} tabular grains is 0.04 μm or more and 0.20 μm or less.

(3) The silver halide color photographic light-sensitive material as described in (1) or (2), wherein the number average aspect ratio of the {100} tabular grains is from 2.5 to 50.

(4) The silver halide according to any one of (1) to (3), wherein the coefficient of variation of the equivalent circle diameter of the {100} tabular grains is from 1% to 20%. Color photographic light-sensitive material.

(5) Any one of (1) to (4), wherein at least one of the emulsion layers contains only two kinds of emulsions, a cubic grain emulsion and a {100} tabular grain emulsion. 2. The silver halide color photographic light-sensitive material according to item 1.

Alternatively, (6) the silver halide color photographic light-sensitive material as described in any one of (1) to (5), wherein the {100} tabular grains have dislocations.

[0015]

Next, the present invention will be described in detail. The {100} tabular grain emulsion used in the present invention can be prepared by known techniques such as those described in JP-A-6-19028 and JP-A-8-3390.
44 and the like. Also, cubic grain emulsions can be prepared with reference to known techniques.

The principal plane is a set of parallel crystal planes having the largest area among the crystal planes constituting the tabular grains, and the {100} tabular grains are defined as {100} crystal planes. Are tabular grains. The fact that the main plane is a {100} crystal plane can be confirmed by an electron diffraction method or an X-ray diffraction method.

Further, {100} tabular grains are characterized by having no twin plane. The twin plane is a plane defect in which crystal lattices are arranged in a mirror-like manner with respect to a certain crystal lattice plane, and the existence thereof can be confirmed by a known technique using a transmission electron microscope.

The equivalent circle diameter indicates the diameter of a circle having an area equal to the main plane of the tabular grains, and the grain thickness indicates the distance between two parallel main planes of the tabular grains. These sizes can be measured by a known technique using an electron microscope.

The grain size of the {100} tabular grains used in the present invention is 0.15 μm or more and 0.5
It is preferably 0 μm or less, more preferably 0.20 μm or more and 0.45 μm or less. The number average sphere equivalent diameter of the cubic particles is 0.13 μm or more and 0.50 or more.
μm or less, preferably 0.15 μm or more.
More preferably, it is 40 μm or less. Here, the sphere equivalent diameter corresponds to the size of the diameter when the particle volume is converted into a sphere.

The cubic particles used in the present invention do not have twin planes, and the particle surfaces are mainly constituted by {100} crystal planes.
The particles have an aspect ratio of 1 or more and less than 1.2. Here, the aspect ratio is a value obtained by dividing a circle equivalent diameter of a particle by a particle thickness. Also, the particle surface is mainly $ 10
To be composed of 0 crystal planes means that the occupation ratio of the {100} plane is 60% or more, and the occupation ratio of the {100} is J. Imaging Sci., 29 (5), 165-171 ( 1985) can be measured with reference to a method using dye adsorption described in, for example.

The number average aspect ratio of the {100} tabular grains used in the present invention is preferably 1.2 or more and 100 or less, more preferably 2.1 or more and 70 or less, and more preferably 2.5 or more. Most preferably, it is 20 or less.

The number average thickness of the {100} tabular grains used in the present invention is preferably from 0.04 μm to 0.25 μm, and more preferably from 0.08 μm to 0.20 μm.

The coefficient of variation of the equivalent circle diameter is a value obtained by dividing the standard deviation of the equivalent circle diameter by the average value of the equivalent circle diameter and multiplying by 100, and is expressed in%.

In the present invention, the coefficient of variation of the equivalent circle diameter of {100} tabular grains mixed in the same layer is preferably 1% or more and 25% or less, more preferably 1% or more and 20% or less.

The dislocations of the {100} tabular grains that can be used in the present invention can be observed by a known method using a transmission electron microscope.

In the present invention, tabular grains preferably have dislocation lines. Dislocation lines of tabular grains are described, for example, in J. Am. F. H
amilton, Photo. Sci. Eng. , 1
1, 57, (1967); Shiozawa, J .;
Soc. Photo. Sci. Japan, 35, 21
3, (1972), can be observed by a direct method using a transmission electron microscope at a low temperature. That is, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocation lines on the grains are placed on a mesh for observation with an electron microscope, and the sample is prepared so as to prevent damage (printout, etc.) by the electron beam. Observation is carried out by a transmission method in a state where is cooled. At this time, the thicker the particle, the more difficult it is for an electron beam to pass. Therefore, a high-voltage (200 kV or more for a 0.25 μm-thick particle) electron microscope can be observed more clearly. . From the photograph of the particles obtained by such a method, the position and the number of dislocation lines for each particle when viewed from the direction perpendicular to the main plane can be obtained.

The number of dislocation lines is preferably one or more on average per grain. More preferably, the average is 2 or more per particle. The average number of dislocation lines per particle is determined as a number average by counting the number of dislocation lines for 100 particles or more. Dislocation lines can be introduced, for example, near the outer periphery of tabular grains.

The silver halide color photographic light-sensitive material of the present invention has at least one silver halide emulsion layer on a support, and at least one of the emulsion layers contains a cubic grain emulsion and a {100} tabular grain emulsion. It is characterized by being contained in the same layer. It is further preferred that at least one of the emulsion layers of the silver halide color photographic light-sensitive material of the present invention contains only two kinds of emulsions, a cubic grain emulsion and a {100} tabular grain emulsion, in the same layer.

The coating amount of the cubic grain emulsion is usually 0.01 g / m ^{2 to} 5.0 g / m ² , preferably in terms of silver amount,
^{0.03g / m 2 ~2.0g / m 2} , the coating amount of the {100} tabular grain emulsions are usually silver amount conversion, 0.02 g / m ² ~
10.0 g / m ² , preferably 0.15 g / m ² -7.
It can be set to 5 g / m ² . There is no particular limitation on the mixing ratio of the cubic grains, the emulsion and the {100} tabular grain emulsion.

The cubic grain emulsion and the {100} tabular grain emulsion have an effect when contained in any of the color-sensitive layers, but are preferably contained in the low-speed emulsion layer.

The {100} tabular grains and cubic grains used in the present invention are silver chloride, silver iodochloride, silver bromide, silver chlorobromide,
Any combination of silver iodobromide and silver iodochlorobromide can be used.

When preparing both {100} tabular grain and cubic grain emulsions used in the present invention, for example, during grain formation,
In the desalting step, at the time of chemical sensitization, the presence of a metal ion salt before coating is preferable depending on the purpose. When the metal ion salt is doped into the grains, it is preferable to add the metal ion salt after the grain formation and before the completion of the chemical sensitization when the metal ion salt is used for modifying the grain surface or as a chemical sensitizer. In addition to doping the entire metal particle with the metal ion salt, only the core portion or only the shell portion of the particle,
Alternatively, it is also possible to dope only the epitaxial portion or only the base particles. Examples of the metal ions include Mg, Ca, Sr, Ba, Al, Sc, Y, and L.
a, Cr, Mn, Fe, Co, Ni, Cu, Zn, G
a, Ru, Rh, Pd, Re, Os, Ir, Pt, A
The ions of u, Cd, Hg, Tl, In, Sn, Pb, and Bi can be used. These metal ions may be in the form of a salt that can be dissolved at the time of particle formation, such as an ammonium salt, an acetate, a nitrate, a sulfate, a phosphate, a hydroxide, or a six-coordinate complex or a four-coordinate complex. Can be used. Such salts include, for example, CdBr ₂ , C
dCl ₂ , Cd (NO ₃ ) ₂ , Pb (NO ₃ ) ₂ , Pb
(CH ₃ COO) ₂ , K ₃ [Fe (CN) ₆ ], (NH ₄ )
₄ [Fe (CN) ₆ ], K ₃ IrCl ₆ , (NH ₄ ) ₃ RhC
_{l 6, K 4 Ru (CN} ) 6 , and the like. The ligand of the coordination complex can be selected from, for example, halo, aquo, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo, and carbonyl. These metal ion salts may be used alone or in combination of two or more.

The metal ion salt is preferably dissolved in water or a suitable solvent such as methanol or acetone and added. To stabilize the solution, an aqueous solution of hydrogen halide (eg, HCl, HBr) or an alkali halide (eg, KCl, NaCl, KBr, NaBr) can be added. If necessary, for example, an acid or an alkali may be added. The metal ion salt may be added to the reaction vessel before the formation of the particles, or may be added during the formation of the particles. In addition, a metal ion salt is converted to a water-soluble silver salt (eg, AgN
O ₃ ) or an aqueous alkali halide solution (eg, Na
Cl, KBr, KI) and can be added continuously during the formation of silver halide grains. Further, a solution of a metal ion salt may be prepared independently of the water-soluble silver salt and alkali halide, and may be continuously added at an appropriate time during grain formation. It is also preferable to combine various addition methods.

A method of adding a chalcogenide compound during preparation of an emulsion as described in US Pat. No. 3,772,031 is sometimes useful. In addition to S, Se, Te, cyanide, thiocyanate, selenocyanic acid, carbonate,
Phosphates and acetates may be present.

Emulsions used in the present invention include sulfur sensitization, selenium sensitization, noble metal sensitization (eg, gold sensitization, palladium sensitization),
At least one of the reduction sensitizations can be performed in any step of the production process of the silver halide emulsion. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which a chemical sensitizing nucleus is embedded in the grain, a type in which the chemical sensitizing nucleus is embedded in a position shallow from the grain surface, and a type in which a chemical sensitizing nucleus is formed on the surface. In the emulsion used in the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose. Generally, the case where at least one type of chemical sensitization nucleus is formed near the surface is preferred.

One of the chemical sensitizations which can be preferably carried out in the present invention is a chalcogenide sensitization and a noble metal sensitization alone or in combination, and these chemical sensitizations are carried out by James (TH James).
s) Author, The Photographic Process, 4th Edition,
Macmillan, 1977, (TH James, The Theor
y of the Photographic Process, 4th ed, Macmillan,
1977) on pages 67-76, and can be performed using active gelatin, and is also described in Research Disclosure 120, April 1974, 12008; Research Disclosure 34, June 1975, 1
3452; U.S. Pat. Nos. 2,642,361;
Nos. 297,446, 3,772,031, 3,857,711, 3,901,714, 4,266,018, and 3,904,41.
5, pAg 5-10, pH 5-8 and temperature 30 as described in GB 1,315,755.
At 〜80 ° C., sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of these sensitizers can be used. In precious metal sensitization,
Noble metal salts such as gold, platinum, palladium, and iridium can be used as the sensitizer, and the noble metal sensitization is particularly preferably gold sensitization, palladium sensitization, or a combination of both. In the case of gold sensitization, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide,
Known gold sensitizers such as gold selenide can be used. Palladium sensitizer is palladium divalent salt or 4
It is a valent salt. Preferred palladium sensitizers are R ₂ Pd
Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group represented by X ₆ or R ₂ PdX ₄ .
X represents a halogen atom, and represents a chlorine, bromine or iodine atom. Specifically, K ₂ PdCl ₄ , (NH ₄ ) ₂
PdCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdC
l ₄ , Li ₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂
PdBr ₄ is preferred. The gold sensitizer and the palladium sensitizer are preferably used in combination with a thiocyanate or a selenocyanate.

As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat. No. 3,857,
Nos. 711, 4,266,018 and 4,0
No. 54,457 can be used.

The preferred amount of the gold sensitizer is 1 × 10 ^-4 to 1 × 10 ^-7 mol, more preferably 1 × 10 ^{-5 to} 5 × 10 ^-7 mol, per mol of silver halide. . The preferred range of the palladium sensitizer is 1 × per mole of silver halide.
It is 10 ⁻³ to 5 × 10 ⁻⁷ mol. The preferred range of the thiocyan compound or selenocyan compound is from 5 × 10 ⁻² to 1 × 10 ⁻⁶ mol per mol of silver halide.

The preferred amount of sulfur sensitizer used in the emulsion used in the present invention is 1 × 10 5 per mol of silver halide.
^-4 to 1 × 10 ^-7 mol, more preferably 1 × 1
It is 0 ^{-5 to} 5 × 10 ^-7 mol.

Selenium sensitization is a preferred sensitization method for the emulsion used in the present invention. In selenium sensitization,
Using a known unstable selenium compound, specifically, colloidal metal selenium and selenoureas (for example, N, N-
Selenium compounds such as dimethylselenourea, N, N-diethylselenourea), selenoketones, and selenoamides can be used. It may be preferable to use selenium sensitization in combination with sulfur sensitization and / or noble metal sensitization. The addition amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the type and size of silver halide, the ripening temperature and time, and the like. 1 × 1 per mole
0 ^-8 or more. More preferably 1 × 10 ⁻⁷ mol or more 5
× 10 ^-5 mol or less. The temperature of chemical ripening when a selenium sensitizer is used is preferably 45 ° C or higher, more preferably 50 ° C or higher and 80 ° C or lower. pAg and p
H is optional.

Chemical sensitization can be carried out in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during chemical sensitization, such as azaindene, azapyridazine and azapyrimidine. Examples of chemical sensitization aid modifiers are described in U.S. Pat.
Nos. 11,914 and 3,554,757,
No.-126526 and the aforementioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143.

The emulsion used in the present invention is preferably subjected to reduction sensitization during grain formation, after grain formation and before or during chemical sensitization, or after chemical sensitization.

As the reduction sensitization, a method of adding a reduction sensitizer to a silver halide emulsion, a pAg 1
7, a method of growing or ripening in a low pAg atmosphere, or a method of growing or ripening in a high pH atmosphere of pH 8-11 called high pH ripening. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method since the level of reduction sensitization can be finely adjusted.

As reduction sensitizers, for example, stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid,
Silane compounds and borane compounds are known. For the reduction sensitization of the present invention, these known reduction sensitizers can be used, and two or more compounds can be used in combination. Stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and derivatives thereof are preferred compounds as reduction sensitizers. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but an appropriate range is from 10 ^-7 to 10 ^-3 mol per mol of silver halide.

The reduction sensitizer is dissolved in water or an organic solvent such as alcohols, glycols, ketones, esters, and amides and added during grain formation. Although it may be added to the reaction vessel in advance, it is preferable to add it at an appropriate time during grain growth. Alternatively, a reduction sensitizer may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and silver halide grains may be precipitated using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains grow, or to add the solution continuously for a long time.

During the production process of the emulsion used in the present invention,
Preferably, an oxidizing agent is used. Oxidation to silver
An agent acts on metallic silver to convert it into silver ions.
Refers to a compound that has the action of Especially for silver halide grains
Extremely by-produced during formation and chemical sensitization
Compounds that convert small silver particles into silver ions are effective
It is. The silver ions generated here are silver halide,
Even if it forms a silver salt that is hardly soluble in water like silver chloride and silver selenide
Also, even if silver salt easily soluble in water like silver nitrate is formed
Good. Oxidizing agents for silver can be inorganic or organic.
It may be. Inorganic oxidants include ozone and peracid
Hydrogen chloride and its adducts (eg, NaBO_Two・ H_TwoO_Two
・ 3H_TwoO, 2NaCO_Three・ 3H_TwoO_Two , Na_FourP_TwoO₇・
2H_TwoO_Two, 2Na_TwoSO_Four・ H_TwoO_Two・ 2H_TwoO), Peru
Xylate (eg, K_TwoS_TwoO₈ , K _TwoC_TwoO₆ , K_TwoP
_TwoO₈), Peroxy complex compounds (eg, K_Two[Ti
(O_Two) C _TwoO_Four ] ・ 3H_TwoO, 4K_TwoSO_Four・ Ti
(O_Two) OH ・ SO_Four・ 2H_TwoO, Na_Three[VO (O_Two)
(C_TwoH_Four)_Two・ 6H_TwoO], permanganate (eg, K
MnO_Four), Chromates (eg, K_TwoCr_TwoO₇)As
Oxyacid salts, halogen elements such as iodine and bromine,
Genoates (eg, potassium periodate), high-valent metals
(Eg, potassium hexacyanoferrate) and
And thiosulfonates. Also, with organic oxidants
Quinones such as p-quinone, peracetic acid and
Release of organic peroxides such as perfumes and active halogens
Compounds (for example, N-bromosuccinimide, chloramine
T, chloramine B) are mentioned by way of example.

Preferred oxidizing agents used in the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizing agents of thiosulfonates and organic oxidizing agents of quinones.

It is a preferred embodiment to use the above-mentioned reduction sensitization and an oxidizing agent for silver in combination. A method of using an oxidizing agent followed by reduction sensitization, a reverse method thereof, or a method of coexisting both can be used. These methods can be applied to both the grain formation step and the chemical sensitization step.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, thiazoles (eg, benzothiazolium salts), nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines, mercaptotriazines, thioketo compounds (eg oxadrinethione),
Azaindenes (for example, triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3
a, 7) Many compounds known as antifoggants or stabilizers, such as tetraazaindenes), pentaazaindenes) can be added. For example, U.S. Patent Nos. 3,954,474 and 3,982,947
And JP-B No. 52-28660 can be used. One of the preferred compounds is disclosed in
There are compounds described in US Pat. Antifoggants and stabilizers are used at various times before, during and after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added according to the purpose. In addition to exhibiting the original antifogging and stabilizing effects by adding during emulsion preparation, control the crystal habit of the grains, reduce the grain size, reduce the solubility of the grains, control the chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

The photographic emulsion used in the present invention is preferably spectrally sensitized by a methine dye or the like to exhibit the effects of the present invention. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. These dyes may contain any nucleus commonly used in cyanine dyes as a basic heterocyclic nucleus. Such nuclei include, for example, a pyrroline nucleus,
Oxazoline nucleus, thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus; nucleus in which alicyclic hydrocarbon ring is fused to these nuclei; A nucleus in which hydrogen rings are fused, that is, indolenine nucleus, benzindolenin nucleus, indole nucleus, benzoxazole nucleus,
Naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus and quinoline nucleus can be mentioned. These nuclei may have a substituent on a carbon atom.

The merocyanine dye or the complex merocyanine dye includes, as nuclei having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, and a thiazolidine-2,4-nucleus.
It can have a 5-6 membered heterocyclic nucleus such as a dione nucleus, a rhodanine nucleus, a thiobarbituric acid nucleus.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,977,
Nos. 229 and 3,397,060 and 3,522,0
No. 52, 3,527, 641, 3,617, 29
3, 3,628,964, 3,666,480
Nos. 3,672,898 and 3,679,428
Nos. 3,703,377 and 3,769,301
No. 3,814,609 and 3,837,862
No. 4,026,707 and British Patent No. 1,344.
No. 281, No. 1, 507, 803, JP-B-43-49
No. 36, No. 53-12375, JP-A-52-1106
No. 18, 52-109925.

In addition to the sensitizing dye, the emulsion may contain a dye which has no spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

The sensitizing dye may be added to the emulsion at any stage in the preparation of the emulsion which has hitherto been known to be useful. Most commonly, it is performed after completion of chemical sensitization but before coating, but US Pat.
As described in JP-A-8-969 and JP-A-4225666, spectral sensitization may be carried out simultaneously with chemical sensitization by simultaneous addition with a chemical sensitizer.
It can be carried out prior to chemical sensitization as described in No. 928, or it can be added before completion of silver halide grain precipitation to start spectral sensitization. Furthermore, as taught in U.S. Pat. No. 4,225,666, these sensitizing dyes are added separately, i.e., some of these sensitizing dyes are added prior to chemical sensitization and the remainder is added. It can be added after chemical sensitization, and may be at any time during the formation of silver halide grains, including the method disclosed in U.S. Pat. No. 4,183,756.

The sensitizing dye was used in an amount of 4 per mole of silver halide.
It can be used in an amount of from × 10 ^-6 to 8 × 10 ^-3 mol, but a more preferable silver halide grain size is from 0.2 to 1.2 μm.
Is about 5 × 10 ^-5 to 2 × 1 per mol of silver halide.
0 ^-3 mol is more effective.

The above-mentioned various additives are used in the light-sensitive material according to the present technology, but other various additives can be used according to the purpose.

These additives are described in more detail in Research Disclosure Item 17643 (Jan.
(February), Item 18716 (November 1979) and Item 308119 (December 1989), and the relevant locations are summarized in Table 1 below.

In the color light-sensitive material of the present invention, provided that at least one of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer is provided on a support. The number and order of the silver halide emulsion layers and the non-light-sensitive layers are not particularly limited. As a typical example, a support has at least one photosensitive layer (unit photosensitive layer) composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. A silver halide photographic material,
The unit photosensitive layer has color sensitivity to any of blue light, green light, and red light. In the multilayer silver halide color photographic light-sensitive material preferred in the present invention, the arrangement of the unit light-sensitive layers is generally arranged in order from the support side in the order of red-sensitive layer, green-sensitive layer, and blue-sensitive layer. But,
Depending on the purpose, the order of installation may be reversed, or the order of installation may be such that photosensitive layers having different color sensitivity are sandwiched between layers having the same color sensitivity.

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.

For the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
Couplers, DIR compounds, and the like as described in JP-A Nos. 61-20037 and 61-20038 may be contained, and a color mixture inhibitor may be contained as usually used.

As described in West German Patent No. 1,121,470 or British Patent No. 923,045, a plurality of silver halide emulsion layers constituting each unit photosensitive layer may be composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer. A two-layer constitution of an emulsion layer 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,
JP-A-57-112751, 62-200350
As described in JP-A Nos. 62-206541 and 62-206543, a low-speed emulsion layer may be provided on the side farther from the support and a high-speed emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low-sensitivity blue-sensitive layer (BL) / High-sensitivity blue-sensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
And so on.

As described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. JP-A-56-25738 and JP-A-62-6393.
As described in the specification of JP-A No. 6, the blue light-sensitive layer / GL / RL / GH / RH may be arranged in this order from the farthest side from the support.

As described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. Further, an arrangement is also possible in which a silver halide emulsion layer having a lower sensitivity is further disposed, and an arrangement is formed of three layers having different sensitivities in which the sensitivities are successively decreased toward the support. Even in the case of three layers having different sensitivities, as described in JP-A-59-202264, a medium-sensitivity emulsion from the side farther from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers.

In addition, a high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or a low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer may be arranged in this order. Also, 4
The arrangement may be changed as described above even in the case of more than layers.

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

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is about 30 mol%.
Silver iodobromide, silver iodochloride, or silver iodochlorobromide containing the following silver iodide. Particularly preferred is from about 2 mol% to about 1 mol%.
Silver iodobromide or silver iodochlorobromide containing up to 0 mol% of silver iodide.

The silver halide grains in the emulsions that can be used in the light-sensitive material of the present invention other than the emulsions to be mixed in the same layer of the present invention are as follows unless cubic and {100} tabular grains are present in the same layer. Cubes, octahedrons, those having regular crystals such as tetradecahedrons, spheres, those having irregular crystal forms such as plates, those having crystal defects such as twin planes,
Alternatively, a composite form thereof may be used.

The silver halide grains usable in the light-sensitive material of the present invention other than the emulsion mixed in the same layer of the present invention can have a projected area diameter of about 10 .mu.m
Large-sized grains up to and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the light-sensitive material of the present invention other than the emulsion mixed in the same layer of the present invention includes:
For example, Research Disclosure (RD) No. 17
643 (Dec. 1978), pp. 22-23, "I. Emulsion preparation and types", and No. 18716 (November, 1979), p.
No. 307105 (November 1989), 863-86
Page 5, and Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chemie et Phisiqu)
e Photographique, Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G.
F. Duffin, Photographic Emulsion Chemistry (Focal
Press, 1966)), "Manufacture and Coating of Photographic Emulsions", by Zelikman et al., Published by Focal Press (VL Zelikman e).
t al., Making and Coating Photographic Emulsio
n, Focal Press, 1964).

US Pat. Nos. 3,574,628;
655,394 and British Patent 1,413,748.
Monodisperse emulsions described in Nos. 1 and 2 are also preferred.

Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineering.
gineering), 14, 248-257 (1970).
U.S. Pat. Nos. 4,434,226 and 4,41.
No. 4,310, No. 4,433,048, No. 4,43
No. 9,520 and British Patent No. 2,112,157 can be easily prepared.

The crystal structure is uniform, and the inside and the outside may be composed of different halogen compositions, or may have a layered structure. Further, silver halides having different compositions may be bonded by epitaxial bonding, or 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 a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which a latent image is formed inside a grain, or a type having a latent image on both the surface and the inside. Type emulsion. Of the internal latent image type, the core / core described in JP-A-63-264740 is used.
It may be a shell type internal latent image type emulsion. A method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-13.
No. 3542. 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.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. Additives used in such a process are described in Research Disclosure Nos. 17643, 18716 and No. 18716.
308119, and the corresponding portions are summarized in Table 1 below.

The light-sensitive material of the present invention comprises a light-sensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more emulsions differing in at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the inside of the grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are covered. Silver halide grains and colloidal silver can be preferably used for a light-sensitive silver halide emulsion layer and / or a substantially light-insensitive 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. . A method for preparing silver halide grains having the inside or the surface of the grains fogged 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 / shell 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, but the average grain size is 0.01 to 0.7.
5 μm, particularly preferably 0.05 to 0.6 μm, is preferred. Also,
The grain shape is not particularly limited, and may be regular grains or polydispersed emulsions, but may be monodispersed (at least 95% of the weight or the number of silver halide grains is within ± 40% of the average grain size). Having a particle size of 1).

In the light-sensitive material of the present invention, it is preferable to use non-light-sensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably 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
Alternatively, it may contain silver iodide. Preferably silver iodide,
It contains 0.5 to 10 mol%.

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

The fine grain silver halide can be prepared in the same manner as in the case of ordinary light-sensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized,
Also, spectral sensitization is not required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in the layer containing fine silver halide grains.

Known photographic additives which can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in Table 1 below.

[0085]

[Table 1]

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat.
It is preferable to add a compound capable of being fixed by reacting with formaldehyde described in JP-A No. 7 or 4,435,503 to the photosensitive material.

The light-sensitive material of the present invention may be added to US Pat.
0,454, 4,788,132, JP-A-62
It is preferable to include a mercapto compound described in JP-A-18539 and JP-A-1-283551.

The light-sensitive material of the present invention is prepared by adding
No. 52, it is preferable to contain a compound which releases 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.

The light-sensitive material of the present invention may be added to International Publication WO88 /
No. 04794, a dye dispersed by the method described in JP-A No. 1-502912 or EP 317,308A,
U.S. Pat. No. 4,420,555;
The dye described in No. 8 is preferably contained.

The photographic light-sensitive material of the present invention has at least one silver halide emulsion layer and at least one non-light-sensitive layer provided on a support, and is preferably a multilayer color photographic light-sensitive material. A support having at least two silver halide emulsion layers sensitive to light in different wavelength ranges, more preferably a color image forming unit comprising a red-sensitive silver halide emulsion, and a green-sensitive silver halide emulsion layer. Color image forming units and a color image forming unit comprising a blue-sensitive silver halide emulsion layer on a support.
Further, the photographic light-sensitive material of the present invention contains, in a silver halide emulsion layer, at least one kind of non-diffusible color-forming coupler which forms a dye by coupling with an oxidized aromatic primary amine developing agent, and more preferably. A blue-sensitive silver halide emulsion layer containing a yellow coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a red-sensitive silver halide emulsion layer containing a cyan coupler. The multilayer color photographic light-sensitive material of the present invention is exposed and developed, and then processed with a bleaching solution or a bleach-fixing solution.

In the present invention, the silver halide emulsion contains a binder and silver halide, and is produced by grain formation, physical ripening, desalting (washing with water) and chemical sensitization in the presence of a hydrophilic colloid. Usually, the emulsion is preferably a silver halide emulsion containing gelatin as a main component of the binder, and is preferably chemically sensitized and further subjected to spectral sensitization.

In the present invention, the silver halide grains are photosensitive, chemically sensitized, and preferably further spectrally sensitized.

In the method for producing a photographic light-sensitive material of the present invention, a photographic useful substance is usually added to a photographic coating solution, that is, a hydrophilic colloid solution.

In the light-sensitive material of the present invention, the photographic light-sensitive material is usually processed after image exposure with an alkali developing solution containing a developing agent. After color development, the color photographic light-sensitive material has a bleaching ability containing a bleaching agent. An image forming method of processing with a processing liquid having the same is performed.

Various color couplers can be used in the light-sensitive material of the present invention, and specific examples thereof are described in Research Disclosure No. 17643, VII-C to G, and
And No. 307105, VII-CG.

As the yellow coupler, for example, US Pat. Nos. 3,933,501 and 4,022,620
No. 4,326,024 and 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107
No. 39, British Patent Nos. 1,425,020 and 1,4
No. 76,760; U.S. Pat. Nos. 3,973,968; 4,314,023; 4,511,649;
Those described in EP 249,473A and the like are preferred.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable. US Pat. Nos. 4,310,619 and 4,351,897
No. 3,073,636; U.S. Pat.
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984
), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, and 60-
No. 35730, No. 55-118034, No. 60-18
No. 5,951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, and WO88 / 04795 are particularly preferable.

Examples of the cyan coupler include phenol-based and naphthol-based couplers.
No. 52,212, No. 4,146,396, No. 4,
Nos. 228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826,
No. 3,772,002 and No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A and 249,453A, U.S. Patent Nos. 3,446,622, and 4,333,999.
No. 4,775,616, No. 4,451,55
No. 9, No. 4,427,767, No. 4,690, 8
No. 89, No. 4,254,212, No. 4,296,
199 and JP-A-61-42658 are preferred.

Typical examples of polymerized dye-forming couplers are described in US Pat. Nos. 3,451,820 and 4,082.
No. 0,211, No. 4,367,282, No. 4,4
Nos. 09,320, 4,576,910, British Patent 2,102,137, and European Patent No. 341,188A.

Examples of couplers in which a coloring dye has an appropriate diffusivity include US Pat. No. 4,366,237, British Patent No. 2,125,570, and European Patent No. 96,570.
Those described in West German Patent (Published) No. 3,234,533 are preferred.

A colored coupler for correcting unnecessary absorption of a coloring dye is described in Research Disclosure No.
VII-G of 17643, VII of No. 307105
Section G, U.S. Pat. No. 4,163,670, JP-B-57
-39413; U.S. Pat. Nos. 4,004,929 and 4,138,258; British Patent 1,146,36.
No. 8 is preferable. Also, U.S. Pat.
No. 74,181, a coupler capable of correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling, or a dye capable of reacting with a developing agent described in U.S. Pat. No. 4,777,120 to form a dye. It is also preferable to use a coupler having a dye precursor group as a leaving group.

Compounds which release a photographically useful residue upon coupling can also be preferably used in the present invention.
The DIR coupler releasing the development inhibitor is the RD1 described above.
No. 7643, VII-F and No. 307105, VII-
Patent described in section F, JP-A-57-151944,
Preferred are those described in JP-A-57-154234, JP-A-60-184248, JP-A-63-37346, JP-A-63-37350, U.S. Pat. Nos. 4,248,962 and 4,782,012.

Examples of couplers which release a nucleating agent or a development accelerator in an image-like manner during development include British Patent No. 2,099.
7,140,2,131,188, JP-A-59
Preferred are those described in JP-A-157638 and JP-A-59-170840. Also, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-44940.
Also preferred are compounds capable of releasing a fogging agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized form of a developing agent described in US Pat.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
No. 4,283,47.
No. 2, No. 4,338,393, No. 4,310,6
No. 18, etc .;
No. 950, DIR described in JP-A-62-24252 and the like.
Redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 1
Nos. 73,302A and 313,308A, couplers capable of releasing a dye that recolors after release, U.S. Pat.
55,477, etc., couplers releasing leuco dyes described in JP-A-63-75747, couplers releasing fluorescent dyes described in U.S. Pat. No. 4,774,181, and the like. Can be

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 and the like. The boiling point at normal pressure used for the oil-in-water dispersion method is 17
Specific examples of the high boiling point organic solvent having a temperature of 5 ° C. or higher include phthalic acid esters (eg, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl)) Phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), phosphoric acid or phosphonic acid esters (for example, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2
-Ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphonate), benzoic acid esters (for example, 2-ethylhexyl benzoate, dodecyl benzoate,
-Ethylhexyl-p-hydroxybenzoate), amides (for example, N, N-diethyldodecaneamide,
N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg, isostearyl alcohol, 2,4-di-tert)
-Amylphenol), aliphatic carboxylic esters (e.g., bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate),
Examples include aniline derivatives (eg, N, N-dibutyl-2-butoxy-5-tert-octylaniline), hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene). As the auxiliary solvent, for example, the boiling point is about 30 ° C. or more, preferably 50 ° C.
An organic solvent having a temperature of about 160 ° C. or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
No. 63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol and JP-A-63-257747 and JP-A-63-257747 are used.
272248, and JP-A-1-80941, 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, It is preferable to add various preservatives or fungicides such as-(4-thiazolyl) benzimidazole.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers.

Suitable supports that can be used in the present invention are described, for example, in RD. No. 17643, page 28, No. 18
No. 716, from the right column on page 647 to the left column on page 648, and
307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less, more preferably 16 μm or less.
Further, the film swelling speed T _1/2 is preferably 30 seconds or less, and more preferably 20 seconds or less. The film thickness means a film thickness measured at 25 ° C. and a relative humidity of 55% (2 days), and the film swelling speed T
_1/2 can be measured according to techniques known in the art. For example, A. Green
n) et al. Photographic Science and
Engineering (Photogr.Sci.Eng.), Vol. 19, No. 2,
It can be measured by using a serometer (swelling meter) of the type described on pages 124 to 129, and T _1/2 is the maximum swollen film thickness reached when the color developing solution is processed at 30 ° C. for 3 minutes 15 seconds. Is defined as the saturated film thickness, and defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling speed T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is preferably from 150 to 400%. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above, according to the formula: (maximum swelling film thickness-film thickness) / film thickness.

In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm is preferably provided on the side opposite to the side having the emulsion layer. The back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent, and the like. The swelling ratio of this back layer is 150
~ 500% is preferred.

The color photographic light-sensitive material according to the present invention is prepared according to the RD. No. 17643, pp. 28-29, No. 18
716, left column to right column, and No. 307105
880-881.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine-based color developing agent. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-
N, N-diethylaniline, 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-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof are exemplified. Among these, in particular, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline sulfate is preferred. These compounds can be used in combination of two or more depending on the purpose.

The color developing solution may be a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride, a bromide, an iodide, a benzimidazole, a benzothiazole or a mercapto compound. It generally contains such a development inhibitor or antifoggant. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine, catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agents, aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, various chelating agents represented by phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cycloalkyl Hexane diamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene--
1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N
-Tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as typical examples.

When the reversal process is performed, color development is usually performed after black and white development. In this black and white developer,
Known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone and aminophenols such as N-methyl-p-aminophenol can be used alone or in combination. . The color developing solution and the black-and-white developing solution generally have a pH of 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 liters or less per square meter of the photographic material, and can be reduced to 500 mL or less by reducing the bromide ion concentration in the replenishing solution. You can also. 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 contact area between the photographic processing solution and air in the processing tank can be represented by the following aperture ratio. That is, aperture ratio = contact area (cm ² ) between processing liquid and air ÷ capacity of processing liquid (cm ³ ) The above-mentioned opening ratio is preferably 0.1 or less, more preferably 0.001 to 0. .05. As a method of reducing the aperture ratio in this manner, in addition to providing a shield such as a floating lid on the surface of the photographic processing solution in the processing tank, Japanese Patent Application Laid-Open No.
No. 033, a method using a movable lid,
And a slit developing method described in JP-A-216050. Reducing the aperture ratio is not only in both the color development and black-and-white development steps, but also in the subsequent steps,
For example, it is preferably applied in all steps such as bleaching, bleach-fixing, fixing, washing with water, and stabilization. The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for the color developing process is usually set to 2 to 5 minutes. However, the processing time can be further reduced by using a high temperature and high pH and using a high concentration of the color developing agent. it can.

The photographic emulsion layer after color development is usually subjected to bleaching. 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 continuous bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, compounds of a polyvalent metal such as iron (III), peracids, quinones, and nitro compounds are used. Typical bleaching agents are organic complex salts of iron (III),
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid or citric acid, tartaric acid, malic acid, etc. Complex salts can be used. Among these, iron (III) complex salts of aminopolycarboxylic acid such as iron (III) complex salt of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. . 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 from 4.0 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent Nos. 1,290,812, 2,059,988, JP Nos. 53-32736, 53-57831, 53
No. 37418, No. 53-72623, No. 53-95
No. 630, No. 53-95731, No. 53-10423
No. 2, No. 53-124424, No. 53-141623
Compounds having a mercapto group or disulfide group described in Research Disclosure No. 17129 (July, 1978); thiazolidine derivatives described in JP-A-50-140129; -8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,706,5
No. 61; thiourea derivative; West German Patent No. 1,12
7,715; iodide salts described in JP-A-58-16235; West German Patent Nos. 966,410 and 2,748,4.
Polyoxyethylene compounds described in No. 30;
Polyamine compounds described in JP-A-5-8836; and JP-A-49-40943, JP-A-49-59644 and JP-A-53-96444.
No. 94927, No. 54-35727, No. 55-265
Nos. 06 and 58-163940; bromide ions and the like. Among them, a compound having a mercapto group or a disulfide group is preferred in view of a large accelerating effect, and in particular, U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and JP-A-53-95630.
Are preferred. Further, U.S. Pat.
The compounds described in JP 52,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

The bleaching solution and the bleach-fixing solution preferably contain an organic acid in addition to the above compounds for the purpose of preventing bleaching stain. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, specifically acetic acid,
Propionic acid, hydroxyacetic acid and the like are preferred.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide. Is common, and in particular, ammonium thiosulfate can be used most widely. It is also preferable to use a combination of a thiosulfate and a thiocyanate, a thioether-based compound, thiourea, or the like. As a preservative of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct, or a sulfinic acid compound described in EP-A-294769A is preferable. Further, it is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixing solution or the bleach-fixing solution contains a compound having a pKa of 6.0 to 9.0, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, It is preferable to add imidazoles such as methyl imidazole in an amount of 0.1 to 10 mol / l.

The total time of the desilvering step is preferably shorter as long as the desilvering failure does not occur. Preferred time is 1 minute to 3
Minutes, more preferably 1 to 2 minutes. Further, the processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method of strengthening the stirring, a method described in JP-A-62-183460, in which a jet of a processing solution is made to impinge on the emulsion surface of a light-sensitive material, or a method using a rotating means described in JP-A-62-183461, is used. A method for improving the effect, a method for moving the photosensitive material while bringing the wiper blade provided in the solution into contact with the emulsion surface, and making the emulsion surface turbulent to improve the stirring effect, and a circulation of the entire processing solution. There is a method of increasing the flow rate. Such stirring improving means include a bleaching solution, a bleach-fixing solution,
It is effective in any of the fixing solutions. It is considered that improving the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and as a result, increases the desilvering speed. Further, the above-described means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator.

The automatic developing machine used for the light-sensitive material of the present invention is described in JP-A-60-191257 and JP-A-60-19125.
No. 8, No. 60-191259. JP-A-60-1
As described in Japanese Patent No. 91257, such a conveying means can significantly reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing liquid from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely.
Of these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture a.
nd Television Engineers, vol. 64, p. 248-2
53 (May 1955). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be significantly reduced, but bacteria increase due to an increase in the residence time of water in the tank, and the generated floating substances adhere to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. Japanese Patent Application Laid-Open No. 57-8
No. 542, chlorinated fungicides such as isothiazolone compounds and thiabendazoles, chlorinated sodium isocyanurate, and other benzotriazoles. "Sterilization, Sterilization, and Mold Prevention Techniques of Microorganisms" edited by the Sanitary Technology Association (1982).
986) can also be used.

The pH of the washing water in the processing of the light-sensitive material of the present invention is from 4 to 9, preferably from 5 to 8. The washing temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the use, etc., but are generally at 15 to 45 ° C. for 20 seconds to 10 minutes,
Preferably, a range of 30 seconds to 5 minutes at 25 to 40 ° C is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization process, JP-A-57-8543 and 58-58
All known methods described in JP-A-14834 and JP-A-60-220345 can be used.

In some cases, a stabilization treatment may be performed after the water washing treatment. For example, a stabilization treatment containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photography, may be used. Baths can be mentioned. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the washing and / or replenishment of the stabilizing solution can be reused in other steps such as a desilvering step.

In the processing using an automatic developing machine or the like, when the above-mentioned processing solutions are concentrated by evaporation, it is preferable to add water to correct the concentration.

In the silver halide color light-sensitive material of the present invention, a color developing agent may be incorporated for the purpose of simplifying and speeding up the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, U.S. Pat.
No. 342,597, indoaniline compounds, No. 3,342,599, Research Disclosure
Nos. 14,850 and 15,159, Schiff base compounds, aldol compounds, described in US Pat. No. 13,924, metal salt complexes described in U.S. Pat. No. 3,719,492, There can be mentioned urethane compounds described in JP-A-135628.

The silver halide color light-sensitive material of the present invention comprises:
If necessary, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339 and JP-A-57-14.
Nos. 4547 and 58-115438.

Various processing solutions in the present invention may be used at a temperature of 10 ° C. to 50 ° C.
Used at ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature promotes the processing and shortens the processing time, and a lower temperature achieves an improvement in the image quality and an improvement in the stability of the processing solution. be able to.

The silver halide light-sensitive material of the present invention is disclosed in US Pat. No. 4,500,626 and JP-A-60-1334.
No. 49, 59-218443, 61-23805
No. 6, EP 210,660 A2 and the like.

The silver halide light-sensitive material of the present invention, when applied to a film unit with a lens described in, for example, Japanese Patent Publication No. 2-3261 and Japanese Utility Model Publication No. 3-39784, easily exerts its effects and is effective. It is.

[0138]

Next, the present invention will be described in more detail by way of examples, but embodiments of the present invention are not limited thereto.

Embodiment 1 First, using known technology, $ 1
Silver iodobromide was prepared by grain formation of 11｝ tabular, {100｝ tabular, and cubic emulsions. Then, the following ExS-9
Sensitizing dye, potassium thiocyanate, potassium chloroaurate and sodium thiosulfate were added and the mixture was aged at 65 ° C. for spectral and chemical sensitization. The amounts of the various additives and the aging time were adjusted so that the sensitivity at 1/100 second exposure was the highest. Table 2 summarizes these emulsion grains.

[0140]

[Table 2]

On a cellulose triacetate film support having an undercoat, each layer having the following composition was applied in multiple layers to prepare a sample 101 as a multilayer color photosensitive material.

(Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: Gelatin hardener ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and the silver halide indicates the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol units per mol of silver halide in the same layer.

First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.355 Gelatin 1.70 ExM-1 0.10 ExF-1 2.0 × 10 ^-3 Solid Disperse Dye ExF-2 0.030 Solid Disperse Dye ExF-3 0.040 HBS-1 0.15 HBS-2 0.02.

Second layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A silver 0.02 silver iodobromide emulsion B silver 0.05 ExS-1 3.3 × 10 ^-4 ExS-2 1.4 × 10 ^-5 ExS-3 4.6 × 10 ^-4 ExC-1 0.11 ExC-2 0.02 ExC-3 0.04 ExC-4 0.07 ExC-5 0.020 ExC-6 0.010 ExM-4 0.005 ExY-1 0.01 Cpd-2 0.025 HBS-1 0.10 Gelatin 1.10.

Third layer (medium-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion B silver 0.32 silver iodobromide emulsion C silver 0.32 ExS-1 4.2 × 10 ^-4 ExS-2 1.8 × 10 ^-5 ExS-3 5.9 × 10 ^-4 ExC-1 0.18 ExC-2 0.05 ExC-3 0.06 ExC-4 0.07 ExC-5 0.02 ExC-6 0.02 ExM-4 0.02 ExY-1 0.005 Cpd-4 0.02 Cpd-2 0.02 HBS-1 0.10 Gelatin 0.80.

Fourth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 0.27 ExS-1 3.5 × 10 ^-4 ExS-2 1.5 × 10 ^-5 ExS-3 4.9 × 10 ^-4 ExC-1 0.02 ExC-2 0.018 ExC-3 0.015 ExC-6 0.001 ExC-7 0.010 ExM-4 0.003 Cpd-2 0.040 Cpd-40 0.040 HBS-1 0.22 HBS-2 0.050 gelatin 1.10.

Fifth layer (intermediate layer) Cpd-1 0.060 Solid disperse dye ExF-4 0.030 HBS-1 0.040 Polyethyl acrylate latex 0.15 Gelatin 1.10.

Sixth layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion E silver 0.15 silver iodobromide emulsion F silver 0.102 silver iodobromide emulsion G silver 0.15 ExS-7 7.5 × 10 ^-4 ExS-8 3.4 × 10 ^-4 ExS-4 2.5 × 10 ^-5 ExS-5 9.0 × 10 ^-5 ExS-6 4.3 × 10 ^-4 ExM-3 0.30 ExM-4 0.09 ExY-1 0.01 ExY-5 0.0020 HBS-1 0.30 HBS-3 0.015 Cpd-4 0.010 Gelatin 0.95.

Seventh Layer (Medium Speed Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion G Silver 0.2 Silver Iodobromide Emulsion H Silver 0.2 ExS-4 3.6 × 10 ^-5 ExS-7 1.7 × 10 ^-4 ExS-8 8.0 × 10 ^-4 ExC-8 0.0020 ExM-3 0.12 ExM-4 0.02 ExY-1 0.02 ExY-4 0.005 ExY-5 0.002 Cpd-4 0.015 HBS-1 0.13 HBS-3 4.4 × 10 ^-3 gelatin 0.80.

Eighth Layer (High-Sensitivity Red-Sensitive Emulsion Layer) Silver Iodobromide Emulsion I Silver 0.28 ExS-4 6.3 × 10 ^-5 ExS-7 1.7 × 10 ^-4 ExS-8 7.8 × 10 ^-4 ExC-6 0.01 ExM-4 0.02 ExM-2 0.005 ExM-5 0.001 ExM-6 0.001 ExM-3 0.04 Cpd-3 0.001 Cpd-40 0.040 HBS-1 0.25 polyethyl acrylate latex 0.15 gelatin 1.33.

Ninth Layer (Yellow Filter Layer) Yellow Colloidal Silver Silver 0.015 Cpd-1 0.16 Solid Disperse Dye ExF-5 0.060 Solid Disperse Dye ExF-6 0.060 Oil-soluble Dye ExF-7 010 HBS-1 0.60 Gelatin 0.60.

Tenth layer (low-sensitivity blue-sensitive emulsion layer) Emulsion See Tables 2 and 4. ExS-9 8.4 × 10 ^-4 ExC-1 0.03 ExC-8 7.0 × 10 ^-3 ExY-1 0.07 ExY-2 0.72 ExY-3 0.02 ExY-4 0.01 Cpd-2 0.005 Cpd-4 0.005 Cpd-3 0.004 UV-2 0.054 UV-30. 054 HBS-1 0.28 gelatin 2.60.

Eleventh layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J silver 0.24 ExS-9 6.0 × 10 ^-4 ExY-2 0.005 ExY-3 0.24 ExY-40 .0050 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 Cpd-4 5.0 × 10 ^-3 UV-2 0.012 UV-3 0.012 HBS-1 0.075 Gelatin 0.55 .

Twelfth Layer (First Protective Layer) Silver Iodobromide Emulsion K Silver 0.10 UV-1 0.13 UV-2 0.10 UV-3 0.16 UV-4 0.025 ExF-80 0.03 ExF-9 0.005 ExF-10 0.005 ExF-10 0.02 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 Gelatin 1.8.

13th layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 0.04 B-2 (1.7 μm diameter) 0.09 B-3 0.13 ES- 1 0.20 Gelatin 0.70.

In order to improve the storability, processing property, pressure resistance, fungicide / antibacterial property, antistatic property and coatability of each layer, W-1 to W-3, B-4 to B- 6, F-
1 to F-18 and iron salts, lead salts, gold salts, platinum salts, palladium salts, iridium salts, and rhodium salts.

Average Ag of Emulsions A to K Used in the Samples
The I content and particle size are shown in Table 3 below.

[0158]

[Table 3]

In Table 3, (1) Emulsion J was subjected to reduction sensitization during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions C, D and GI were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Sensitization has been applied. (3) For preparing tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) When a high-pressure electron microscope is used for the tabular grains, dislocation lines as described in JP-A-3-237450 are observed. (5) Emulsions A to I contain optimal amounts of Rh, Ir, and Fe. The tabularity is defined as Dc / t ² , where Dc is the average equivalent circle diameter in the projected area of the tabular grains and t is the average thickness of the tabular grains.

Preparation of Dispersion of Organic Solid Disperse Dye
xF-2 was dispersed by the following method. That is, 21.7 mL of water
Then, 3 mL of a 5% aqueous solution of p-octylphenoxyethoxyethoxyethoxyethanesulfonic acid sodium salt and 0.5 g of a 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10) were placed in a 700 mL pot mill, and the dye ExF-2 was added. 5.0 g and 500 mL of zirconium oxide beads (diameter 1 mm) were added, and the contents were dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After dispersing, take out the contents, 12.5
% Gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the fine dye particles was 0.44 μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the fine dye particles are 0.24 μm, 0.45 μm, and 0.52 μm, respectively.
m. ExF-5 was dispersed by the microprecipitation dispersion method described in Example 1 of EP-A-549,489A. The average particle size was 0.06 μm.

The compounds used for each layer of the above sample are shown below.

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The emulsion composition of the tenth layer (low-sensitivity blue-sensitive emulsion layer) was as shown in Table 4. In addition, this first
With respect to the 0 layer, samples prepared when a solution in which the emulsion of the 10th layer and other additives were all mixed were kept for 1 hour (A) and for 10 hours (B) after coating was applied. 101A, 101B to 106A, 106B
Was prepared. During this holding time, the mixed solution was 4 times.
Stirring was continued at 0 ° C.

[0181]

[Table 4]

These samples were exposed to sensitometry (1/100 second) and subjected to the following color development processing. Note that the color development process was performed in two processes of 2 minutes and 15 seconds and 3 minutes and 15 seconds.

(Processing Step) Process Processing Time Processing Temperature Color Development 2 min 15 sec 38 ° C. or 3 min 15 sec 38 ° Bleaching 1 min 00 sec 38 ° Bleaching Fix 3 min 15 sec 38 ° C. Rinse (1) 40 sec 35 ° C water washing (2) 1 minute 00 seconds 35 ° C Stability 40 seconds 38 ° C Drying 1 minute 15 seconds 55 ° C.

Next, the composition of the processing solution will be described. (Color developing solution) (unit: g) Diethylenetriaminepentaacetic acid 1.0 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 5 mg hydroxylamine sulfate 2.4 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 Add water and add 1.0 L pH (to potassium hydroxide and sulfuric acid) Adjusted) 10.05.

(Bleaching solution) (Unit: g) Sodium ferric ethylenediaminetetraacetate dihydrate 120.0 Disodium ethylenediaminetetraacetate 10.0 Ammonium bromide 100.0 Ammonium sulfate 10.0 Bleaching accelerator 0.005 mol _{(CH 3) 2 N-CH} 2 -CH 2 -S-S-CH 2 -CH 2 -N (CH 3) 2 · 2HCl aqueous ammonia (27%) 15.0 mL water to make 1.0 L pH (ammonia (Adjust with water and sulfuric acid) 6.3.

(Bleach-fixing solution) (unit: g) Ferric ammonium ethylenediaminetetraacetate dihydrate 50.0 Disodium ethylenediaminetetraacetate 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (700 g / L) 240.0 mL Aqueous ammonia (27%) 6.0 mL Add water 1.0 L pH (adjusted with aqueous ammonia and sulfuric acid) 7.2.

(Washing water) Tap water was replaced with H-type strongly acidic cation exchange resin (Amberlite IR- manufactured by Rohm and Haas Company).
120B) and a mixed bed column packed with an OH type strongly basic anion exchange resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentration to 3 m.
g / L or less, followed by sodium isocyanurate dichloride 20 mg / L and sodium sulfate 0.15 g / L
Was added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) (Unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 Disodium ethylenediaminetetraacetate 0.05 1, 2,4-Triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Add water 1.0 L pH 8.5.

The concentration of the treated sample was measured with a blue filter. The sensitivity is defined as the reciprocal of the exposure amount giving a density of 2.5 (SD2.5), and is shown in Table 5 as a relative value with the value of the 2'15 "treatment of sample 101A being 100.

[0190]

[Table 5]

From Table 5, it can be seen that Sample 101 prepared using the emulsion containing only the {111} tabular grains had a time (from the time when the solution in which the emulsion of the tenth layer and all other additives were mixed) was prepared until the solution was applied ( It can be seen from the comparison of the A and B samples that there is no change in sensitivity even when the time is referred to as “aging time”. However, the sensitivity is lower than the sample of the present invention. Also 2
The difference (ΔSD2.5) from the sensitivity of the processing for 15 minutes is large, and the processing time is unfavorably large with respect to the development processability.

Sample 102A in which cubic emulsion was mixed with sample 101A had high sensitivity to 101A and improved developability, but the longer the aging time, the lower the sensitivity was, and the lower the sensitivity. Sample 102 is inferior
It can be seen from the comparison with the result of B.

It can be seen from the comparison between Samples A and B that Sample 103 prepared using an emulsion of only {100} tabular grains had no change in sensitivity even when the aging time was increased. Further, although the developing property is slightly improved with respect to the sample 101,
Lower sensitivity than the sample of the present invention.

The sample 104A of the present invention in which the cubic emulsion was mixed with the sample 103A had high sensitivity to 103A and improved development processing properties. It is clear from the comparison with the result of 104B that the sample is stable.

It can be seen that Sample 105, which has a smaller coefficient of variation of the equivalent circle diameter of {100} tabular grains than Sample 104, is superior to Sample 104 in all of sensitivity, development processing property, and production stability.

The aspect ratio of {100} tabular grains is 2.
0 sample 106 is different from samples 101 to 103
It can be seen that the sample 104 or 105 is low in sensitivity, but excellent in sensitivity, development processability and production stability.

Embodiment 2 FIG. Emulsions 1 to 5 used in Example 1
Was used to prepare a multilayer color photosensitive material comprising the following layers on an undercoated cellulose triacetate film support having a thickness of 127 μm. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the use described.

First layer: Antihalation layer Black colloidal silver 0.28 g Gelatin 2.20 g Ultraviolet absorber U-1 0.27 g Ultraviolet absorber U-3 0.08 g Ultraviolet absorber U-4 0.08 g High boiling organic solvent Oil-1 0.29 g Dye D-3 10.0 mg Dye D-5 0.12 mg.

Second layer: Intermediate layer Gelatin 0.38 g Compound Cpd-H 3.5 mg Ultraviolet absorber U-2 3.0 mg High boiling organic solvent Oil-4 0.06 g Dye D-1 0.01 g Dye D-2 0.01 g Dye D- 4 0.01 g.

Third layer: Intermediate layer Yellow colloidal silver Amount of silver 0.007 g Gelatin 0.40 g Compound Cpd-J 1.0 mg High boiling organic solvent Oil-3 2.0 mg.

Fourth layer: low-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion A silver amount 0.27 g silver iodobromide emulsion B silver amount 0.23 g silver iodobromide emulsion C silver amount 0.23 g gelatin 0.85 g coupler C-1 0.04 g Coupler C-2 0.09 g High boiling organic solvent Oil-2 0.09 g.

Fifth layer: middle-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion D Silver amount 0.43 g Gelatin 0.65 g Coupler C-1 0.05 g Coupler C-2 0.11 g High boiling organic solvent Oil-2 0.09 g.

Sixth layer: High-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion E Silver amount 0.50 g Gelatin 1.56 g Coupler C-3 0.63 g Additive P-1 0.16 g High boiling organic solvent Oil-2 0.04 g.

Seventh layer: Intermediate layer Gelatin 0.50 g Compound Cpd-D 0.02 g Compound Cpd-J 0.02 g High boiling organic solvent Oil-3 0.04 g.

Eighth layer: Intermediate layer Yellow colloidal silver Silver amount 0.01 g Gelatin 0.90 g Compound Cpd-J 0.07 g High boiling organic solvent Oil-3 0.15 g.

Ninth layer: low-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion F silver content 0.42 g silver iodobromide emulsion G silver content 0.38 g silver iodobromide emulsion H silver content 0.32 g Shell type fine grain silver bromide emulsion (average particle size 0.11 μm) Silver amount 0.08 g Gelatin 1.53 g Coupler C-7 0.07 g Coupler C-8 0.17 g Compound Cpd-B 0.30 mg Compound Cpd-C 2.00 mg Polymer latex P-2 0.02 g High boiling organic solvent Oil-2 0.10 g.

Tenth layer: medium-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion I Silver amount 0.16 g Silver iodobromide emulsion J Silver amount 0.34 g Gelatin 0.57 g Coupler C-4 0.20 g Compound Cpd-B 0.03 g Polymer latex P-2 0.01 g High boiling organic solvent Oil-2 0.01 g.

Eleventh layer: High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion K Silver amount 0.44 g Gelatin 0.69 g Coupler C-4 0.34 g Compound Cpd-B 0.06 g Polymer latex P-2 0.01 g High boiling organic solvent Oil -2 0.02 g.

Twelfth layer: Yellow filter layer Yellow colloidal silver Amount of silver 0.002 g Gelatin 0.73 g Microcrystal dispersion of dye E-1 0.24 g Compound Cpd-J 0.06 g High boiling organic solvent Oil-3 0.09 g Polymer M-1 0.23g.

Thirteenth layer: low-sensitivity blue-sensitive emulsion layer Emulsion See Tables 2 and 7. Gelatin 0.55 g Coupler C-5 0.20 g Coupler C-6 4.00 g Coupler C-9 0.02 g Compound Cpd-E 0.07 g.

Fourteenth layer: Medium-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion L Silver amount 0.06 g Silver iodobromide emulsion M Silver amount 0.10 g Gelatin 0.75 g Coupler C-5 0.35 g Coupler C-6 5.00 g Coupler C -9 0.30 g Compound Cpd-E 0.04 g.

Fifteenth layer: high-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion N Silver amount 0.20 g Silver iodobromide emulsion O Silver amount 0.02 g Gelatin 2.40 g Coupler C-6 0.09 g Coupler C-9 0.90 g Compound Cpd -E 0.09 g Compound Cpd-K 0.05 mg High boiling organic solvent Oil-2 0.40 g Additive P-2 0.10 g.

Sixteenth layer: First protective layer Gelatin 1.00 g UV absorber U-1 0.10 g UV absorber U-2 0.03 g UV absorber U-5 0.20 g Compound Cpd-F 0.40 g Compound Cpd-J 0.06 g High boiling organic solvent Oil-3 0.30 g.

17th layer: 2nd protective layer Fine grain silver iodobromide emulsion (average particle size 0.06 μm, AgI content 1 mol%) Silver amount 0.10 g Gelatin 0.70 g UV absorber U-1 0.06 g UV absorber U- 2 0.02 g UV absorber U-5 0.12 g High boiling organic solvent Oil-1 0.07 g.

[0215]

In addition to the above composition, additives F-1 to F
-7, F-10 to F-11 were added. Further, in addition to the above composition, gelatin hardener H-1 and surfactants W-3, W-4, W-5 and W-6 for coating and emulsification were added to each layer.

Further, phenol and 1,1 are used as antiseptic and antifungal agents.
2-Benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, p-hydroxybenzoic acid butyl ester were added.

Table 6 shows the photosensitive emulsions used for the samples.

[0219]

[Table 6]

(Preparation of Dispersion of Organic Solid Disperse Dye) Dye E-1 was dispersed by the following method. That is, 70 g of water and W-4 were added to 1400 g of a dye wet cake containing 30% of water, followed by stirring to obtain a slurry having a dye concentration of 30%. Next, Ultra Viscomil (UVM-2) manufactured by Imex Co., Ltd.
Fill 1700 mL of zirconia beads with an average particle size of 0.5 mm,
Peripheral speed about 10m / sec through slurry, discharge rate 0.5L / min
Milled for 8 hours. The beads were removed by filtration, heated at 90 ° C. for 10 hours for stabilization, and diluted with water and gelatin to a dye concentration of 3%. The average particle size of the obtained dye fine particles is
0.4 μm, and the size of the particle size distribution (particle size standard deviation x 100
/ Average particle size) was 18%.

The emulsion constitution of the thirteenth layer (low-sensitivity blue-sensitive emulsion layer) was as shown in Table 7. In addition, this first
Regarding the three layers, samples prepared when a solution in which the emulsion of the thirteenth layer and other additives were all mixed were kept for 1 hour (A) and for 10 hours (B) from the time of coating until coating. 201A, 201B to 206A, 206B
Was prepared. During this holding time, the mixed solution was 4 times.
Stirring was continued at 0 ° C.

[0222]

[Table 7]

The fabricated samples 201A, B to 206A, B
2000 Lux, 1/50 second, color temperature 480
Wedge exposure was carried out using a 0K white light source, the following development processing was carried out, sensitometry was carried out, and the sensitivity was measured by the relative value of the reciprocal of the relative exposure amount giving a yellow density of 2.0.

The development processing conditions used are as follows. (Processing) Processing process Time Temperature Tank capacity Replenishment amount First development 6 minutes 38 ° C 12L 2200mL / m ² First water wash 2 minutes 38 ° C 4L 7500mL / m ² Inversion 2 minutes 38 ° C 4L 1100mL / m ² Color development 6 minutes 38 ° C 12L 2200mL / m ² Pre-bleaching 2 minutes 38 ° C 4L 1100mL / m ² Bleaching 6 minutes 38 ° C 2L 220mL / m ² Fixed 4 minutes 38 ° C 8L 1100mL / m ² Second water washing 4 minutes 38 ° C 8L 7500 mL / m ² Final rinse 1 minute 25 ° C ² L 1100 mL / m ² .

The composition of each processing solution was as follows. [First developer] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 1.5 g 1.5 g Diethylenetriaminepentaacetic acid / 5 sodium salt 2.0 g 2.0 g Sodium sulfite 30 g 30 g Potassium hydroquinone monosulfonate 20 g 20 g Potassium carbonate 15 g 20 g Sodium bicarbonate 12 g 15 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g 2.0 g Potassium bromide 2.5 g 1.4 g Potassium thiocyanate 1.2 g 1.2 g Potassium iodide 2.0 mg-Diethylene glycol 13 g 15 g Water was added to 1000 mL 1000 mL pH 9.60 9.60 The pH was adjusted with sulfuric acid or potassium hydroxide.

[Inversion liquid] [Tank liquid] [Replenishment liquid] Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 3.0 g Same as tank liquid Stannous chloride dihydrate 1.0 g p-amino acid Phenol 0.1g Sodium hydroxide 8g Glacial acetic acid 15mL Water was added to 1000mL pH 6.00 The pH was adjusted with acetic acid or sodium hydroxide.

[Color developing solution] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 2.0 g 2.0 g Sodium sulfite 7.0 g 7.0 g Trisodium phosphate / 12 hydrate 36g 36g Potassium bromide 1.0g-Potassium iodide 90mg-Sodium hydroxide 3.0g 3.0g Citrazinic acid 1.5g 1.5g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline 3/2 sulfuric acid monohydrate 11g 11g 3,6-dithiaoctane-1,8-diol 1.0g 1.0g Water was added to 1000mL 1000mL pH 11.80 12.00 The pH was adjusted with sulfuric acid or potassium hydroxide.

[Pre-bleaching] [Tank liquid] [Replenisher] Ethylenediaminetetraacetic acid disodium salt dihydrate 8.0 g 8.0 g sodium sulfite 6.0 g 8.0 g 1-thioglycerol 0.4 g 0.4 g sodium formaldehyde sodium bisulfite adduct 30g 35g Water was added and 1000mL 1000mL pH 6.30 6.10 pH was adjusted with acetic acid or sodium hydroxide.

[Bleaching solution] [Tank solution] [Replenisher] Ethylenediaminetetraacetic acid disodium salt dihydrate 2.0 g 4.0 g Ethylenediaminetetraacetic acid Fe (III) ammonium ammonium dihydrate 120 g 240 g potassium bromide 100 g 200 g Ammonium nitrate 10 g 20 g Water was added 1000 mL 1000 mL pH 5.70 5.50 The pH was adjusted with nitric acid or sodium hydroxide.

[Fixing solution] [Tank solution] [Replenisher] Ammonium thiosulfate 80 g To the tank solution was added the same sodium sulfite 5.0 g sodium bisulfite 5.0 g water, and the mixture was adjusted to 1000 mL pH 6.60 with acetic acid or aqueous ammonia.

[Stabilizing solution] [Tank solution] [Replenishing solution] 1,2-benzisothiazolin-3-one 0.02 g 0.03 g polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 g 0.3 g polymaleic acid ( Average molecular weight 2,000) 0.1 g 0.15 g Water was added to make 1000 mL 1000 mL pH 7.0 7.0.

The chemical formulas and the like of the compounds used in Example 2 are as follows.

[0233]

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[0234]

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[0235]

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[0236]

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[0237]

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[0238]

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[0239]

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[0240]

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[0241]

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[0242]

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[0243]

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[0244]

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[0245]

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[0246]

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[0247]

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[0248]

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Similarly to the result of Example 1, it was found that the silver halide color photographic light-sensitive material of the present invention has excellent development processing property, wide latitude, and excellent production stability.

Embodiment 3 FIG. After performing corona discharge treatment on the surface of a support obtained by coating both sides of the paper with a polyethylene resin, a gelatin subbing layer containing sodium dodecylbenzenesulfonate is provided, and a photographic composition of the first to seventh layers is further provided. The layers were sequentially coated to prepare a sample (301) of a silver halide color photographic light-sensitive material having the following layer constitution. The coating solution for each photographic constituent layer was prepared as follows.

Preparation of Coating Solution for Fifth Layer 300 g of cyan coupler (ExC-1), 250 g of color image stabilizer (Cpd-1), 1 color image stabilizer (Cpd-9)
0 g, color image stabilizer (Cpd-10) 10 g, color image stabilizer (Cpd-12) 20 g, ultraviolet absorber (UV-1) 1
4 g, UV absorber (UV-2) 50 g, UV absorber (UV-3) 40 g and UV absorber (UV-4) 6
0 g was dissolved in 230 g of a solvent (Solv-6) and 350 mL of ethyl acetate, and this solution was added to a surfactant (Cpd-
Emulsified dispersion C was prepared by emulsifying and dispersing in 6500 g of a 10% aqueous gelatin solution containing 25 g of 14).

[0252]

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On the other hand, the silver chlorobromide emulsion C shown in Table 8 was used. Samples 301A and B and 302A and B shown in Table 9 were produced. Here, A and B indicate the results of the holding process performed in the first embodiment.

[0254]

[Table 8]

[0255]

[Table 9]

This emulsion has a red-sensitive sensitizing dye G shown below.
And H per mole of silver are respectively 12.0 to 10 ^-5 mol per mol of the 9.0 × 10 ^-5 mol, respectively, also for the small size emulsion C to the large size emulsion C.
The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer.

The emulsified dispersion C and the silver chlorobromide emulsion C were mixed and dissolved to prepare a fifth layer coating solution having the composition described below. The emulsion coating amount indicates a coating amount in terms of silver amount.

The coating solutions for the first to fourth layers and the sixth to seventh layers were prepared in the same manner as the coating solution for the fifth layer. Examples of gelatin hardeners for each layer include H-1, H-2 and H-3.
Was used.

Further, Ab-1, Ab-2, Ab-
3 and Ab-4 in a total amount of 15.0 mg /
^{m 2, 60.0mg / m 2,} 5.0mg / m 2 and 1
It was added to a concentration of 0.0 mg / m ² .

[0260]

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The following spectral sensitizing dye and crystal habit controlling agent 1 were used in the silver chlorobromide emulsion of each photosensitive emulsion layer.

Blue-sensitive emulsion layer

[0263]

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(Sensitizing dyes A and C were used in an amount of 0.42 × 1
^0-4 mol and 0.50 × 10 ^-4 mol were added to the small-sized emulsion. Sensitizing dye B was added in an amount of 3.4 × 10 ⁻⁴ mol for the large-size emulsion and 4.1 × 10 ⁻⁴ mol for the small-size emulsion per mol of silver halide).

Green-sensitive emulsion layer

[0266]

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(Sensitizing dye D was added per mole of silver halide,
3.0 × 10 for large emulsions ^-FourMol, small size
3.6 × 10 for emulsion^-FourMol and sensitizing dye E
Per mole of silver halide and for large emulsions
4.0 × 10^-Five7.0 × for mole, small size emulsions
10^-FiveMole of sensitizing dye F per mole of silver halide.
2.0 × 10^-FourMol, small sa
2.8 × 10^-FourMol).

Red-sensitive emulsion layer

[0269]

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(Sensitizing dyes G and H were converted to silver halide 1
8.0 × 10 ^-5 mol of the large-size emulsion and 10.7 × 10 ^-5 mol of the small-size emulsion were added per mol).

Further, the following compound I was added to the red-sensitive emulsion layer in an amount of 3.0 × 10 ^-3 mol per mol of silver halide.

[0272]

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Also, 1- (3-methylureidophenyl) -5-mercaptontetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer in an amount of 3.3 × per mole of silver halide. 10 ^-4 mol, 1.0 × 10
^-3 mol and 5.9 × 10 ^-4 mol were added.

Furthermore, the second layer, the fourth layer, the sixth layer, and the
0.2mg / m each for 7 layers ^Two0.2 mg / m
^Two, 0.6 mg / m^Two0.1 mg / m^TwoSo that
Was added.

Also, 4-hydroxy-6-methyl-1,3,3a, 7 was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
Tetrazindene was added in an amount of 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide.

The red-sensitive emulsion layer contained 0.05 g / weight of a copolymer latex of methacrylic acid and butyl acrylate (weight ratio 1: 1, average molecular weight 2,000,000 to 400,000).
m ² was added.

In the second, fourth and sixth layers, disodium catechol-3,5-disulfonate was added in an amount of 6% each.
mg / m ² , 6 mg / m ² and 18 mg / m ² .

In order to prevent irradiation, the following dyes were added (in parentheses, the coating amount is shown).

[0279]

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(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion is
It represents the silver equivalent coating amount.

Support Polyethylene resin laminated paper 白色 White pigment (TiO ₂ ;
Content: 16% by weight, ZnO; content: 4% by weight), fluorescent whitening agent (4,4'-bis (5-methylbenzoxazolyl) stilbene; content: 0.03% by weight), bluish dye ( Ultramarine blue).

First Layer (Blue-Sensitive Emulsion Layer) Silver chlorobromide emulsion A (cubic, 5: 5 mixture of large-size emulsion A having an average grain size of 0.72 μm and small-size emulsion A having an average grain size of 0.60 μm (silver mole The coefficient of variation of the grain size distribution was 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride in each emulsion. ) 0.24 Gelatin 1.25 Yellow coupler (ExY) 0.57 Color image stabilizer (Cpd-1) 0.07 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0 0.07 Color image stabilizer (Cpd-8) 0.02 Solvent (Solv-1) 0.21.

Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture prevention layer (Cpd-4) 0.09 Color image stabilizer (Cpd-5) 0.018 Color image stabilizer (Cpd-6) 0.13 Color image stabilizer (Cpd-7) 0.01 Solvent (Solv-1) 0.06 Solvent (Solv-2) 0.22.

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion B (cubic, 1: 3 mixture of large-size emulsion B having an average grain size of 0.45 μm and small-size emulsion B having an average grain size of 0.45 μm (silver mole The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively, and 0.4 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride in each size emulsion. 0.1) Gelatin 1.36 Magenta coupler (ExM) 0.15 UV absorber (UV-A) 0.14 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd-4) 002 Color image stabilizer (Cpd-6) 0.09 Color image stabilizer (Cpd-8) 0.02 Color image stabilizer (Cpd-9) 0.03 Color image stabilizer (Cpd-10) 0.01 colors Image stabilizer (Cpd-11) 0.0001 Solvent (Solv-3) 0 11 solvent (Solv-4) 0.22 solvent (Solv-5) 0.20.

Fourth layer (color mixture prevention layer) Gelatin 0.71 Color mixture prevention layer (Cpd-4) 0.06 Color image stabilizer (Cpd-5) 0.013 Color image stabilizer (Cpd-6) 0.10 Color image stabilizer (Cpd-7) 0.007 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.16.

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion C (see Tables 8 and 9) 0.20 Gelatin 1.11 Cyan coupler (ExC-1) 0.30 Cyan coupler (ExC-2) 0.02 UV absorber (UV-A) 0.29 Color image stabilizer (Cpd-1) 0.25 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-12) 0.02 Solvent (Solv-6) 0.23.

Sixth layer (ultraviolet absorbing layer) Gelatin 0.46 Ultraviolet absorber (UV-B) 0.45 Solvent (Solv-7) 0.25.

Seventh layer (protective layer) Gelatin 1.00 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01.

The compounds used for each layer of the above sample are shown below.

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[0291]

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[0296]

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For each sample, a photometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K) was used.
A gray tone exposure was provided. The exposure at this time was performed so that the exposure amount was 250 CMS with an exposure time of 0.1 second.

Hereinafter, the processing steps will be described.

Process A The above photosensitive material 108 was processed into a roll having a width of 127 mm, and imagewise exposed using a minilab printer processor PP1258AR manufactured by Fuji Photo Film Co., Ltd .. Until double replenishment,
Continuous processing (running test) was performed. The processing using the running liquid was referred to as processing A.

Processing Step Temperature Time Replenishment amount ^* Color development 38.5 ° C 45 seconds 45mL Bleaching and fixing 38.0 ° C 45 seconds 35mL Rinse (1) 38.0 ° C 20 seconds-Rinse (2) 38.0 ° C 20 sec - rinse (3) ** 38.0 ° C. 20 seconds - rinse (4) rinse the replenishment rate ** Fuji Photo Film Co., Ltd. rinse cleaning system RC50D of ** 38.0 ° C. 30 seconds 121 mL * photosensitive material 1 m ² per Install in (3), take out the rinsing liquid from rinsing (3) and send it to reverse osmosis membrane module (RC50D) by pump. The permeated water obtained in the tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 mL / min, and the temperature was circulated for 10 hours a day.

(Rinsing was performed in a tank countercurrent system from (1) to (4)).

The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 mL 800 mL Dimethylpolysiloxane-based surfactant 0.1 g 0.1 g (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) Tri (isopropanol) amine 8.8 g 8.8 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Polyethylene glycol (molecular weight 300) 10.0 g 10.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.5 g 0.5 g Potassium chloride 10.0 g-potassium bromide 0.040 g 0.010 g Triazinylaminostilbene-based fluorescence 2.5 g 5.0 g Whitening agent (Hakor FWA-SF / Showa Chemical Co., Ltd.) Sodium sulfite 0.1 g 0.1 g Disodium-N, N-bis ( Sulfonatoethyl) hydroxyamine 8.5 g 11.1 g -Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-amino-4-aminoaniline / 3/2 sulfuric acid monohydrate 5.0 g 15.7 g Potassium carbonate 26.3 g 26.3 g water 1000 mL 1000 mL pH (adjusted at 25 ° C./potassium hydroxide and sulfuric acid) 10.15 12.50.

[Bleach-fixing solution] [Tank solution] [Replenisher] Water 700 mL 600 mL Iron (III) ammonium ethylenediaminetetraacetate 47.0 g 94.0 g 1.4 g 2.8 g m-carboxybenzeneflufinic acid 8 0.3 g 16.5 g nitric acid (67%) 16.5 g 33.0 g imidazole 14.6 g 29.2 g ammonium thiosulfate (750 g / l) 107.0 mL 214.0 mL ammonium sulfite 16.0 g 32.0 g ammonium bisulfite 23.1 g 46.2 g Add water 1000 mL 1000 mL pH (adjusted at 25 ° C./acetic acid and ammonium) 6.0 6.0.

[Rinse solution] [Tank solution] [Replenisher] 0.02 g 0.02 g of chlorinated sodium isocyanurate Deionized water (conductivity of 5 μs / cm or less) 1000 mL 1000 mL pH 6.5 6.5.

Samples 301A, B, 30
As a result of evaluating 2A and B, the silver halide color photographic light-sensitive material of the present invention was found to be similar to the result of Example 1 or 2.
It was found to have excellent development processing properties, a wide latitude, and excellent production stability.

[0306]

The silver halide color photographic light-sensitive material of the present invention has excellent development processing properties, a wide latitude, and excellent production stability.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 7/00 520 G03C 7/00 520 530 530

Claims (6)

[Claims] 1. A silver halide color photographic material having at least one silver halide emulsion layer on a support, wherein at least one of the emulsion layers contains a cubic grain emulsion and a {100} tabular grain emulsion. A silver halide color photographic light-sensitive material comprising: 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the number average grain thickness of said {100} tabular grains is 0.04 μm or more and 0.20 μm or less. 3. The silver halide color photographic light-sensitive material according to claim 1, wherein the number average aspect ratio of said {100} tabular grains is from 2.5 to 50. 4. The silver halide color photograph according to claim 1, wherein the coefficient of variation of the equivalent circle diameter of the {100} tabular grains is 1% or more and 20% or less. Photosensitive material. 5. The method according to claim 1, wherein at least one of the emulsion layers contains only two kinds of emulsions, namely, a cubic grain emulsion and a {100} tabular grain emulsion. The silver halide color photographic light-sensitive material described in the above. 6. The silver halide color photographic light-sensitive material according to claim 1, wherein the {100} tabular grains have dislocations.