JPH0321942A - Manufacture of silver halide color reversal photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance maximum density and graininess by adding to a reaction vessel the silver halide grains prepared outside there and then carrying out at least one part of grow of crystals in the vessel. CONSTITUTION:The crystal grow of silver halide grains is carried out in the reaction vessel for causing formation of silver halide nuclei and grow of crystals or in a mixing vessel also performing circulation with the reaction vessel, with out directly adding an aqueous solution of silver salts and an aqueous solution of halogen salts necessary for forming silver halide grains, thus permitting the grains not to be exposed to solutions high in silver ion concentration, and the obtained silver halide grains to be reduced in formation of fogged nuclei inside the grains, and accordingly, a color reversal photographic sensitive mate rial high in the maximum density and superior in graininess to be obtained.

Description

[Detailed Description of the Invention] (Prior Art) Color reversal photographic materials generally have not only high sensitivity but also high sensitivity.
High quality is required in terms of image quality such as gradation, contrast, color reproduction, graininess, and sharpness.

Color reversal photographic light-sensitive materials usually involve a process of black-and-white negative development (first development), a process of covering the remaining silver halide after the first development by a light or chemical method, and a process of covering the remaining silver halide after the first development. Color development (second
'4.1i (1) refers to processing through a series of steps including the step of developing (developing). In particular, the first developing step is an important The developing process is 1z.The developing solution in the first developing step contains silver halide solvents such as rhodan salts and sulfites, and in the first development, the particles are developed while being dissolved. Not only the latent image formed by the exposure, but also the fog nuclei pre-existing inside the particles are exposed and developed as the development time progresses.

In particular, fog inside the particles reduces the maximum density of the color image in a non-imagewise manner during the second development. Reducing fog nuclei is one important means for providing color reversal photographic materials with high maximum density and excellent graininess. but,
Conventional methods for producing silver halide grains have had the problem that fog nuclei cannot be avoided within the grains during the grain growth stage.

Generally speaking, silver halide grains are formed in a colloidal aqueous solution.
It is produced by reacting an aqueous silver salt solution with an aqueous halogen salt solution. In the single gene method, a protective colloid such as gelatin and a halogen salt aqueous solution are placed in a reaction vessel, and a silver salt aqueous solution is added thereto for a certain period of time while stirring, or a gelatin aqueous solution is placed in a reaction vessel and a halogen salt aqueous solution is added thereto. A double dienoto method is known in which a silver salt aqueous solution is added for a certain period of time, but in any case, the silver ion or halide ion concentration created by the silver salt aqueous solution and the halogen salt aqueous solution added to the reaction vessel is uneven, especially at high silver concentrations. The presence of ion-concentrated portions is a source of fogging nuclei generated by reduction inside the particles during particle growth. In order to prevent this, it is necessary to uniformly mix the silver ion or halogen ion concentration in the reaction vessel by quickly and uniformly mixing the chloride salt aqueous solution and the halogen salt aqueous solution supplied in the colloid aqueous solution to cause the reaction. is necessary. For example, in a method in which a halogen salt aqueous solution and a silver salt aqueous solution are added to the surface of a colloidal aqueous solution in a reaction vessel, areas with high concentrations of halogen ions and silver ions are generated near the addition positions of each reaction solution, and inside the particles. It has been difficult to produce silver halide grains with few fog nuclei. As a method to improve this local concentration bias, US Pat.
No. 5650, British Patent No. 1323464, US Patent No. 36
The technology disclosed in the 92283 bow is known. These methods include: 1. A reaction vessel filled with an aqueous colloid solution, a medium-sized cylinder having a slit in the wall, rotating a hollow }R reactor (the inside of which is filled with an aqueous colloid solution, and more preferably mixing). The chamber is divided into two upper and lower chambers by a disk.) is installed so that its axis of rotation is vertical, and a halogen salt aqueous solution and a silver salt aqueous solution are fed through supply pipes from the upper and lower open ends and rotated at high speed. The halogen salt aqueous solution and the silver salt aqueous solution supplied to the upper and lower chambers are diluted by the colloid aqueous solution filled in each chamber, respectively. In this method, silver halide particles produced by centrifugal force generated by the rotation of the mixer are discharged into a colloidal aqueous solution in a reaction vessel and grown.

Furthermore, Japanese Patent Publication No. 10545/1983 discloses a technique for preventing local concentration deviations. In this method, an aqueous halogen salt solution and an aqueous silver salt solution are separately fed into a reactor filled with an aqueous colloid solution from the open lower end of a mixer filled with an aqueous colloid solution through supply pipes. The reaction liquid is rapidly stirred and mixed by a lower stirring blade (turbine blade) installed in the mixer to grow silver halide, and then immediately stirred and mixed by a lower stirring blade (turbine blade) installed in the mixer. This is a technique in which silver halide grains elongated by a stirring blade are discharged from the opening of an upper mixer into an aqueous colloid solution in a reaction vessel. JP-A No. 57-92523 discloses a manufacturing method that similarly attempts to improve this non-uniformity of concentration. In this method, a halogen salt aqueous solution and a silver salt aqueous solution are separately supplied from the opened lower end of a reaction vessel filled with a colloidal aqueous solution to a mixer, the inside of which is filled with a colloidal aqueous solution. Both reaction solutions were diluted with the colloidal aqueous solution, and the reaction solutions were rapidly stirred and mixed using a lower stirring blade provided in a mixer, and immediately the d
In a production method or apparatus in which silver halide grains grown from an opening above the mixer are discharged into an aqueous colloid solution in a reaction vessel, both reaction solutions diluted with the aqueous colloid solution are passed through the gap between each blade of the stirring blades. The mixture is passed through a gap formed between the inner wall of the mixer and the outer side of the tip of the blade of the stirring blade, and the two reaction liquids are rapidly mixed in the gap and reacted. discloses a manufacturing method and apparatus for producing silver halide grains.

(Problem to be Solved by the Invention) However, with the manufacturing method and apparatus described so far, although it is possible to completely eliminate the local concentration non-uniformity of silver ions and halogens in the reaction vessel, This concentration non-uniformity still exists within the vessel, and there is particularly a fairly large concentration distribution near the nozzles that supply the silver salt aqueous solution and halogen salt aqueous solution, as well as at the bottom of the stirring blade and in the stirring section. Furthermore, when the silver halide grains supplied to the mixer together with the protective colloid grow in places with such non-uniform concentration distribution, they come to have fog nuclei inside the grains.

In other words, in these manufacturing methods and apparatuses, a concentration distribution exists in the mixer, and the purpose of elongating silver halide to a certain extent without concentration distribution cannot be achieved.

Furthermore, in order to eliminate the uneven distribution of the concentrations of these silver ions and halogen ions through more complete mixing, the reaction vessel and mixer were made independent, and the aqueous silver salt solution and aqueous halogen salt solution were supplied to the mixer and rapidly mixed. Attempts have been made to increase the power of silver halide grains. For example, JP-A-53
-37414 and Japanese Patent Publication No. 48-21045, a protective colloid aqueous solution (containing silver halide particles) in the reaction vessel is circulated by a bomb from the bottom of the reaction vessel, a mixer is installed in the middle of this circulation system, and this mixing A manufacturing method and apparatus are disclosed in which a silver salt aqueous solution and a halogen aqueous solution are supplied to a vessel, and the two aqueous solutions are rapidly mixed in the mixer to grow and solidify silver halide grains. Furthermore, in US Pat. No. 3,897,935, a protective colloid aqueous solution (containing silver halide particles) is circulated in the reaction vessel by a pump from the bottom of the reaction vessel, and a halogen salt aqueous solution and a silver salt aqueous solution are pumped in the middle of this circulation system. A method of injecting is disclosed. Special UrI 1975
No. 3-47397, a protective colloid aqueous solution (containing a silver oxide emulsion) is circulated in the reaction vessel by a pump from the reaction vessel, and an alkali metal halide salt aqueous solution is first injected into the circulation system so that it is uniformly distributed. After the silver salt aqueous solution is injected into the system and mixed, silver halide grains are formed. Two manufacturing methods and devices are disclosed. It is true that these methods can independently change the flow rate of the aqueous solution in the reaction vessel flowing into the circulation system and the stirring efficiency of the mixer, making it possible to grow particles under conditions with a more uniform concentration distribution. However, in the end, the silver halide crystals sent from the reaction vessel together with the protective colloid aqueous solution have uneven concentrations at the injection ports for the silver salt aqueous solution and the halogen salt aqueous solution. Therefore, as mentioned above, it is impossible in principle to eliminate the concentration distribution in the mixing area or around the injection date, that is, the purpose of growing silver halide in a state without concentration distribution cannot be achieved.

On the other hand, Japanese Patent Publication No. 46-7772, U.S. Patent No. 2,
No. 146,938, Japanese Patent Application Publication No. 57-23932, Japanese Patent Application No. 7851-1983, Japanese Patent Application No. 63-7853, and Japanese Patent Application Publication No. 63-7853.
No. 195,778 discloses a grain shape or method of intensifying grains while adding silver halide grains prepared in advance or immediately before addition to a reaction vessel; There is no mention that silver halide grains prepared using silver halide grains are useful for color reversal photographic materials as grains with few fog nuclei inside the grains, and there are no examples of them actually being used for color reversal photographic materials. do not have.

Therefore, an object of the present invention is to provide a method for producing a silver halide color reversal photographic light-sensitive material that has a high maximum purulence and excellent graininess.

(Means for Solving the Problems) The above objects of the present invention are a red-sensitive silver halide emulsion with a low fI:<1, a green-sensitive halogenated IR''7L emulsion,
and a method for producing a color reversal photographic light-sensitive material in which a blue-sensitive silver halide emulsion is produced, and each of the emulsions is further coated on a support to form a Mi layer, wherein at least 1 of the grain nuclei of the emulsion or A silver halide color reversal photograph characterized in that silver halide grains prepared outside the reaction vessel are added to a reaction vessel in which crystal growth is caused, and then at least part of the crystal growth is carried out in the reaction vessel. This is achieved through the manufacturing method of photosensitive materials.

According to the present invention, a silver salt aqueous solution necessary for forming silver halide grains is directly added to a reaction vessel in which silver halide nuclei or crystal growth is caused, or to a mixing vessel with circulation with the reaction vessel. And grain crystallization is carried out without adding an aqueous halogen salt solution. Therefore, it is possible to obtain silver halide grains with reduced formation of capri nuclei inside the grains without exposing the grains to an atmosphere with high silver ion concentration, and it is possible to obtain silver halide grains with a high maximum concentration and excellent graininess. A reversal photographic material is obtained.

The present invention will be explained in detail below.

The silver halide color reversal photographic light-sensitive material of the present invention usually has a blue-sensitive layer, a green-sensitive layer, a red-sensitive layer, etc. on a support. ri
It has a different number of color-sensitive layers. Further, each color-sensitive layer is composed of one or more silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. The number of these silver halide emulsion layers having different sensitivities is usually 2 to 3N.
The effects of the present invention can be obtained even when the silver halide emulsion of the present invention is used in any of these emulsion layers.

The following two methods can be mainly used to produce gI silver halide grains in the present invention.

■ A method of adding a roughly prepared fine-grain silver halide emulsion.

For example, Tokukai No. 63-7852, No. 63-7853,
As described in No. 63-194861 and No. 63-194862, a fine-grain silver halide emulsion having fine-sized grains prepared in advance is added to a reaction vessel to perform nucleation and/or grain growth. At this time, the grain size of the roughened emulsion was 0.1 μm in average diameter.
The following is preferable, more preferably 0.06, r1m or less. In this method, no aqueous solution of a water-soluble root salt or an aqueous solution of a water-soluble halide is added to the reaction vessel in which nuclear formation and/or grain lengthening occur, except for adjusting l'lAg of the emulsion in the reaction vessel. It is preferable not to add it. This pre-prepared emulsion may be washed with water and/or solidified before being added to the reaction vessel.

Additionally, a silver halide melt can be used to increase the grain growth rate. As halogenated W&solvent,
Examples include water-soluble bromides, water-soluble chlorides, thiocyanates, ammonia, thioethers, and thioureas.

For example, thiocyanate (U.S. Pat. No. 2,222,264)
No. 2,448,534, No. 3,320.0 (
i9, etc.), ammonia, thioether compounds (e.g., U.S. Pat. No. 3,271,157, U.S. Pat. No. 3,574,
No. 628, No. 3,704,130, No. 4,297
．． 439, 4.276,347, etc.), thione compounds (e.g., JP-A-53-144319, JP-A-53-144319, JP-A-53-144319, JP-A-53-144319)
-82408, No. 55-77737, etc.), amine compounds (e.g., JP-A-54-100717, etc.), thiourea derivatives (e.g., JP-A-55-2982), itadazoles (e.g., JP-A-54-100717, etc.) No. 100717), substituted mercaptotetrazoles (e.g. JP-A-57-2025
No. 31).

■ A method of supplying fine silver halide particles from a mixer outside the reaction vessel.

As an efficient method for supplying fine particles, a powerful and efficient mixer is installed outside the reaction vessel, and an aqueous solution of a water-soluble root salt, an aqueous solution of a water-soluble halide, and an aqueous protective colloid are supplied to the mixer, and the mixture is rapidly mixed to produce extremely fine particles. As soon as silver halide grains are generated, they are continuously fed into the reaction vessel. Similar to the method at that time, an aqueous solution of water-soluble root salts and water? 8 Moriha [
No aqueous solution of Igen salt is supplied to the reaction vessel.

Regarding the above method, the above-mentioned Japanese Patent Application No. 63-1852,
No. 63-7853, No. 63-194861, No. 63
-194862 as well as 637851 and 63
-195778 can be preferably used in the present invention.

The silver halide fine particles formed in the mixer have very high solubility due to their fine particle size, and when added to the reaction vessel, they dissolve and become silver ions and halide ions again, which are already present in the reaction vessel. It deposits on particles and causes particle growth, but at that time, because the fine particles have high solubility, so-called Ostwald ripening occurs between the fine particles, and the particle size increases. The solubility decreases, the dissolution in the reaction vessel becomes slow, and the rate of particle growth decreases significantly, and in some cases, the particles no longer dissolve, but instead become nuclei themselves and cause growth.

This problem is solved by the following three techniques.

■ Immediately after forming the microparticles in the mixer, add them to the reaction vessel.

In addition, by providing a mixer very close to the reaction vessel and shortening the residence time of the additive liquid in the mixer, this Ostwald precept can be prevented by immediately adding the formed particles to the reaction vessel. I made sure not to have it. Specifically, the residence time L of the liquid added to the mixer is expressed as follows.

In the production method of the present invention, t is IO minutes or less, preferably 5 minutes or less, more preferably 1 minute or less, even more preferably 20 seconds or less. The fine particles thus obtained in the mixer are immediately added to the reaction vessel without their particle size increasing.

O Perform powerful and efficient stirring with a mixer.

James (T.H. Ja+*es) The Theory
Obza Fo1 Graph Inc. Process Il. p.
93 states, ``Along with Ostwald ripening, another form is 'coalescence.' In coalescence ripening, crystals that were previously far away come into direct contact and come together to form larger crystals. "Osttwald ripening and coalescence ripening occur not only after the end of deposition, but also during deposition." Coalescence V!
This is particularly likely to occur when the particle size is very small, and is especially likely to occur if stirring is insufficient. In extreme cases, it may even create coarse, clumpy particles. By using a closed-type mixer, the stirring blades in the reaction chamber can be rotated at high rotational speeds, which was not possible with conventional open-type reaction vessels. If you do so, the liquid will be blown away by centrifugal force, causing problems with foaming.
Not practical. ) Powerful and efficient stirring and mixing can be performed, the above-mentioned coalescence ripening can be prevented, and as a result, fine particles with a very small particle size can be obtained.

The rotation speed of the stirring blade is 1000r. p. m or more, preferably 2000 r. p. m or more, preferably 3000 r. p. m or more.

O Injection of protective colloid aqueous solution into mixer The aforementioned core reflex deterioration can be significantly prevented by protective colloid of silver halide fine particles. In the present invention, the protective colloid aqueous solution is added to the mixer by the following method.

■ Inject the protective colloid aqueous solution alone into the mixer.

The concentration of the protective colloid is preferably 1% by weight or more, preferably 2%, and the flow rate is at least 20%, preferably at least 50%, of the sum of the flow rates of the silver nitrate solution and the aqueous halide solution.
More preferably, it is 100% or more.

■ Add protective colloid to the halogen salt aqueous solution.

The concentration of the protective colloid is at least 1% by weight, preferably at least 2% by weight.

■ Add a protective colloid to the silver nitrate aqueous solution.

The concentration of the protective colloid is at least 1% by weight, preferably at least 2% by weight. When gelatin is used, it is better to mix the silver nitrate solution and the protective colloid solution immediately before use, since gelatin roots are formed from silver ions and gelatin, and the root colloid is produced by photolysis and thermal decomposition.

Further, the above methods (1) to (4) may be used alone or in combination, or three may be used at the same time. As the protective colloid used in the present invention, gelatin is usually used, but other hydrophilic colloids can also be used.
It is described in section ■.

In the present invention, among the above methods (1) to (0), method (2) is most preferred.

Thus, the particle size of the fine particles obtained by the Φ~0 technique can be confirmed by placing the particles on a mesh and using a transmission electron microscope at a magnification of 20,000 to 40,000 times.

The size of the fine particles is 0.06 μm or less, preferably 0.06 μm or less.
0.03 μm or less, more preferably 0.03 μm or less. It is less than 1 μm.

In this way, it becomes possible to supply particles of extremely fine size to the reaction vessel, resulting in a higher dissolution rate of fine particles,
Therefore, a higher growth rate of silver halide grains in the reaction vessel can be obtained. Although the method no longer requires the use of silver halide solvents, silver halide solvents may be used if desired to obtain higher growth rates or for other purposes. Halogenated! ! The solvent is as described in Method (■). According to this method, the supply rate of silver ions and halide ions to the reaction vessel can be freely controlled. Although a constant feed rate may be used, it is preferable to increase the addition rate. The method is Tokuko Sho 4B-3
6890, 52-16364. The rest is as stated in ■Law. Furthermore, according to this method, it is possible to control the silver iodide content during growth to a white peak, for example, to maintain a constant silver iodide content during the growth of silver halide grains, or to continuously increase the silver iodide content. It is possible to change the silver iodide content at some point by slowing or freezing.

The reaction temperature in the mixer is preferably 60°C or lower, preferably 50°C or lower, more preferably 40°C or lower. At a reaction temperature of 35° C. or lower, ordinary gelatin tends to coagulate, so it is preferable to use low molecular weight gelatin (average molecular weight 1300000 or less).

In the present invention, irrespective of the method (1) or (2), the method of the present invention is used from the nucleation stage to the growth stage, and the nucleation is determined by the conventional method, which is a part of the grain growth. A sufficiently large effect can be obtained even when the present invention is applied only to. The silver halide grains that form the core of the silver halide of the present invention are:
P. Che+wie et Ph by Glafkides
isiquePhotographique (Pau
(Published by Monte 1, 1967) G, F. Duff
in Author Photographic En+ulsion
Chemistry (The Focal Pres.
s, 1966), V. L. Zeliksanet
Makin8and Coating Pho by al
tographicEmulSion (The Fo
Cal Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble root salt with the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. .

A method in which particles are formed under an excess of silver ions (so-called back mixing method) can also be used.

As one type of simultaneous mixing method, a method in which p8g in a liquid phase in which silver halide is controlled to be kept constant, that is, a so-called controlled double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

When preparing the nuclei of silver halide grains, it is preferable that the halogen composition be constant.

When the inner core is iodobromide, it is preferable to use the double jesotho method or the control double jeso method.

Nuclear! The pAg when producing Pl varies depending on the reaction temperature and the 4IIfl of the silver halide solvent, but is preferably 7 to 11. Further, it is preferable to use a halogenated S carrier because the particle formation time can be shortened.

For example, commonly known halogenated solvents such as annimore and thioether can be used.

The shape of the nucleus may be plate-shaped, spherical, twinned, octahedral, cubic, tetradecahedral, or mixed.

Further, the nuclei may be polydisperse or monodisperse, but it is more preferable that the nuclei be monodisperse. Here, "monodisperse" has the same meaning as described above.

In addition, to make the particle size uniform, British Patent No. 1,53
No. 5,016, Special Publication No. 4B-36890, No. 52-16
364, etc., there is a method of changing the addition rate of octopus acid root or aqueous alkali halide solution according to the particle growth rate, and U.S. Pat. As described above, it is preferable to use the method of changing the concentration of the aqueous solution to rapidly increase the concentration within a range that does not exceed the critical supersaturation degree.These methods do not cause re-nucleation and each silver halide grain is uniform. It is also preferably used when introducing a coating layer, which will be described later. In the process of nucleus formation or physical ripening of silver halide grains, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or their complex salts, rhodium salts or their complex salts, iron salts or iron complex salts, etc. are allowed to coexist. It's okay.

The composition of the silver halide emulsion grains of the present invention may be pure silver bromide, pure silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, or silver chloroiodide, but usually iodide Silver content is 30 mol% or less,
More preferred is silver iodobromide of 10 mol% or less.

Regarding silver iodobromide that can be used in the present invention, the position of the phase containing silver iodide within the grain may be in the center of the silver halide grain, over the entire grain, or in the outer part. May exist. Further, the number of phases in which silver iodide is present may be one or more. Generally, the phase containing silver iodide is
Although a layered structure is often created due to the grain growth mechanism, it may be a specific portion. For example, by taking advantage of the difference in properties between the ethos and corners of tabular grains, it is possible to form an iodized root phase only in the ethos or only in part of the corners.

Furthermore, by forming a shell on the outside, it is also possible to create halide daughter grains that have silver iodide at specific points that do not have a layered structure inside the grain. The method for preparing silver halide grains of the present invention can be used both when forming a silver iodobromide phase and when forming a pure silver iodide layer. % or less of silver iodobromide phase or pure silver iodide phase is preferable because the present invention has a higher effect of reducing fog inside the grains.

The shape of the silver halide grains of the present invention is hexahedral, octahedral,
It may have a regular crystal shape (normal product particle) such as dodecahedron, dodecahedron, icosahedron, or tetraoctahedron, or it may have an irregular crystal shape such as spherical or diagonal shape. Furthermore, particles of various shapes having one or more twin planes,
Among these, hexagonal tabular grains and triangular tabular twin grains having two or three parallel twin planes may be used.

Further, the silver halide emulsion grains in the present invention may have any grain size distribution, but 95% or more of the total grain number or weight is ±40% of the volumetric average grain size defined by the following formula. , preferably within ±30%. The silver halide grains of the present invention may have silver halides of different compositions bonded together by epitaxial bonding. It may be bonded with a compound other than silver. These emulsion grains are described in U.S. Pat.
900, No. 4459.353, British Patent No. 2.038
, 792, U.S. Patent No. 4,349,622, 4,
No. 395.478, No. 4,433.501, No. 4,4
No. 63,087, 3.65G. No. 962, 3,85
No. 2,067, Japanese Patent Application Laid-Open No. 5'J-162540, etc.

Silver halide grain formation or thing p! ! In the process of meditation, cadmium salts, zinc salts, lead salts, taliurium salts, iridium salts or complex salts thereof, rhodium salts or stirrup salts thereof, iron complex salts, etc. may be co-present.

In order to remove soluble silver salts from emulsions before and after physical examination, Nudel water washing flocculation sedimentation method or ultra-i
Follow the law, etc.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example I1. Frisel (l1.
Frieser & f, Die Grundlagcn
derPhotography Prozes
se mit Silberhalogeniden)
(Academi Soche Fuerlagus Geserschacht 196
B) The method described on pages 675 to 734 can be used.

That is, sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapsilicates, etc.)
sulfur sensitization method using reducing substances (e.g. stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); noble metal compounds (e.g. In addition to gold complex salts, complex salts of metals in group II of the periodic table such as pt, Ir, and Pd)
A noble metal sensitization method using a sensitizer can be used alone or in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as penzothiazolium salts, nitroindazoles, triazoles, henz 1 liazoles, penzimidazoles (particularly nitro or halogen substituted); heterocyclic merkabut compounds such as mercap I thiazoles,
Mercaptobenzothiazoles, mercaptohenzigodazoles, mercap-1hethiadiazoles, mercaptotetrazoles (especially l-phenyl 5-mercaptotetrazole), mercaptopyrimidines; Heterocyclic mercapto compounds: thioketo compounds such as oxazolinthione; azaindenes such as tetraazaindenes (especially 4-hydroxy substituted (1,3.3a,7) tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acids A number of compounds known as antifoggants or stabilizers can be added, such as;

The timing of adding these antifoggants or stabilizers is usually after chemical sensitization, but it is more preferable to add them during chemical sensitization or before the start of chemical sensitization. During the silver salt emulsion grain formation process, both during the addition of the silver salt solution and after the addition until the start of chemical ripening, during the chemical ripening process (during the chemical ripening time,
(preferably within 50% of the time from the start, more preferably within 20% of the time).

Additives used in the manufacturing process of silver halide emulsions are listed in Research Disclosure 1kl7643 and tl.
hl8716, and the relevant parts are summarized in the table below.

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

Additive type R port 17643 RD1B716
l Chemical sensitizer 23 @ Page 648 Right column 2 Sensitivity increasing agent Same as above 4 jl Whitening agent Page 24 Ultraviolet absorber 8 Dye image stabilizer Page 25 9 Hardening agent Page 26 Page 651 Left column 10 Binder Page 26 Same as above Invention The silver halide grains may be ordinary surface latent image type silver halide grains or may be internal latent image type silver halide grains which mainly form a latent image inside. Particles with improved pressure characteristics and a ratio of surface sensitivity to internal sensitivity of 0.5 to 2 can also be preferably used.

In the present invention, 0.6μ or less, preferably 0.6μ or less is used. A non-light-sensitive fine grain emulsion having no fog nuclei of 2 μm or less may be added to the silver halide emulsion layer, intermediate layer or protective layer for the purpose of improving retention, making effective use of reflected light, etc. Further, a fine grain silver halide emulsion in which the light-sensitive emulsion layer of the present invention or an adjacent non-light-sensitive intermediate layer is coated with the surface or interior described in U.S. Pat. No. 2,319,369 or JP-A-59-214852. can be used to make the interimage effect as large as J.

Various color couplers can be used preferably in the emulsion layer of the silver halide color reversal photographic light-sensitive material of the present invention. It is described in the patents listed in C-G.

As a yellow coupler, for example, U.S. Patent No. 3,93
No. 3,501, No. 4.022.620, No. 4.3
No. 26,024, No. 4.401.752, Special Publication No. 5
No. 8-10739, British Patent No. 1.425,020,
No. 1,476,760, etc. are preferred.

As Mazenk Kabler, 5-pyrazolone-based and virazoloazole-based compounds are preferred, and Yoneda Patent No. 4, 31
No. 0.619, No. 4.351897, European Patent No. 7
3, (No. 36, U.S. Patent No. 3,061,432, U.S. Patent No. 3,725.067, Research Disk rJ-Jar Th2 4 2 20 (June 1984), JP-A-60-33552 , Research Disclosure 1
1h24230 (.June 1984), JP-A-60-4
3659″;'f, U.S. Patent No. 4,500.630°C;
Particularly preferred are those described in 4.540.654. Furthermore, pyrazolone-based and virazoloazole-based magenta couplers can be used in combination, if necessary.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4,052,212.
No. 4,146.39 (No. i, No. 4,228,2)
No. 33, No. 4, 29 (i, No. 200, No. 2,
No. 369,929, No. 2,801,171, No. 2,
No. 772,162, No. 2,895.826, No. 3
, 772,002, 3,758,308, 4,334, Oll, 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121
, 365A, U.S. Patent No. 3,446,622 Kidney, U.S. Patent No. 4,333,999, U.S. Patent No. 4,451.559, U.S. Patent No. 4,427,767, European Patent No. 1131.62E
Those described in No. IA etc. are preferred.

Typical examples of polymerized dye forms or couplers are U.S. Pat. No. 3,451,820, U.S. Pat.
It is described in No. 173, etc. Couplers that release photographically useful residues upon camping are also preferably used in the present invention. DIR couplers that release development inhibitors are disclosed in the patents described in the above-mentioned RD17643, sections ① to F, and JP-A-57-151944 and JP-A-57-1-542.
No. 34, No. 60-184248, U.S. Patent No. 4.24
8,962 is preferred.

As a coupler that releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,097,140;
No. 2.13L No. 188, JP-A-59-15763
Preferably, those described in US Pat. 1. ro, 427, etc., U.S. Pat. No. 4,283,472, U.S. Pat.
Tatorei Kabler described in No. 1, etc., JP-A-60-18595
Examples include the DIR redox compound releasing force puller of Amnesty, and the coupler that releases a dye that restores color after separation, as described in European Patent No. 173,302A.

The coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods.

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

The steps and effects of the latex dispersion method and specific examples of latex for impregnation are described in U.S. Pat. No. 4,199,363, West German Patent Application No. He has been forgiven three times.

The light-sensitive material of the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular limitations on the number and order of layers and non-photosensitive layers. A typical example is a silver halide photograph having on a support at least one light-sensitive layer selected from a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. It is a photosensitive material, and the photosensitive layer is a unit photosensitive layer that is sensitive to blue light, green light, or red light. In multilayer silver halide color photographic light-sensitive materials, generally The layers are arranged in this order from the support side: a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

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

The intermediate layer includes JP-A-61-437-48, JP-A No. 59-113438, JP-A No. 59-113440.
, No. 61-20037, and No. 61-200388, D I +? Compounds etc. may be included, and a color mixing inhibitor may be included as commonly used.

Does each unit constitute a photosensitive layer? A number of silver halide emulsion layers are described in West German Patent No. 1.121. A two-layer structure consisting of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer can be preferably used as described in No. 47o or British Patent No. 923,045. Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also, JP-A No. 57112751, No. 62-200350, No. 62
As described in No. 206541 and No. 62-206543, a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

In addition, the special public interest public corporation Sho 49-1. As described in 5-4-9-5, the upper layer is a halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with a lower sensitivity, and the lower layer is a silver halide emulsion layer with a lower sensitivity than the middle layer. A low silver halide emulsion layer is placed with a sensitivity of 111 towards the support.
An example is an arrangement composed of three layers having different photosensitivity, which are 11 orders of magnitude lower.

As mentioned above, the layer structure and arrangement of the ridges can be selected depending on the purpose of each photosensitive material. In addition, the photosensitive material of the present invention contains a hydroquinone neck that releases a development-inhibiting compound described in U.S. Pat. No. 3,379,529 and U.S. Pat. Naphthohydroquinone and the like can be preferably used.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D. Page 28 of 17643 and 6 of 18716
It is described from the right column on page 47 to the left column on page 648. The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main ingredient. Although aξnophenol compounds are also useful as color developing agents, p-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N,N-diethylaniline, 3 -methyl-4-amino-N-ethyl-N
monoβ-hydroxyethylaniline, 3-methyl4-aξ
No-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-
Examples include β-methoxyethylaniline and their sulfates, hydrochlorides, and P-}luenesulfonates. Two or more of these compounds can be used in combination depending on the purpose. Color developers may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors such as bromide salts, iodide salts, benzimidazoles, penzothiazoles or mercapto compounds. It generally contains an agent or an antifoggant.

When processing the color reversal photosensitive material obtained according to the present invention, black and white development is usually performed, followed by color development. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or a≧nophenols such as N-methyl-p-aminophenol. It can be used alone or in combination.

The par of these color developing solutions and black and white developing solutions is 9 to 12
It is common that After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, processing in two continuous bleach-fix baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be carried out as desired depending on the purpose. Examples of bleaching agents include iron (■) and cobalt (II).
Compounds of polyvalent metals such as I), chromium (■), and copper (IT), peracids, quinones, and nitro compounds are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (II1) or cobal (Ill), such as ethylenediayonetetraacetic acid, diethylenetrianepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, Aminobocarboxylic acids such as 1.3-diaminopropanetetraacetic acid 1, glycol ether diamine tetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.; persulfates; bromates; permanganates; nitrobenzenes etc. can be used. A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts. The silver halide color photographic light-sensitive material of the present invention is generally subjected to a water washing and/or stabilization process after desilvering treatment.
The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the material used, such as a coupler), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. It can be set over a wide range.Among these, the relationship between the number of water washing tanks and the amount of water in the multistage countercurrent method is
Urnalof the So+jety of Mo
tion Picture and Televisi
onEngrneers Volume 64, P. 24B-253
(May 1955 issue).

The pH of the washing water in the processing of the photosensitive material of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15-45°C, preferably 20 minutes.
A range of 30 seconds to 5 minutes at 5 to 40°C is selected. Furthermore,
The photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8,543 and 58-14.8
All known methods described in No. 34, No. 60-220.345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

It is also possible to add various calcining agents and densification agents to this stabilizing bath.

Various processing solutions in the present invention are used at 10°C to 50'C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can improve image quality and stability of the processing solution. can do.

(Example) The present invention will be explained in detail below using examples.

Example-1 Various emulsions were prepared as shown below.

Bromization! l Fine grain emulsion 1-a 1.2M silver nitrate solution and 1.17M odor were added to 2.61% gelatin solution containing 0.026M potassium bromide using the double gelatin method while stirring. Each halogen salt aqueous solution containing 12001R1 and 0.03M potassium iodide was added over 5 minutes.
During this time, the gelatin solution was kept at 35°C. After this, the emulsion was washed using the conventional flocculation method and 30 g of gelatin was added.
was added and dissolved, pH 6.5, pAgs. Adjusted to 6. The obtained silver iodobromide fine grains (silver iodide content: 2.5 mol) had an average grain size of 0.07 μm. The total weight of the emulsion was 1440 g. Silver iodobromide fine grain emulsion 1-b 2.6 Il of a 2.0% gelatin solution containing 0.026 M potassium bromide was mixed with a 1.2 M silver nitrate solution using the double jet method while stirring; A halogen salt aqueous solution containing 1.14 M potassium bromide and 0.06 M potassium iodide was added at 1200 m each over 15 minutes.
During this time, the gelatin solution was kept at 35°C. After this, the emulsion was washed using the conventional flocculation method and 30 g of gelatin was added.
was added and dissolved, and the pI was adjusted to 16.5 and pAg to 8.6. The obtained silver iodobromide fine particles (silver iodide content 5%)
> had an average particle size of 0.07 μm. The total weight of the emulsion was 1440 g.

Silver Iodobromide Fine Grain Emulsion 1-c Add 1.61% of 2.0% by weight gelatin 5 solution containing 0.026M potassium bromide to 1.61% of 1.2M nitric acid by double jet method while stirring. solution and an aqueous halogen salt solution containing 1.2 M potassium bromide were added at 120 ld each over 15 minutes.

During this time, the gelatin solution was kept at 35°C. After this, the emulsion was washed using the conventional flocculation method and 30 g of gelatin was added.
After adding and dissolving pll6.5, pAgs. Adjusted to 6. The obtained silver iodobromide fine particles had an average particle size of 0.07 μm.

The total weight of the emulsion was 1440 g.

Emulsion 1-A (comparative emulsion) 3 containing 0.06M potassium bromide kept at 75°C
．． 1.2 L of 0% by weight gelatin aqueous solution, 50 cc of 0.3 M silver nitrate aqueous solution, 0.293 M potassium bromide and 0.0
50cc of an aqueous solution containing 075M potassium iodide was added to pAg.
9.0 and added over 3 minutes using the double jet method. As a result, 0.13 nm silver iodobromide core particles were obtained (nucleation stage).

Subsequently, 250 ad of 1.0 M silver nitrate and 0.
An aqueous solution containing 975 M potassium bromide and 0.025 M potassium iodide, 250 ml, was added over 20 minutes using the double diesoto method at a pAg of 9.0 (particle lengthening stage!). Furthermore, 1.0M silver nitrate 25 at 75°C
0-, 250 ml of an aqueous solution containing 0.975M potassium bromide and 0.025M potassium iodide was heated to pA over 20 minutes.
It was added by the double diesotho method at g9.0 (particle length stage ■). Thereafter, it was washed with water at 35°C by a known flocculation method, 50g of gelatin was added, and the pH was 6.2 and the pAg was 8.
In step 8, potassium chloroaurate and sodium thiosulfate were added to optimally gold-sulfur sensitize. The finished particle is 0.40μ
The silver iodide distribution within the grains was octahedral monodisperse grains without a layered structure.

Emulsions 1-B to 1-S (comparative emulsions) Table 1 shows the composition of the aqueous halogen solution added to emulsion 1-A at the nucleus formation stage and grain growth stage, the addition time at each stage, and I) Ag. Eleven types of emulsions, Emulsion IB to Emulsion 1-L, were prepared by changing the grain size, layered structure of silver iodide distribution within the grains, and crystal habit as shown in FIG. Emulsions 1-B to 1-L were washed with water and redispersed in the same manner as Emulsion 1-D, and optimally gold-sulfur sensitized.

Emulsion 1-M (emulsion according to the invention) Nucleation was carried out in exactly the same manner as Emulsion 1-A. followed by 75
Fine grain emulsion at °C! -a was added over 50 minutes at pAg 9.0 (particle growth stage I). Even fine grain emulsion! 250 g of -a was added over 50 minutes at pAg 9.0 (particle growth stage ■). This emulsion was washed with water, redispersed, and optimally gold-sulfur sensitized in the same manner as Emulsion 1-D. Emulsion 1-N to Emulsion 1-X (emulsion according to the present invention) Emulsion 1-
The composition and addition time of the halogen aqueous solution added to M in the nuclear shape control and I) Ag and the type of fine grain silver halide emulsion added in the growth stage, addition time, and p and Ag were varied as shown in Table 2. Emulsions 1-N to 1-X with different sizes, layered structures of silver iodide distribution within grains, and crystal habits
was prepared. Emulsions 1-N to 1-X were washed with water and re-divided in the same manner as Emulsion 1-D, and optimally gold-sulfur sensitized.

Next, each layer of the composition shown below was coated on an undercoated cellulose triacetate film support having a thickness of 127 μm to prepare color reversal photographic materials, Samples 101 to 112. The numbers represent the amount of coating per R. Samples 101-11
2, 4th N, 5th layer, 6th N, 9th N, 10th layer, lth layer
The silver halide emulsions in each of the photosensitive emulsion layers 1N, 15th layer, 16th layer, and 17N are as shown in Table 3. Samples 101-106 are comparative examples, and wipes 107-112 are examples according to the present invention.

1st layer: antihalation layer black colloid l O. 25g gelatin 1.9gU-10.04
g U-20. lg U-30.1g Oi1-10.1g 2nd layer: Intermediate layer gelatin 0.40gCpd-
D 10■Oil ~3
40 ■ 3rd J] Intermediate layer gelatin 0.4g 4th layer: Low-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-t and S-2 Silver Mouse 0.4g gelatin
0.8g coupler C-1
0.20g coupler C-90.05g Oi1 -1 0.1cc 5th
Layer: Medium red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes s-i and S-2 Silver amount 0.4 g gelatin
0.8g Cabler C-1
0.2g coupler C-2 0
．． 05g Cobrar C-30.2g Of1-1 0.1cc 6th layer: High sensitivity red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 Silver amount 0.4g gelatin
1.1g coupler C-3
0.7g coupler c-1 0.
3g 7th layer: Intermediate layer gelatin 0.6g Dye D-1
0.02g 8th layer: Intermediate layer gelatin 1, OgCpd-A
0.2g 9th layer: Low-speed green-sensitive emulsion layer Iodobromide root emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 Silver 1 0.5g gelatin
0.5g Cobrar C-40.10g Cobrar C~7 0. log coupler C-8 0.10gCpd-B
O. 03gCpd-E0.1g Cpd-F0.1g Cpd-GO. 1g Cpd-H 0.1g 1st
O layer: medium-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 Silver amount 0.4 g gelatin
0. 6g coupler (,-4
0. 1g coupler C-7
0.1g coupler C-8 0.
IgCpd-8 0.03gC
pd-E0.1g Cpd-F0.1g Cpd-G O. 05gCpd
-H O. 05g 11th layer: High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 ilI O. 5g gelatin
1. Og coupler C-4
0.4g Cabler C-7
0.2g coupler c-8 0.2
gCpd-BO. 08g
Cpd-IE o. Ig
Cpd-F0.1g cpa-c o. IgCp
d-1-1 0.18th l
2nd layer: middle layer gelatin 0.6g dye D-2
0.05g 3rd layer: Yellow filter layer Yellow colloid root Silver amount 0. lg gelatin
1.1gCpd-A
O. Olg No. 14N: Intermediate layer gelatin 0.6g No. 15N:
Low-speed blue-sensitive emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6
SilverFli 0.6g gelatin
0.8g Couvler C-50.6g 16th layer: Medium-speed blue-sensitive emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6
! ! 1 0.4g geladine
0.9g coupler C-5
0.3g coupler C-6
0.3g 17th layer: High-speed blue-sensitive emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6
Silver amount 0.4g geladine
1.2g coupler C-60.1g 18th WJ: 1st protective layer gelatin 0.7gU-10.
04g U-30.03g U-40.03g U-50.05g U-60.05g Cpd-C0.8g Dye D-30.05g No. 191: Fine grain silver iodobromide emulsion covered with second protective layer (average Particle size 0.06μ
, Ag + content 1 mol%) Silver amount 0.1g Gelatin 0.4g 20th FF
: Third protective layer gelatin 0.4g polymethyl methacrylate (average particle size 1.5μ>0.1g 4=6 copolymer of methyl methacrylate-1- and acrylic acid (average particle size 1.5μ) O. lg silicone oil 0.03g surfactant W l
3. Qn@Each layer contains the above Mi
In addition to the sacraments, gelatin hardening agent H1, coating and emulsifying surfactants, etc. were added.

The compounds used in this example are shown below.

C 1 011 C-2 0H C-3 011 C-4 C-6 C 7 C-8 C-9 Cpd E C. I+, 0 straight Cpd-H C1 011 01 1-1 Diptyl phthalate 0i1-2 tricresyl phosphate Cpd-A 01! cp d-D 0H U-4 In tJ-5 U-6 S-1 S 6 S (hlN (C2115) 3 SO, D 7 SO3K SO3K D 2 So,K SOsκ S 2 0 CJs C. I+, (CH) 4SO3.

C, I+, S0311N (CZI+5) 3 D 3 1I l CIIz? 1■S O■C HKC O N H C Hz?
IIz= C 1I S O■CIIzCONHCH
(2) W-1 C11 Film pieces were prepared from these samples #4i 0 1 to 112, and each was subjected to wedge exposure using a 4800'K white light source and 11 light beams passed through a pattern for measuring RMS graininess. The exposed samples were processed in the following steps.

Processing process A L Time Temperature First development 6 minutes 38℃ Water washing 2 minutes inversion 2 minutes color development 6 minutes adjustment 2 minutes bleaching 6 minutes Fixation
Wash with water for 4 minutes Stable for 4 minutes Dry at room temperature Use treatment solution Mi or the following.

Fudejiri hemostatic water 700a
d Sodium tetrabolyphosphate Sodium sulfite Hydroquinone monosulfonate Sodium carbonate (monohydrate) ]-Phenyl 4-methyl 4-hydroxymethyl-3 vilazolidone Potassium thiocyanate Potassium iodide (0.1% solution) Water Add 2g 20g 30g 30g 2g 2. 5g 1. 2g 2-100. 〇1l) (pHlo. Anti-Five Precepts Water Nitro/N-N-N-trimethylenephosphonic acid/6Na chloride Stannous chloride (dihydrate) 700Nd p-Aminophenol Sodium hydroxide Add glacial acetic acid water and dilute Rinzo Chosui Sodium Liumium Tetrabolyphosphate g @ Sodium Tertiary Sodium Phosphate (1decahydrate) Potassium Bromide Potassium Iodide (0.1% Solution) Sodium Hydroxide Citrazate N Ethyl N- (β -methanesulfonamidoethyl) 13-methyl-4-aminoaniline sulfate ethylenediamine Add water and prepare 0.1g 8g 151Rl 1 0 0 0 d 700N4 2g 7g 36g Ig 90ad 3g 1.5g 11g 3g 1000d Nissei Kaisui Sodium ethylenediamine sulfite, sodium tetraacetate (dihydrate) Add thioglycerin glacial acetic acid water and rehydrate Sodium ethylenediaminetetraacetate (dihydrate) Ethylenediaminetetraacetate iron(II+) ammonium (dihydrate) Potassium bromide water Add 700d l2g 8g O,4d 31000td 80 12.0g 120.0g 100.0g 1000sj 80180.0g Sodium sulfite 5.0g Sodium bisulfite 5.0g Water plus
1 0 0 0 m Onodeda Kosui 800 - Formalin (37% by weight) 5. Oli
Fuji Drywell 5. O. j Add water for 1000m After the above treatment, the wedge-exposed sample shows a cyan image, a magenta image,
Sensitometry was performed on the and yellow image, and R
For samples exposed through the MSfi standard pattern, the RMS value of each image was measured and the graininess was compared. The results are shown in Table 4. As can be seen from Table 4, Samples 107 to 112 containing emulsions whose grains were grown by the method of the present invention are compared to Comparative Sample 1 whose crystal habit was grown by the conventional double gent method.
It has a higher maximum concentration and better graininess than 01-106.
(Sample r4101 is 106, sample 102 is 108, sample 103 is 109, sample 104 is 110, sample 10
Sample 5 corresponds to 1lI, and sample 106 corresponds to sample 112 as samples containing grains having the same grain crystal habit and layered structure of silver iodide distribution. ) Example 2 Emulsion 2-Δ (emulsion according to the present invention) Kernel analysis was carried out in exactly the same manner as Emulsion 1-A. Next, a powerful and efficient mixer installed near the reaction vessel was used. 0 M61'lftHD aqueous solution 25
0 ml and 0.975 M potassium bromide and Q. 025M
an aqueous solution containing potassium iodide of 2 50 rsl and 2
At the same time, 150 mffi of a 5t% aqueous gelatin solution was added over 50 minutes. The polar imitation particles generated in the mixer were immediately introduced into a reaction vessel continuously maintained at 75° C. pAg = 9.0 during the particle growth stage (■). Furthermore, in the same mixing container, 25 oml of 1.0 Mu acid forging solution and 0.97
250d aqueous solution containing 5M potassium bromide and 0.025M potassium iodide and 15% gelatin aqueous solution
0M1 was added at the same time at °C for 50 minutes, and the cured ultrafine particles were immediately and continuously introduced into a reaction vessel maintained at 75 °C pAg = 9.0 (particle growth stage n). Emulsion 2-A
was washed with water and redispersed in the same manner as Emulsion 1A, and optimally gold-sulfur sensitized. Emulsions 2-B to 2-L (emulsions according to the present invention) The composition of the halogen aqueous solution added to the reaction vessel and mixer at the nucleation stage and grain growth stage, the addition time and pAg at each stage for emulsion 2-A are Eleven types of emulsions, Emulsions 2-B to 2-L, were prepared by changing the grain size, the layered structure 1n of iodide distribution within the grains, and the crystal habit as shown in Table 5. Emulsions 2-B to 2-L were washed with water and re-split in the same manner as Emulsion 2-A to optimally sensitize gold-sulfur seedlings.

/ / These emulsions 2-A to 2-I. gi (El 1 0 1
Samples 201-2 coated with the same composition as ~106
03 was produced.

The wipes 201 to 206 were subjected to the same wave exposure and RMS measurement pattern as in Example 1 as in Samples 101 to 106, and were subjected to the same processing as in Example 1 to perform sensitometry and RMS. The 4111 determination of 4a was carried out. The results are shown in Table 7.

As can be seen from Table 7, the test r'l 2 0 according to the present invention
Samples 1 to 206 had a higher maximum concentration and good granularity than comparative samples 101-106.

(Composition of each layer) IN = Antihalation layer Black colloidal silver UV absorber U-1 UV absorber U-2 High boiling point solvent Oi 1-1 Gelatin 2nd layer: Intermediate layer-1 CpdD High boiling point organic solvent Oil -3 0. 25g/m 0. 1g/m 0. 1g/m 1. 9g/of l O■/m 40I! t/n? 3rd gelatin layer: Intermediate layer-2 4th gelatin layer; 1st red-sensitive emulsion layer sensitizing dyes S-t and S Silver iodobromide emulsion coupler C-1 C-2 High boiling point g9 solvent Qil Gelatin o. 4g/n { 0. Amount of silver spectrally sensitized at 4 g/m 2 0.4 g/m 0.2 g/td O. 05g/rd 2 Q, lee/n? 0. 8 g/rrr 5th layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (monodispersed Agl-containing 4 mol% N with average grain size 0.4 μm) Cubic emulsion> Silver amount 0.4g/rd O.2g/m O.2g/n { 0.05glrd +-2 0.1cc/m 0.8g/i Coupler C-1 C-3 C-2 High boiling point organic Solvent Oi Gelatin 6th layer: 3rd red-sensitive emulsion layer sensitizing dyes S-1 and S Silver iodobromide emulsion coupler C-3 Gelatin 7th layer: Intermediate layer-3 Dye D-1 Gelatin 8th layer: Intermediate Layer-4 Amount of silver spectrally sensitized with compound CpdA 2 0.4g/〆0.7g/Ba 1.1g/% 0.02g/m Q,6g/m 0.2g/td Gelatin 1.0g/rd 9th
N=silver iodobromide emulsion spectrally sensitized with leveling dyes S-3 and S-4 in the first green-sensitive emulsion layer Silver amount 0. 5g/rrl coupler C-
4 0.3g/rd Compound Cpd8
0.03g/rd gelatin
0.5g/n? 10th layer: Second green-sensitive emulsion layer Silver iodobromide emulsion containing auxiliary dyes S-3 and S-4 (
Monodispersed cubes with average particle size of 0.5 μm and Agl content of 5 mol%) Ginya 0.4 g/m Kabler C-4 0.3 g/r+? Compound Cpdl3 0.03g/m Gelatin 0. 6g/r+? 1st layer:
3rd} 3rd sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-3 and S-4
Silver bond 0.5g/Pocopler C-4
0.13g/m Compound CpdB
O. 0 8 glrd gelatin
1.0g/% 12th layer: Intermediate layer-5 Dye D-20.05g/gelatin resistant 0.6g/m No. 13WJ
:Yellow filter layer yellow colloidal silver 0, Ig/po compound C
pdA O. Olg/m gelatin
1.1g/n? 147th W: Middle fJl layer-6 Gelatin 0.4 g/m 15th layer:
First blue-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-5 and S-6 (
Monodispersed cubic emulsion with average grain size of 0.35 μm and Agl content of 3 mol %) Silver amount 0.6 g/nf Coupler C-5 0. 6g/rrr
Gelatin 0.8g/m 16th layer:
Second blue-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-5 and S-6 (
Average diameter: 0.75μm, average aspect ratio of all particles: 4
:1, tabular grains with Agl content of 2 mol%) Silver circumference 0
．． 4g/n (Coupler C-5 0.3g
/n{C-6 0.3g/m Gelatin 0.9g/m 17th layer:
Third emulsion layer Silver iodobromide emulsion containing melting dyes S-5 and S-6 (
Average diameter 1.0/lm, average aspect ratio of all particles 4
:l, Ag + tabular grains with a content of 2 mol%) Silver amount
0.1/mf coupler C-6 0.7g
/+Igelatin 1. 2g/n
{18th layer: 1st protective layer ultraviolet absorber ui U-3 U-4 U-5 U-6 Compound CpdC Dye D-3 0.04 g/m o. 03g/n { 0. 03g/n { 0.05g/10. 05g/nf 0. 8g/i 0. 05g/rd Gelatin 0.7g/Ba 19th layer:
2nd protective layer fine-grain silver iodobromide emulsion (average grain size 0.08 μmAg + content 1 monore%) 0.1 g/polymethyl methacrylate grain (average grain size 1.5 μm)
O. Ig/n {4:6 copolymer of methyl methacrylate and acrylic acid (particle size 1.5μ) 0. 1g/% Silicone oil 0.03g/Ifluorine-containing surfactant W-1 3■/, {gelatin
In addition to the above ingredients, gelatin hardener H1 and a surfactant were added to each layer at 0.8 g.

Structure of the compound used in Example 3
l+. ．． , C-2 tc, I+ Oi1 C-5 C-3 011 CG COOCiHt(iso) S l (CH2). S.O. .

C. llS S 2 0 (CHHz):lSO3e (Cll!) 3SO3NB (Cllz)-S(L+.

C, It U 4 110 Lノ5 U 6 ○ il 1 Dibutyl fuculate Oil 2 Tricresyl phosphate SO311N (C2+15) 3 S 6 SO311N (Czlls) c SO3 CpdA 011 Cllr-Clh 0 CpdD 0H D ■ D 2 S.O. Na H l W-1 C II z = C H SO z C H 2
C O N H C 11 t? I■=C! IS
O■C H z C O N H C H tC11
, / (Effects of the Invention) According to the method of the present invention, it is possible to change a silver halide color reversal photographic light-sensitive material that has a sufficiently high maximum density and a significantly better graininess while having an equivalent or higher sensitivity. Recognize.

Claims (1)

[Claims] Production of a color reversal photographic light-sensitive material by producing at least one red-sensitive silver halide emulsion, a green-sensitive silver halide emulsion, and a blue-sensitive silver halide emulsion, and further coating and laminating each of the above-mentioned emulsions on a support. In the method, silver halide grains prepared outside the reaction vessel are added to a reaction vessel in which grain nucleation or crystal growth of the at least one emulsion occurs, and then at least a portion of the crystal growth is caused in the reaction vessel. 1. A method for producing a silver halide color reversal photographic light-sensitive material.