JP2505262B2 - Method for producing silver halide emulsion - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a silver halide photographic emulsion which provides a light-sensitive material having high sensitivity and low fog. The present invention also relates to a method for producing a silver halide photographic emulsion which gives a light-sensitive material having less fluctuations in sensitivity and fog during the storage aging period.

[Prior art]

The basic performance required for a photographic silver halide emulsion is high sensitivity, low fog and fine grain.

In order to increase the sensitivity of the emulsion, (1) increase the number of photons absorbed by one grain, (2) increase the efficiency of conversion of photoelectrons generated by light absorption into silver clusters (latent images), And (3) it is necessary to enhance the developing activity in order to effectively utilize the latent image formed. Increasing the size increases the number of absorbed photons in one particle, but reduces the image quality. Increasing the development activity is also an effective means for increasing the sensitivity, but in the case of parallel type development such as color development, grain deterioration is generally accompanied. In order to increase the sensitivity without deterioration of graininess, it is most preferable to increase the efficiency of converting photoelectrons into a latent image, that is, increase the quantum sensitivity. In order to enhance the quantum sensitivity, it is necessary to eliminate inefficient processes such as recombination and latent image dispersion as much as possible. It is known that a method of reduction sensitization in which a small silver nucleus having no developing activity is formed inside or on the surface of silver halide is effective for preventing recombination.

Attempts at reduction sensitization have been studied for a long time. Carroll
(Carroll) reduced tin compounds in US Patent No. 2,487,850, Lowe et al. Reduced polyamine compounds in US Patent No. 2,512,925, and Fallens (Farence) reduced thiourea dioxide compounds in British Patent No. 789,823. It has been disclosed that it is useful as a sensitizer. Furthermore Co
llier is Photographic Science and Engine
ering, Vol. 23, p. 113 (1979), compares the properties of silver nuclei produced by various reduction sensitization methods. She adopted the methods of dimethylamine borane, stannous chloride, hydrazine, high pH aging, low pAg aging. The method of reduction sensitization is further U.S. Pat.Nos. 2,518,698 and 3,201,254,
No. 3,411,917, No. 3,779,777, and No. 3,930,867. Regarding the improvement of reduction sensitization method as well as the selection of reduction sensitizer, Japanese Examined Patent Publication Nos. 57-33572 and 58-1410
No. Among these, conventionally known reduction sensitizers are listed, and ascorbic acid is described therein. However, compounds such as thiourea dioxide are preferred and the examples also show thiourea dioxide, silver aged and hydrazine. Therefore, favorable properties of the ascorbic acid compound as a reduction sensitizer have not been found. Regarding further improvement, JP-A-57-179
No. 835 is disclosed.

However, in order to put reduction sensitization into practical use, it is necessary to overcome the problem of storage stability of the light-sensitive material. Regarding the technique for improving the storage stability of reduction-sensitized emulsions, JP-A-57-82831,
Although it is disclosed in No. 60-178445, it has not reached a sufficient level of improvement. In spite of many studies as described above, the range of increase in sensitivity was insufficient as compared with hydrogen sensitization in which a photosensitive material was treated with hydrogen gas under vacuum. This is Journal of Imaging Science, Vol. 29, p. 233 (1985).
Have been reported by Moisar et al. At the same time, improvement of the storage stability of the light-sensitive material containing a reduction sensitizer has been awaited.

[Problems to be solved by the invention]

Conventional reduction sensitization technology has been unsatisfactory in response to the recent demand for high sensitivity and high image quality. One is that the sensitivity and fog of the light-sensitive material containing the emulsion subjected to reduction sensitization have large fluctuations during storage. The second is that the range of increase in sensitivity due to reduction sensitization is insufficient.

An object of the present invention is to provide a method for producing an emulsion which provides a light-sensitive material having high sensitivity and low fog. In particular, it is an object of the present invention to provide a method for producing a highly sensitive light-sensitive material in which fluctuations in sensitivity and fogging during storage aging are small. A second object is to provide a color light-sensitive material, particularly a color photographic light-sensitive material, which has high sensitivity, low fog, and little performance fluctuation during storage aging.

[Means for solving problems]

An object of the present invention is to carry out reduction sensitization by 5 × 10 ^-5 to 1 × 10 ^-1 mol of ascorbic acid or at least one derivative thereof per mol of silver halide during the growth of silver halide grains. It was achieved by a method for producing a characteristic silver halide emulsion. It was achieved by the above-mentioned method for producing a silver halide emulsion, which is preferably reduction-sensitized in the presence of at least one compound represented by the general formula [I], [II] or [III].

_{[I] RSO 2 S-M} [II] RSO 2 S-R 1 [III] RSO 2 S-L m -SSO 2 - ² wherein, R, R ^1, R ² are either the same or different Also, it may represent an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1.

The compounds of the general formulas [I] to [III] may be a polymer containing a divalent group derived from the structure represented by [I] to [III] as a repeating unit.

 The present invention will be described in detail below.

The manufacturing process of silver halide emulsion is roughly divided into the processes of grain formation, desalting, chemical sensitization, coating, and the like. Particle formation is nucleation
Divided into aging and growth. These steps are not performed uniformly, but the order of the steps is reversed or the steps are repeatedly performed. The fact that reduction sensitization is performed during the production process of a silver halide emulsion basically means that it may be performed at any process. The reduction sensitization may be carried out during nucleation, which is an initial setting stage of grain formation, during physical ripening, during growth, or before or after chemical sensitization. When chemical sensitization is performed in combination with gold sensitization, it is preferable to carry out reduction sensitization prior to chemical sensitization so that unfavorable fog does not occur. Most preferred is a method of reduction sensitization during growth of silver halide grains. The term "during growth" here also refers to a method in which silver halide grains are subjected to reduction sensitization while they are physically ripening or are being grown by the addition of a water-soluble silver salt and a water-soluble alkali halide,
It means that the method also includes a method of performing further reduction sensitization in the state where the growth is temporarily stopped during the growth and then further growing.

Specific examples of ascorbic acid and its derivatives (hereinafter referred to as "ascorbic acid compound") include the following.

(A-1) L-ascorbic acid (A-2) Sodium L-ascorbate (A-3) Potassium L-ascorbate (A-4) DL-Ascorbic acid (A-5) Sodium D-ascorbate (A -6) L-ascorbic acid-6-acetate (A-7) L-ascorbic acid-6-palmitate (A-8) L-ascorbic acid-6-benzoate (A-9) L-ascorbic acid-5,6 -Diacetate (A-10) L-ascorbic acid-5,6-O-isopropylidene To add the above-mentioned ascorbic acid compound in the process for producing the silver halide emulsion of the present invention, they are directly dispersed in the emulsion. Alternatively, it may be added in the manufacturing process after being dissolved in a solvent such as water, methanol or ethanol alone or in a mixed solvent.

The ascorbic acid compound used in the present invention is preferably used in a large amount as compared with the addition amount in which a reduction sensitizer is conventionally used. For example, in Japanese Examined Patent Publication No. 57-33572, "the amount of reducing agent usually does not exceed 0.75 × 10 ^-2 milliequivalents (8 × 10 ^-4 mol / AgX mol) per g of silver ion. Amount of 0.1-10 mg per kg of silver nitrate. (As ascorbic acid, 10 ^-7 to 10 ^-5
Mol / AgX mol) is often effective. (The converted value depends on the inventors). US-2,487,850 describes that "a tin compound can be used as a reduction sensitizer as an addition amount of 1 × 10 ^{-7 to} 44 × 10 ^-6 mol".
Further, in JP-A-57-179835, it is described that it is appropriate to use about 0.01 mg to about 2 mg of thiourea dioxide per mol of silver halide and about 0.01 mg to about 3 mg of stannous chloride. ing. The ascorbic acid compound used in the present invention includes emulsion grain size, halogen composition, emulsion preparation temperature,
The preferable addition amount depends on factors such as pH and pAg, but it is desirable to select from the range of 5 × 10 ^-5 mol to 1 × 10 ^-1 mol per mol of silver halide. More preferably 5
It is preferably selected from the range of x10 ^-4 mol to 1 x 10 ^-2 mol. Especially preferred is to select from the range of 1 × 10 ⁻³ mol to 1 × 10 ⁻² mol.

The ascorbic acid compound of the present invention may be added at any stage of the emulsion production process, but the method of addition during grain growth is particularly preferred. It may be added to the reaction vessel in advance, but it is more preferable to add it at an appropriate time for particle formation. It is also possible to add a reduction sensitizer to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide in advance and use these aqueous solutions to form grains. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains are formed, or to add the solution continuously for a long time.

The method of reduction sensitization using the ascorbic acid compound of the present invention is more sensitive than the conventionally known reduction sensitization method,
Although it is excellent in fog and stability over time, it is more preferable in some cases to combine it with other reduction sensitization methods. However, it can be used only as an auxiliary means for reduction sensitization, and it is better to use an ascorbic acid compound as the main means for reduction sensitization. As a combination method, a known reducing agent is added to the silver halide emulsion, a method of growing or aging in a low pAg atmosphere of pAg 1 to 7 called silver ripening, a pH 8 to 11 called high pH ripening.
Any of the method of growing or aging in a high pH atmosphere can be selected.

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

Stannous salts as reduction sensitizers, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid,
Although silane compounds and borane compounds are known, ascorbic acid compounds give superior results to these known reduction sensitizers.

In the reduction sensitization of the present invention, at least one selected from the compounds represented by the general formulas [I], [II] and [III] is obtained by subjecting the reduction sensitization to an ascorbic acid compound in the production process of a silver halide emulsion. It is preferred to add two compounds during the manufacturing process.

[I] in R-SO ₂ S-M [II] R-SO ₂ S-R ¹ (III) _{R-SO 2 S-Lm-} SSO 2 -R 2 Formula, R, R ^1, also R ² is the same They may be different and represent an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1.

The compounds of the general formulas [I], [II] and [III] will be described in more detail. When R, R ¹ and R ² are aliphatic groups,
Preferably, an alkyl group having 1 to 22 carbon atoms and 2 carbon atoms
To 22 alkenyl groups and alkynyl groups, which may have a substituent. As an alkyl group,
For example, methyl, ethyl, propyl, butyl, pentyl,
Hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl and t-butyl can be mentioned.

Examples of the alkenyl group include allyl and butenyl.

Examples of the alkynyl group include propargyl and butynyl.

The aromatic group of R, R ¹ and R ² preferably has 6 to 20 carbon atoms, and examples thereof include phenyl and naphthyl. These may be substituted.

The heterocyclic group for R, R ¹ and R ² includes nitrogen, oxygen,
3- to 15-membered ring having at least one element selected from sulfur, selenium and tellurium, for example, pyrrolidine,
Examples thereof include piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole, imidazole, benzothiazole, benzoxazole, benzimidazole, selenazole, benzoselenazole, tellurazole, triazole, benzotriazole, tetrazole, oxadiazole and thiadiazole.

Examples of the substituents of R, R ¹ and R ² include an alkyl group (eg, methyl, ethyl, hexyl), an alkoxy group (eg, methoxy, ethoxy, octyl), an aryl group (eg, phenyl, naphthyl, tolyl), a hydroxy group, Halogen atom (eg fluorine, chlorine, bromine, iodine etc.), aryloxy group (eg phenoxy), alkylthio group (eg methylthio, butylthio), arylthio group (eg phenylthio), acyl group (eg acetyl, propionyl, butyryl, valeryl), A sulfonyl group (eg, methylsulfonyl, phenylsulfonyl),
Acylamino group (eg, acetylamino, benzamino), sulfonylamino group (methanesulfonylamino,
Benzsulfonylamino), an acyloxy group (eg, acetoxy, benzoxy), a carboxyl group, a cyano group, a sulfo group, an amino group and the like.

L is preferably a divalent aliphatic group or a divalent aromatic group. Examples of the divalent aliphatic group of L include CH _{2 n
(N = 1~12), -CH 2} -CH = CH-CH 2 -, -CH 2 C = CCH 2 -, Examples include a xylylene group and the like. Examples of the divalent aromatic group of L include phenylene and naphthylene.

These substituents may be further substituted as the above-mentioned substituents.

M is preferably a metal ion or an organic cation. Examples of metal ions include lithium ions, sodium ions, and potassium ions. As the organic cation, ammonium ions (for example, ammonium,
Examples thereof include tetramethylammonium, tetrabutylammonium), phosphonium ions (tetraphenylphosphonium), and guanidine groups.

Specific examples of the compound represented by the general formula [I], [II] or [III] are shown in Table A, but are not limited thereto.

The compound of the general formula [I] can be easily synthesized by the method described in JP-A-54-1019 and British Patent 972,211.

The compound represented by the general formula [I], [II] or [III] is preferably added in an amount of 10 ^-7 to 10 ^-1 mol per mol of silver halide. From 10 ^-6 to 10 ^-2 , especially from 10 ^-5
An addition amount of 10 ⁻³ mol / mol Ag is preferable.

For adding the compounds represented by the general formulas [I] to [III] during the production process, a method usually used when adding an additive to a photographic emulsion can be applied. For example, a water-soluble compound is an aqueous solution having an appropriate concentration, and a compound that is insoluble or hardly soluble in water is a suitable organic solvent that is miscible with water, for example, alcohols, glycols, ketones, esters, amides and the like. Among them, it can be dissolved in a solvent that does not adversely affect the photographic properties and added as a solution.

The compound represented by the compound [I], [II] or [III] may be added at any stage during grain formation of the silver halide emulsion, before or after chemical sensitization and during production. Preferred is a method of adding the compound before or during the reduction sensitization. Particularly preferred is the method of addition during grain growth.

It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time for particle formation. Alternatively, the compounds [I] to [III] may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and particles may be formed using these aqueous solutions. In addition, it is also a preferable method to add the solutions of the compounds [I] to [III] in several times with the formation of particles or to continuously add them for a long time.

The most preferable compound of the present invention has the general formula [I].

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention,
Any silver halide such as silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used. Preferred silver halides are silver iodobromide, silver bromide, and silver chlorobromide containing 30 mol% or less of silver iodide.

The silver halide grains used in the present invention may be normal crystals containing no twin planes, for example, as described in P.163, edited by the Photographic Society of Japan, Photograph of Basic Silver Salt Photography of the Photo Industry (Corona), for example, Select from twin twins containing one twin plane, parallel multiple twins containing two or more parallel twin planes, non-parallel multiple twins containing two or more non-parallel twin planes according to the purpose. Can be used. In the case of a normal crystal, a cubic body composed of (100) planes, an octahedron composed of (111) planes, and a dodecahedral particle composed of (110) planes disclosed in JP-B-55-42737 and JP-A-60-222842 are used. Can be used. Furthermore, Journal of Imaging
Science Vol. 30, p. 247 (h11) face particles typified by (211), (hh1) face particles typified by (331), and (hk0) face particles typified by (210) face as reported in 1986. The (hk1) plane particles represented by the (321) plane and the (hk1) plane particles may be selected and used according to the purpose, though the preparation method requires some devise.
A tetrahedral particle in which (100) and (111) planes coexist in one particle, a particle in which (100) and (110) planes coexist, or (11
Particles in which two surfaces or many surfaces coexist, such as particles in which 1) and (110) surfaces coexist, can be selected and used according to the purpose.

The grain size of the silver halide may be fine grains of 0.1 μm or less or large grains having a projected area diameter of up to 10 μm, and may be a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution.

Narrow particle size distribution such that 80% or more of all particles fall within ± 30% of average particle size by number or weight of particles.
So-called monodisperse silver halide emulsions can be used in the present invention. In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes are mixed in the same layer or different layers in an emulsion layer having substantially the same color sensitivity. Can be applied in multiple layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used as a mixture or as a mixture.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (P. Glafkides, Ch.
imie et Physique Photographique Paul Montel, 196
7), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographic Emulsion Chemistry
(Focal Press, 1966), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VLZelikman et.
al, Making and Coating Photographic Emulsion, Focal
Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, a one-sided mixing method, a simultaneous mixing method,
Any combination of them may be used. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

The silver halide emulsion comprising the regular grains,
Obtained by controlling pAg and pH during particle formation.
For more details, see, for example, Photograhic Science and En
gineering) Volume 6, 159-165 (1962); Journal of Photographic Science (Journal of P
hotographic Science, 12: 242-251 (1964), U.S. Pat. No. 3,655,394 and British Patent 1,413,748.

Further, tabular grains having an aspect ratio of 3 or more can be used in the present invention. Tabular grains are described in Cleve, Photography Theory and Pra
ctice (1930), p. 131; Gatov, Photographic Science and Engineering (Gutoff, Pho
tographic Science and Engineering), Volume 14, 245-2
57 pages (1970); U.S. Patent Nos. 4,434,226 and 4,414,310
No. 4,433,048, 4,439,520 and British Patent No. 2,
It can be easily prepared by the method described in 112,157 and the like. The use of tabular grains has advantages such as an increase in covering power and an increase in color sensitization efficiency by a sensitizing dye, which is described in detail in US Pat. No. 4,434,226 cited above.

Tabular grains are preferred as the emulsion of the present invention. Particularly, tabular grains in which grains having an aspect ratio of 3 to 8 occupy 50% or more of the total projected area are preferable.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. These emulsion grains are described in British Patent No. 1,027,146.
And U.S. Pat. Nos. 3,505,068 and 4,444,877 and JP-A-60-14331. 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.

The silver halide emulsion of the present invention preferably has a distribution or structure with respect to the halogen composition in its grains. Typical examples are JP-B-43-13162 and JP-A-61-215.
540, JP-A-60-222845, JP-A-61-75337 and the like, which are core-shell type or double structure type particles having a halogen composition in which the inside and the surface layer of the particles are different. In such particles, the shape of the core part and the entire shape with the shell may be the same or different. Specifically, the core portion has a cubic shape, specifically, the core portion has a cubic shape, and the shape of the particles with shell may be cubic or octahedral.
On the contrary, the core part may be an octahedron and the particles with shell may have a cubic or octahedral shape. Further, although the core portion is a regular regular particle, the particle with shell may be slightly deformed or may have an irregular shape. Further, it is not a mere double structure but a triple structure as disclosed in JP-A-60-222844 or a multilayer structure having more than that, or a different composition on the surface of the core-shell double structure particles. The silver halide contained can be thinly applied.

In order to give a structure to the inside of the particle, not only the wrapping structure as described above but also a so-called junction structure can be formed. These examples are described in JP-A-59-133540, JP-A-58-108526, EP199290A2, JP-B-58-24772,
9-16254. The crystal to be bonded can be generated by bonding to the edge, corner, or face of the host crystal with a composition different from that of the host crystal. Such a junction crystal can be formed even if the host crystal has a uniform halogen composition or has a core-shell type structure.

In the case of a junction structure, it is naturally possible to combine silver halides with each other, but a silver salt compound not having a rock salt structure, such as silver rhodan or silver carbonate, can be combined with silver halide to form a junction structure. In addition, a non-silver salt compound such as PbO may be used as long as a junction structure is possible.

In the case of silver iodobromide grains having these structures, for example, in a core-shell type grain, even if the core portion has a high silver iodide content and the shell portion has a low silver iodide content, conversely The grains may have a low silver iodide content and a high shell portion. Similarly, with respect to the grains having a junction structure, the grains having a high silver iodide content in the host crystal and having a relatively low silver iodide content in the junction crystal may be used, or vice versa.

Further, the boundary portion where the halogen composition of the grains having these structures is different may be a clear boundary or an unclear boundary by forming a mixed crystal due to the composition difference, and it is positively continuous. Those with various structural changes may be used.

The silver halide emulsion used in the present invention is EP-0096727B1, EP
-0064412B1 and the like to give roundness to particles as disclosed in DE-2306447C2, JP-A-60-221320
The surface may be modified as disclosed in US Pat.

The silver halide emulsion used in the present invention is preferably a surface latent image type, but an internal latent image type emulsion may be used by selecting a developing solution or development conditions as disclosed in JP-A-59-133542. it can. A shallow internal latent image type emulsion covered with a thin shell can also be used according to the purpose.

Silver halide solvents are useful in promoting ripening.
For example, it is known to have excess halogen ions present in the reactor to accelerate aging. Therefore, it is clear that mere introduction of a halide salt solution into the reactor can accelerate aging. Other ripening agents can be used, and the total amount of these ripening agents can be added to the dispersion medium in the reactor before the addition of silver and halide salts, or 1 or 2 or more. It is also possible to add the halide salt, silver salt or peptizer of the above and to introduce them into the reactor. As another variant, the ripening agent can be introduced independently at the halide salt and silver salt addition stages.

As ripening agents other than halogen ions, ammonia or amine compounds, thiocyanate salts such as alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used.

In the present invention, it is extremely important to carry out chemical sensitization represented by sulfur sensitization and gold sensitization, and a remarkable effect is exhibited when chemically sensitized. The location of chemical sensitization differs depending on the composition, structure, and shape of emulsion grains and the intended use of the emulsion. In some cases, the chemically sensitized nuclei are embedded in the grain, at a shallow position from the grain surface, or in some cases the chemically sensitized nuclei are formed on the surface. Although it is also effective in the case of the effects of the present invention, it is particularly preferable to form a chemically sensitized nucleus near the surface.
That is, the surface latent image type emulsion is more effective than the internal latent image type emulsion.

Chemical sensitization is described by THJames, The Photographic Process, Fourth Edition, published by Macmillan, 1977, (THJames, The Theory of the Potograp
hic Process, 4 th ed, Macmillan, 1977) p. 67-76, using active gelatin, and also Research Disclosure 120, April 1974, 12008: Research Disclosure, Volume 34, 19
June 1975, 13452, U.S. Patent Nos. 2,642,361, 3,297,44
No. 6, No. 3,772,031, No. 3,857,711, No. 3,901,714,
4,266,018 and 3,904,415, and sulfur, selenium, tellurium, gold at pAg 5-10, pH 5-8 and temperature 30-80 ° C as described in British Patent No. 1,315,755.
It can be carried out using platinum, palladium, iridium or a combination of these sensitizers. Chemical sensitization is optimally carried out in the presence of gold and thiocyanate compounds and also in U.S. Pat. Nos. 3,857,711, 4,266,018 and 4,05.
4,457, a sulfur-containing compound or hypo,
It is carried out in the presence of a sulfur-containing compound such as a thiourea compound and a rhodanin compound. It is also possible to carry out chemical sensitization in the presence of a chemical sensitization aid. The chemical sensitization aids used include azaindene, azapyridazine, and azapyrimidine,
Compounds known to suppress fog and increase sensitivity in the process of chemical sensitization are used. Examples of chemical sensitization aid modifiers are U.S. Pat.Nos. 2,131,038 and 3,411,914,
No. 3,554,757, JP-A-58-126526 and the above-mentioned Daffin's "Photographic Emulsion Chemistry", pages 138-143.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. That is, azoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzenetriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines; Thioketo compounds such as oxadrinethione; azaindenes; such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes, etc. Many compounds can be added, known as antifoggants or stabilizers. For example, U.S. Patent No. 3,954,474,
Nos. 3,982,947 and JP-B-52-28,660 can be used.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or the like. The dyes used include
Cyanine dye, merocyanine dye, complex cyanine dye,
Included are complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are cyanine dyes,
It is a dye belonging to a merocyanine dye and a composite merocyanine dye. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc .; Nucleus fused with an aromatic hydrocarbon ring, that is, indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, An imidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

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

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Typical examples thereof are U.S. Patents 2,688,545, 2,977,229, 3,397,060 and 3,5.
22,052, 3,527,641, 3,617,293, 3,628,96
No. 4, No. 3,666,480, No. 3,672,898, No. 3,679,428,
3,703,377, 3,769,301, 3,814,609, 3,8
37,862, 4,026,707, British Patent 1,344,281, 1,
507,803, JP-B-43-4936, JP-B-53-12,375, JP-A-5
2-110,618 and 52-109,925.

Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

The dye may be added to the emulsion at any stage of emulsion preparation known to be useful so far. Most commonly, it is performed after the completion of chemical sensitization and before coating, but as described in U.S. Pat.Nos. 3,628,969 and 4,225,666, it is added at the same time as the chemical sensitizer and spectral sensitization is performed. The chemical sensitization can be carried out simultaneously with the chemical sensitization or prior to the chemical sensitization as described in JP-A-58-113,928. You can also start sensitization. Furthermore, the addition of these said compounds separately as taught in U.S. Pat.No. 4,225,666, i.e. adding some of these compounds prior to chemical sensitization,
The balance can be added after chemical sensitization and can be at any time during silver halide grain formation, including the method taught in US Pat. No. 4,183,756.

The addition amount is 4 × 10 ⁻⁶ to 8 × per mol of silver halide.
It can be used in an amount of 10 ^-3 mol, but in the case of a more preferred silver halide grain size of 0.2 to 1.2 μm, it is about 5 × 10 ^-5 to 2
× 10 ^-3 mol is more effective.

The above-mentioned various additives are used in the light-sensitive material of the present technology, but various additives other than the above can be used depending on the purpose.

For more information on these additives, see Research Disclosure Item 17643 (December 1978) and Item 188716.
(November, 1979) and the relevant places are summarized in the table below.

Various color couplers can be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG.

As the yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
No. 1,752, JP-B-58-10739, UK Patent No. 1,425,020,
No. 1,476,760 and the like are preferable.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable.
4,310,619, 4,351,897, European Patent No. 73,636,
U.S. Pat.Nos. 3,061,432, 3,725,067, Research
Disclosure No. 24220 (June 1984), JP 60
-33552, Research Disclosure No.24230 (19
June 1984), JP-A-60-43659, U.S. Patent No. 4,500,630
Nos. 4,540,654 and the like are particularly preferable.

Examples of cyan couplers include phenol-based and naphthol-based couplers, and U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, and 4,296,200.
No. 2,369,929, No. 2,801,171, No. 2,772,162
No. 2, No. 2,895,826, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, U.S. Patent No.
Those described in 3,446,622, 4,333,999, 4,451,559, 4,427,767 and EP 161,626A are preferable.

For example, Research Disclosure No. 17643 is a colored coupler for correcting unnecessary absorption of a coloring dye.
VII-G, U.S. Pat. No. 4,163,670, Japanese Examined Patent Publication No. 57-39413.
Nos. 4,004,929 and 4,138,258, and British Patent 1,146,368 are preferred.

As a coupler in which the coloring dye has an appropriate diffusibility,
For example, U.S. Patent No. 4,366,237, British Patent No. 2,125,570
No., European Patent No. 96,570, West German Patent (Publication) No. 3,234,53
Those described in No. 3 are preferable.

Typical examples of polymerized dye-forming couplers are U.S. Pat.Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 2,102,173 and the like.

Couplers that 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 above-mentioned RD17643, VIII-F.
Patents described in paragraphs, JP-A-57-151944 and 57-154234
And Nos. 60-184248 and U.S. Pat. No. 4,248,962 are preferred.

As a coupler that releases a nucleating agent or a development accelerator in an image state during development, for example, British Patent No. 2,097,140,
Those described in JP-A-2,131,188, JP-A-59-157638 and JP-A-59-170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include, for example, competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472, and 4,338,3.
93, No. 4,310,618, etc., multi-equivalent coupler, DIR redox compound or DIR coupler-releasing coupler, DIR coupler-releasing coupler or redox, described in JP-A-60-185950, JP-A-62-24252, and European Patent 173,
Couplers which release dyes that recolor after release as described in 302A, such as RD Nos. 11449 and 24241, bleaching accelerator releasing couplers described in JP-A-61-201247, such as U.S. Pat.
No. 553,477.

The coupler used in the present invention can be introduced into the 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.

Specific examples of the high boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate) and phosphorus. Esters of acids or phosphonic acids (for example, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate), benzoic acid esters (for example, 2-ethylhexyl benzoate, dodecyl) Benzoate, 2-ethylexyl-p-hydroxybenzoate), amides (eg, N, N-diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or pheno Class (e.g., isostearyl alcohol, 2,4-di -tert- aminophenol),
Aliphatic carboxylic acid esters (eg, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate), aniline derivatives (for example,
N, N-dibutyl-2-butoxy-5-tert-octylaniline), hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene) and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used,
Typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone,
Examples include ethoxyethyl acetate and dimethylformamide.

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

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.

When the present invention is applied to a color photographic material, it can be applied to a light-sensitive material having various structures and a light-sensitive material obtained by combining a layer structure and a special color material.

A typical example thereof will be illustrated. JP-B-47-49031, JP-B-49
-3843, JP-B-50-21248, JP-A-59-38147, JP-A-59-60437, JP-A-60-227256, JP-A-61-4043,
A combination of the coupling speed and diffusivity of a color coupler and the layer structure, as in JP-A-61-43743 and JP-A-61-42657. JP-B-49-15495, U.S. Patent 3843469
No. 53-37017, JP-B-53-37018 and JP-A-51-4, in which the same color-sensitive layer is divided into two or more layers.
9027, JP-A-52-143016, JP-A-59-97424, JP-A-53-97831, JP-A-62-200350, and JP-A-59-177551. Examples thereof include those in which the arrangement of sensitivity layers and the arrangement of layers having different color sensitivities are specified.

Suitable supports that can be used in the present invention are, for example, those mentioned above.
RD.No. 17643, page 28, and RD.No. 18716, page 647 From the right column
See page 648, left column.

The color photographic light-sensitive material according to the present invention has the above-mentioned RD.No.
17643, pages 28 to 29, and No. 18716, 651, left column to right column, can be developed by a usual method.

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

Color developing solutions include alkali metal carbonates, pH buffers such as borates or phosphates, bromide salts, iodide salts,
It is common to include a development inhibitor such as benzimidazoles, benzothiazoles or mercapto compounds, or an antifoggant. In addition, if necessary, various kinds such as hydroxylamine, diethylhydroxylamine, sulfite hydrazine, phenylsemicarbazide, triethanolamine, catecholsulfonic acid, triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Preservatives, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, 1-
Auxiliary developing agents such as phenyl-3-pyrazolidone, viscosity-imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic 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, black and white development is usually performed before color development. This black and white developer contains dihydroxybenzenes such as hydroquinone, 1-phenyl-3-
Known black-and-white developing agents such as 3-pyrazolidones such as pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The pH of these color developing solution and black-and-white developing solution is generally 9 to 12. The replenishment amount of these developers is
Although it depends on the color photographic light-sensitive material to be processed, it is generally 3 l or less per 1 m 2 of the light-sensitive material and can be reduced to 500 ml or less by reducing the bromide ion concentration in the replenisher. When the replenishment amount is reduced, the contact area with the air in the processing tank is reduced to evaporate the liquid,
It is preferable to prevent air oxidation. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution.

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

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further processing with two continuous bleach-fix baths,
The fixing treatment before the bleach-fixing treatment or the bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose.
Examples of bleaching agents include iron (III), cobalt (III),
Compounds of polyvalent metals such as chromium (VI) and copper (II), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are ferricyanide; dichromate; iron (II
I) or cobalt (III) organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Aminopolycarboxylic acids such as diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. it can. Of these, aminopolycarboxylic acid iron (II) including ethylenediaminetetraacetic acid iron (III) complex salts
I) Complex salts and persulfates are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, iron (III) aminopolycarboxylate
Complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleach accelerators are described in the specification such as US Pat. No. 3,893,858. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. 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.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but the use of thiosulfates is common,
In particular, ammonium thiosulfate can be used most widely. As a preservative for the bleach-fix solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

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 process depends on the characteristics of the light-sensitive material (for example, depending on the materials used such as couplers), application, and further the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment system such as countercurrent, forward flow, and various other conditions Can be set in a wide range. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture and
It can be obtained by the method described in Televison Engineers Volume 64, P.248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. 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 ion and magnesium ion described in JP-A-61-131632 can be very effectively used. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antifungal agents" The sterilizing agents described in "Microbial Sterilization, Sterilization, and Antifungal Technologies" edited by the Society of Hygiene Technology and "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents can also be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can also be variously set depending on the characteristics of the light-sensitive material, the use, etc., but generally 15-45 ° C. for 20 seconds-10 minutes, preferably 25-40 ° C. for 30 seconds.
A range of seconds-5 minutes is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such a stabilization process, Japanese Unexamined Patent Publication No.
All known methods described in Nos. 8,543, 58-14,834 and 60-220,345 can be used.

Further, there is a case where a stabilizing treatment is further performed after the water washing treatment, and an example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. . Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.

The silver halide color light-sensitive material of the present invention contains various 1-phenyl-containing compounds, if necessary, for the purpose of promoting color development.
You may incorporate 3-pyrazolidones. Typical compounds are JP-A-56-64,339, JP-A-57-144,547, and JP-A-58-11.
No. 5,438 is described.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

Further, the silver halide light-sensitive material of the present invention is described in US Pat.
500,626, JP-A-60-133449, 59-218443, 61-
It can also be applied to the photothermographic materials described in 238056 and European Patent 210,660A2.

 Examples will be shown below for further description.

Example 1 Double twinned grains of silver iodobromide having an average iodine content of 24 mol% and an average sphere-equivalent diameter of 0.8 μm were used as seed crystals, and the core-shell ratio was controlled by a control double jet method in a gelatin aqueous solution.
An emulsion consisting of silver iodobromide twinned grains having an average equivalent spherical diameter of 1.2 μm was formed so that the iodine content of the shell was 2 mol% and the average iodine content was 10 mol%.

After grain formation, the emulsion is subjected to the usual desalination and water washing process at 40 ° C.
Redispersion was carried out under the conditions of pAg8.9 and pH 6.3. The emulsion thus prepared is designated as Em-1. On the other hand, 1 minute before the start of shell formation, the thiosulfonic acid compound 1-
Em-2 to 4 are emulsions in which 2,1-6 and 1-16 were added to the reaction pots shown in Table 1-1 to form grains.

When particles are formed similarly to Em-1, shell formation starts 1
After a minute, the aforementioned reduction sensitizer A-1 (L-ascorbic acid)
And tin chloride were added in the amounts shown in Table 1-2 to prepare emulsions Em-5 to Em.
-6 was produced.

Furthermore, when the same particle formation as Em-1 is performed, 1 minute before the start of shell formation, the thiosulfonic acid compound 1-2,1-6,1
-16 was added, and 1 minute after the start of shell formation, the reduction sensitizer L-
The emulsions of the present invention and comparative emulsion Em-7 shown in Tables 1-3 were prepared by adding ascorbic acid and tin chloride in the optimum amounts.
Em-12 was made.

The emulsion of the present invention and the comparative emulsions 1 to 1 thus prepared
An emulsion of 12 was optimally sensitized with gold and sulfur by using sodium thiosulfate and chloroauric acid.

The emulsion and the protective layer were coated on the triacetylcellulose film support provided with the undercoat layer in the coating amounts shown in Table 1-4.

Table 1-4 (1) Emulsion layer-Emulsion ... Emulsions 1 to 12 (silver 1.7 × 10 ^-2 mol / m ² ) shown in Table 1-1 to Table 1-3-Coupler (1.5 × 10 ^-3 mol / m) ² ) ・ Tricresyl phosphate (1.10 g / m ² ) ・ gelatin (2.30 g / m ² ) (2) protective layer ・ 2,4-dichlorotriazine-6-hydroxy-s-triazine sodium salt (0.08 g / m ²⁾ Gelatin (1.80 g / m ² ) These samples were exposed to sensitometry and subjected to the following color development processing.

The density of the treated sample was measured with a green filter. The obtained photographic performance results are shown in Table 1-5.

 The developing treatment used here was carried out at 38 ° C. under the following conditions.

 1. Color development …… 2 minutes 45 seconds 2. Bleaching …… 6 minutes 30 seconds 3.Washing …… 3 minutes 15 seconds 4. Settling …… 6 minutes 30 seconds 5. Washing …… 3 minutes 15 seconds 6. Stability: 3 minutes 15 seconds The composition of the processing liquid used in each process is as follows.

Color developer Sodium nitrilotriacetate 1.4 g Sodium sulfite 4.0 g Sodium carbonate 30.0 g Potassium bromide 1.4 g Hydroxylamine sulfate 2.4 g 4- (N-ethyl-N-βhydroxyethylamino)-
2-Methyl-aniline sulphate 4.5g Add water 1 Bleach Ammonium bromide 160.0g Ammonia water (28%) 25.0ml Ethylenediamine-ferric acetic acid sodium trihydrate 130
g Glacial acetic acid 14 ml Add water 1 Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (700g / l) 175.0ml Sodium bisulfite 4.6g Add water 1 Stabilizer Formalin 8.0ml Add water 1 exposure was performed for 10 seconds and 1/100 second as usual wedge exposure.

A light source adjusted to a color temperature of 4800 ° K using a filter was used, and blue light was extracted using a blue filter (BPN42 manufactured by Fuji Photo Film Co., Ltd.). The sensitivity was compared from the fog at an optical density of 0.2. The sensitivity is indicated by a sensitivity of 10 for the sample using the emulsion Em-1.
The relative sensitivity was set to 0. (Both the values of 1/100 second and 10 seconds were set to 100. The fog value was a value for a non-exposed portion, which was 1/100 second, and was the same value for 10 seconds.) Table 1-5 As is clear from the above, it can be seen that the emulsion of the present invention has reduced fog and high sensitivity (especially low illuminance).

Samples 1 to 12 coated with the emulsions 1 to 12 were aged for 12 months in an environment of a temperature of 25 ° C. and a humidity of 60%, and then exactly the same sensitometric experiment was conducted. Sample 1 before aging
Table 1-6 shows the results of relative sensitivity, where the sensitivity was 100. It can be seen that the coated sample of the emulsion of the present invention shows little deterioration in sensitivity after time and increase in fog, and exhibits excellent storage stability.

Example 2 In the step of forming an emulsion according to the emulsion preparation method described in Example 1, L-ascorbic acid was added in an amount of 2 × 10 6 per mol of silver.
^-3 mol was added at the following addition time to form an emulsion.
Also, at this time, during particle formation, 1 minute before the start of shell formation, or
Thiosulphonic acid compound 1-2 after particle formation and before water washing step
An emulsion was also formed in which 3 × 10 ⁻⁵ mol of silver was added per mol of silver.

(Time of addition of L-ascorbic acid) a Before particle formation b After 1 minute from the start of shell formation c Immediately after the end of shell formation d Just before the start of chemical sensitization (Time of addition of thiosulfonic acid compound) A 1 minute before the start of shell formation B Particle formation The emulsion prepared after the post-washing step was optimally chemically sensitized by gold / sulfur sensitization. The emulsions 13 to 24 thus prepared are shown in Table 2.
-1.

These emulsions were coated in the same manner as in Example 1 and sensitometric evaluation was performed. The results shown in Table 2-2 were obtained. Similar to Example 1, the evaluation of sensitivity is shown by relative sensitivity with the sensitivity of Em-1 optimally subjected to gold / sulfur sensitization as 100.

Here, Em-16 and 17 are obtained by using Em-5 and 7 with the same ascorbic acid and thiosulfonic acid (I-2) at the same addition time. As shown, the same sensitivity and fog are shown, and it can be seen that the effect of the present invention is reproducible. As shown in Table 2-2, the emulsion of the present invention has a high sensitivity and exhibits the performance of suppressing fog. When the photographic performance of this paint sample was evaluated under the same conditions as in Example 1, the same results as in Example 1 were obtained.

Example 3 A spectrally sensitized emulsion was prepared by adding the following dyes to the chemically sensitized emulsion prepared in Example 1 during chemical sensitization as shown in Table 3-1.

The emulsion thus prepared was coated in the same manner as in Example 1, and a sensitometric experiment was performed.

Dye Group 1 (Red Dye) Dye group 2 (green dye) Dye Group 3 (Blue Sensitive Dye) Sensitizing Dye VIII 2.2 × 10 ^-4 mol / mol Ag For the sensitometric experiment, a yellow filter (SC-52 manufactured by Fuji Photo Film Co., Ltd.) was used instead of the blue filter of Example 1 for the emulsion to which the red and green sensitizing dyes were added, and the emulsion was exposed to blue. The dye-sensitized emulsion was exposed without using the above filter. Other conditions are the same as those in the first embodiment.
Table 3-2 shows the sensitivity of Em-25, -26 and -27 for 10 seconds and 1 respectively.
Em-28 is the relative sensitivity when set to 100 for 100 second exposure.
Shows the sensitivity of Em-33 (fog value is a value for a non-exposed portion, and is the same value at 1/100 seconds and 10 seconds).

As is apparent from Table 3-2, it was found that the emulsion of the present invention can have high sensitivity and low fog even when color sensitization is performed.

Example 4 A sample which is a multilayer color light-sensitive material was prepared by applying multiple layers of the following composition on a subbed cellulose triacetate film support.

(Photosensitive Layer Composition) The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² unit, and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

Sample 1st layer; antihalation layer Black colloidal silver… Silver 0.18 gelatin… 1.40 2nd layer; Intermediate layer 2,5-di-t-pentadecylhydroquinone… 0.18 EX-1… 0.07 EX-3… 0.02 EX-12… 0.002 U-1 ... 0.06 U-2 ... 0.08 U-3 ... 0.10 HBS-1 ... 0.10 HBS-2 ... 0.02 gelatin ... 1.04 Third layer (first red-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (iodinated) Silver 6 mol%, average particle size 0.
6μ, variation coefficient for particle size 0.15) Silver 0.55 Sensitizing dye I… 6.9 × 10 ^-5 Sensitizing dye II… 1.8 × 10 ^-5 Sensitizing dye III… 3.1 × 10 ^-4 Sensitizing dye IV… 4.0 × 10 ^-5 EX-2 0.350 HBS-1 0.005 EX-10 0.020 Gelatin 1.20 Fourth layer (second red emulsion layer) Tabular silver iodobromide emulsion (silver iodide 10 mol%, average grain size 0 .
7μ, average aspect ratio 5.5, average thickness 0.2μ) ... Silver 1.0 Sensitizing dye I… 5.1 × 10 ^-5 Sensitizing dye II… 1.4 × 10 ^-5 Sensitizing dye III… 2.3 × 10 ^-4 Sensitizing dye IV…. 3.0 × 10 ^-5 EX-2 ・ ・ ・ 0.400 EX-3 ・ ・ ・ 0.050 EX-10 ・ ・ ・ 0.015 Gelatin ・ ・ ・ 1.30 Fifth layer (third red emulsion layer) Silver iodobromide emulsion I ・ ・ ・ Silver 1.60 EX-3 ・ ・ ・ 0.240 EX- 4 ... 0.120 HBS-1 ... 0.22 HBS-2 ... 0.10 gelatin ... 1.63 6th layer (intermediate layer) EX-5 ... 0.040 HBS-1 ... 0.020 gelatin ... 0.80 7th layer (first green-sensitive emulsion layer) tabular iodide Silver bromide emulsion (silver iodide 6 mol%, average grain size 0.
6μ, average aspect ratio 6.0, average thickness 0.15μ)… Silver 0.40
Sensitizing dye V: 3.0 × 10 ^-5 Sensitizing dye VI: 1.0 × 10 ^-4 Sensitizing dye VII: 3.8 × 10 ^-4 EX-6: 0.260 EX-1: 0.021 EX-7: 0.030 EX-8: 0.025 HBS-1 ... 0.100 HBS-4 ... 0.010 Gelatin ... 0.75 Eighth layer (second green-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 9 mol%, average grain size 0.1%)
7μ, variation coefficient for particle size 0.18)… Silver 0.80 Sensitizing dye V… 2.1 × 10 ^-5 Sensitizing dye VI… 7.0 × 10 ^-5 Sensitizing dye VII… 2.6 × 10 ^-4 EX-6… 0.180 EX-8 ... 0.010 EX-1 ... 0.008 EX-7 ... 0.012 HBS-1 ... 0.160 HBS-4 ... 0.008 Gelatin ... 1.10 9th layer (third green emulsion layer) Silver iodobromide emulsion II ... Silver 1.2 EX-6 ... 0.065 EX-11 ... 0.030 EX-1 ... 0.025 HBS-1 ... 0.25 HBS-2 ... 0.10 Gelatin ... 1.74 10th layer (yellow filter layer) Yellow colloid ... Silver 0.05 EX-5 ... 0.08 HBS-3 ... 0.03 Gelatin ... 0.95 Eleven layers (first blue-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.
6μ, average aspect ratio 5.7, average thickness 0.15μ) ... Silver 0.24
Sensitizing dye VIII… 3.5 × 10 ^-4 EX-9… 0.85 EX-8… 0.12 HBS-1… 0.28 Gelatin… 1.28 12th layer (2nd blue sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide) 10 mol%, average particle size of 0.
8μ, coefficient of variation for grain size 0.16)… Silver 0.45 Sensitizing dye VIII 2.1 × 10 ^-4 EX-9… 0.20 EX-10… 0.015 HBS-1… 0.03 Gelatin… 0.46 13th layer (3rd blue sensitive emulsion layer) Silver iodobromide emulsion III ... Silver 0.77 EX-9 ... 0.20 HBS-1 ... 0.07 Gelatin ... 0.69 14th layer (first protective layer) Silver iodobromide emulsion (1 mol% silver iodide, average grain size 0.07μ)
... Silver 0.5 U-4 ... 0.11 U-5 ... 0.17 HBS-1 ... 0.90 Gelatin ... 1.00 Fifteenth layer (second protective layer) Polymethyl acrylate particles (diameter about 1.5 µm) ... 0.5
4 S-1 ... 0.15 S-2 ... 0.05 gelatin ... 0.72 In addition to the above components, a gelatin hardening agent H-1 and a surfactant were added to each layer.

 The structural formulas of the compounds used are shown in Table B.

Silver iodobromide emulsion I of the fifth layer, silver iodobromide emulsion of the ninth layer
II, Samples 401 to 403 were prepared in the same manner except that the silver iodobromide emulsion III of the 13th layer was changed.

The samples were exposed for sensitometry and subjected to the following color development processing.

The density of the treated sample was measured with a red filter, a green filter and a blue filter. The obtained results are shown in Table 4-1.
Shown in

Regarding the results of photographic performance, the sensitivity of each of the red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer is shown as a relative sensitivity when the sensitivity of Sample 401 is 100.

Processing Method Color development was carried out at 38 ° C. according to the following processing steps.

Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Washing with water 2 minutes 10 seconds Settling 4 minutes 20 seconds Washing with water 3 minutes 15 seconds Stability 1 minute 05 seconds The processing solution composition used in each step is as follows. It was

Color developing solution Diethylenetriaminepentaacetic acid 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 mg Hydroxylamine sulfate 2.4 g 4- (N- Ethyl-N-β-hydroxyethylamino)
-2-Methylaniline sulfate 4.5g Water added 1.0l pH 10.0 Bleaching solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium bromide 150.0g Ammonium nitrate 10.0g Water added 1.0 l pH 6.0 Fixing solution Ethylenediaminetetraacetic acid disodium salt 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate aqueous solution (70%) 175.0 ml Sodium bisulfite 4.6 g Water was added 1.0 l pH 6.6 Stabilizing solution Formalin (40%) 2.0 ml Polyoxy Ethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3g Water added 1.0l As is clear from Table 4-1, it is understood that the emulsion of the present invention has an effect of sensitization with almost no increase in fog.

Further, when the photographic performance after aging was examined in the same manner as in Example 1, it was found that the sample using the emulsion of the present invention showed good storability.

Example 5 Samples 401 to 403 of the present invention and comparative examples were exposed in the same manner as in Example 4 and then processed by the following method using an automatic processor.

Processing method Processing time Processing temperature Color development 3 minutes 15 seconds 38 ℃ Bleaching 1 minute 00 seconds 38 ℃ Bleaching fixing 3 minutes 15 seconds 38 ℃ Washing with water (1) 40 seconds 35 ℃ Washing with water (2) 1 minute 00 seconds 35 ℃ Stability 40 seconds 38 ℃ Dry 1 minute 15 seconds 55 ℃ Next, write the composition of the treatment liquid.

(Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- [N- Ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 Water was added to 1.0 l pH 10.05 (Bleaching / fixing solution) (Unit: g) Ferric ammonium ethylenediaminetetraacetate dihydrate 50.0
Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 240.0 ml Ammonia water (27%) 6.0 ml Water is added to 1.0 l pH 7.2 (Washing solution) Tap water is H type strong acidic cation exchange resin ( Amberlite IR-120B manufactured by Rohm and Haas Co., Ltd. and water are passed through a mixed bed column packed with OH type anion exchange resin (Amberlite IR-400) to treat calcium and magnesium ions at a concentration of 3 mg / l or less. Then, 20 mg / l of sodium isocyanurate dichloride and 0.15 g / l of sodium sulfate were added. The pH of this solution is in the range 6.5-7.5.

(Stabilizer) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Water is added to 1.0 l pH 5.8-8.0 bottles Inventive Samples 402 and 403 were also as good as Example 4 with this treatment.

Example 6 Samples 401 to 403 of the present invention and the comparative example were exposed in the same manner as in Example 4, and then processed by the following method using an automatic processor.

 Processing method Processing time Processing temperature Color development 2 minutes 30 seconds 40 ℃ Bleach fixing 3 minutes 00 seconds 40 ℃ Washing with water (1) 20 seconds 35 ℃ Washing with water (2) 20 seconds 35 ℃ Stability 20 seconds 35 ℃ Drying 50 seconds 65 ° C Next, the composition of the treatment liquid will be described.

(Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- [N- Ethyl-N-β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 Water was added to 1.0 l pH 10.05 (Washing liquid) Tap water is passed through a mixed bed column filled with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite IR-400). Water was added to control the concentration of calcium and magnesium ions to 3 mg / l or less, and then 20 mg / l of sodium isocyanurate dichloride and 0.15 g / l of sodium sulfate were added.

 The pH of this solution is in the range 6.5-7.5.

(Stabilizer) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Water is added to 1.0 l pH 5.0-8.0 bottles Inventive Samples 402 and 403 were also as good as Example 4 with this treatment.

Example 7 A sample which is a multi-layer color light-sensitive material consisting of each layer having the composition shown below was prepared on an undercoated cellulose triacetate film support.

(Composition of photosensitive layer) The coating amount was represented by g / m ² . However, the amounts of silver halide and colloidal silver are shown in units of g / m ^{2 of} silver, and the sensitizing dyes are shown in the number of moles per mole of silver halide in the same layer.

First layer: Antihalation layer Black colloidal silver Silver coverage 0.2 Gelatin 2.2 UV-1 0.1 UV-1 0.2 Cpd-1 0.05 Solv-1 0.01 Solv-2 0.01 Solv-3 0.08 Second layer: Intermediate layer Fine grain silver bromide (Equivalent sphere diameter 0.07μ) Silver coating amount 0.15 Gelatin 1.0 Cpd-2 0.2 Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, equivalent sphere diameter)
0.7μ, coefficient of variation of equivalent spherical diameter 14%, tetradecahedral grains) Silver coating amount 0.26 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, equivalent spherical diameter)
0.4μ, variation coefficient of equivalent spherical diameter 22%, tetradecahedral grain) Silver coating amount 0.2 Gelatin 1.0 ExS-1 4.5 × 10 ^-4 mol ExS-2 1.5 × 10 ^-4 mol ExS-3 0.4 × 10 ^-4 mol ExS -4 0.3 x 10 ^-4 mol ExC-1 0.33 ExC-2 0.009 ExC-3 0.023 ExC-6 0.14 4th layer: second red-sensitive emulsion layer Silver iodobromide emulsion (AgI 16 mol%, internal high AgI type, sphere) Equivalent diameter 1.
0Myu, sphere variation coefficient of 25% equivalent diameter, the plate-like particles, diameter / thickness ratio 4.0) silver coverage 0.55 Gelatin ^{0.7 ExS-1 3 × 10 -4} ExS-2 1 × 10 -4 ExS-3 0.3 × 10 - ⁴ ExS-4 0.3 × 10 ^-4 ExC-3 0.05 ExC-4 0.10 ExC-6 0.08 Fifth layer: third red-sensitive emulsion layer Silver iodobromide emulsion I (internal high AgI type, equivalent spherical diameter 1.2 μ, sphere Coefficient of variation of equivalent diameter 28%) Silver coating amount 0.9 Gelatin 0.6 ExS-1 2 × 10 ^-4 ExS-2 0.6 × 10 ^-4 ExS-3 0.2 × 10 ^-4 ExC-4 0.07 ExC-5 0.06 Solv-1 0.12 Solv-2 0.12 Sixth layer: Intermediate layer Gelatin 1.0 Cpd-4 0.1 Seventh layer: First green emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, equivalent spherical diameter)
0.7μ, variation coefficient of spherical equivalent diameter 14%, tetradecahedral grain) Silver coating amount 0.2 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, equivalent spherical diameter)
0.4μ, coefficient of variation of equivalent spherical diameter 22%, tetradecahedral grain) Silver coating amount 0.1 Gelatin 1.2 ExS-5 5 × 10 ^-4 ExS-6 2 × 10 ^-4 ExS-7 1 × 10 ^-4 ExM-1 0.41 ExM-2 0.10 ExM-5 0.03 Solv-1 0.2 Solv-5 0.03 Eighth layer: second green emulsion layer Silver iodobromide emulsion (AgI 10 mol%, internal high iodine type, equivalent spherical diameter 1.0 μ, equivalent spherical diameter Coefficient of variation of 25%, tabular particles, diameter /
Thickness ratio 3.0) Silver coating amount 0.4 Gelatin 0.35 ExS-5 3.5 × 10 ^-4 ExS-6 1.4 × 10 ^-4 ExS-7 0.7 × 10 ^-4 ExM-1 0.09 ExM-3 0.01 Solv-1 0.15 Solv-5 0.03 Ninth layer: Intermediate layer Gelatin 0.5 Tenth layer: Third green emulsion layer Silver iodobromide emulsion II (Internal high AgI type, sphere equivalent diameter 1.2 μ, variation coefficient of sphere equivalent diameter 28%) Silver coating amount 1.0 gelatin 0.8 ExS-5 2 × 10 ^-4 ExS-6 0.8 × 10 ^-4 ExS-7 0.8 × 10 ^-4 ExM-3 0.01 ExM-4 0.04 ExC-4 0.005 Solv-1 0.2 11th layer: Yellow filter layer Cpd- 3 0.05 Gelatin 0.5 Solv-1 0.1 12th layer: intermediate layer Gelatin 0.5 Cpd-2 0.1 13th layer: 1st blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 10 mol%, internal high iodine type, equivalent spherical diameter 0.7 μm) , Sphere equivalent diameter variation coefficient 14%, tetrahedral grains) silver coating amount 0.1 silver iodobromide emulsion (AgI 4.0 mol%, internal high iodine type, sphere equivalent diameter 0.4μ, sphere equivalent diameter variation coefficient 22%, 14-sided grain) Silver coating amount 0.05 Gelatin 1.0 ExS ^{8 3 × 10 -4 ExY-1} 0.53 ExY-2 0.02 Solv-1 0.15 14th layer: second blue-sensitive emulsion layer Silver iodobromide emulsion (AgI19.0 mol%, internal high AgI type, sphere-corresponding diameter
1.0μ, Coefficient of variation of sphere equivalent diameter 16%, tetrahedral particle) Silver coating amount 0.19 Gelatin 0.3 ExS-8 2 × 10 ^-4 ExY-1 0.22 Solv-1 0.07 15th layer: Intermediate layer Fine particle silver iodobromide ( AgI 2 mol%, uniform type, sphere equivalent diameter 0.13
μ) Silver coating amount 0.2 Gelatin 0.36 16th layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion III (internal high AgI type, sphere equivalent diameter 1.2 μ, variation coefficient of sphere equivalent diameter 28%) Silver coating amount 1.0 gelatin 0.5 ExS-8 1.5 × 10 ^-4 ExY-1 0.2 Solv-4 0.07 17th layer: 1st protection layer Gelatin 1.8 UV-1 0.1 UV-2 0.2 Solv-1 0.01 Solv-2 0.01 18th layer: 2nd protection Layer Fine grain silver bromide (sphere equivalent diameter 0.07μ) Silver coating amount 0.18 Gelatin 0.7 Polymethylmethacrylate particles (diameter 1.5μ) 0.2 W-1 0.02 H-1 0.4 Cpd-5 1.0 The structural formula of the compound used is shown in Table C. Shown in.

5th layer silver iodobromide emulsion I, 10th layer silver iodobromide emulsion
II, Samples 701 to 703 were prepared in the same manner as each sample except that the silver iodobromide emulsion III of the 16th layer was changed.

These samples were left under conditions of 40 ° C. and 70% relative humidity for 14 hours, then exposed for sensitometry, and then subjected to Example 4
The same color development processing as described above was performed.

The density of the treated sample was measured with a red filter, a green filter and a blue filter. The obtained results are shown in Table 7-1.
Shown in

The results of the photographic performance are shown as relative sensitivities when the sensitivity of Sample 701 is 100, respectively, for the sensitivity of the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer.

As is clear from Table 7-1, the emulsion of the present invention has a high sensitivity effect with almost no increase in fog.

When the photographic performance of this sample was examined after aging in the same manner as in Example 1, samples 702 and 703 using the emulsion of the present invention were obtained.
Have been found to exhibit good photographic performance.

Example 8 A sample which is a multi-layer color light-sensitive material consisting of each layer having the composition shown below was prepared on an undercoated cellulose triacetate film support.

The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dye is shown by the number of moles per mole of silver halide in the same layer. The symbols indicating additives have the following meanings. However, when there are multiple utilities, one of them is listed as a representative.

UV; UV absorber, Solv; high boiling organic solvent, ExF; dye,
ExS: Sensitizing dye, ExC: Cyan coupler, ExM: Magenta coupler, ExY: Yellow coupler, Cpd: Additive first layer (antihalation layer) Black colloidal silver ... 0.15 Gelatin ... 2.9 UV-1 ... 0.03 UV-2 ... 0.06 UV-3 ... 0.07 Solv-2 ... 0.08 ExF-1 ... 0.01 ExF-2 ... 0.01 Second layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform spherical equivalent diameter 0.4 µ, sphere) Equivalent diameter variation coefficient 37%, plate-like particles diameter / thickness ratio 3.0)
Amount of coated silver ・ ・ ・ 0.4 Gelatin ・ ・ ・ 0.8 ExS-1 ・ ・ ・ 2.3 × 10 ^-4 ExS-2 ・ ・ ・ 1.4 × 10 ^-4 ExS-5 ・ ・ ・ 2.3 × 10 ^-4 ExS-7 ・ ・ ・ 8.0 × 10 ^-6 ExC-1 ・ ・ ・ 0.17 ExC -2 ... 0.03 ExC-3 ... 0.13 Third layer (medium-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core-shell ratio 2: 1, internal high A)
gI Equivalent sphere diameter 0.65μ, coefficient of variation of equivalent sphere diameter 25%, tabular grains, diameter / thickness ratio 2.0) Coating silver amount ... 0.65 Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent sphere diameter 0.4
μ, coefficient of variation of equivalent spherical diameter 37%, plate-like particles, diameter / thickness ratio
3.0) Silver coating amount ... 0.1 Gelatin ... 1.0 ExS-1 ... 2 × 10 ^-4 ExS-2 ・ ・ ・ 1.2 × 10 ^-4 ExS-5 ・ ・ ・ 2 × 10 ^-4 ExS-7 ・ ・ ・ 7 × 10 ^-6 ExC-1 ・ ・ ・0.31 ExC-2… 0.01 ExC-3… 0.06 4th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion I (internal high AgI type with core-shell ratio 1: 2, sphere equivalent diameter 0.75μ, sphere equivalent diameter Coefficient of variation 25%) Silver coating amount ... 0.
9 Gelatin ... 0.8 ExS-1 ... 1.6 × 10 ^-4 ExS-2 ・ ・ ・ 1.6 × 10 ^-4 ExS-5 ・ ・ ・ 1.6 × 10 ^-4 ExS-7 ・ ・ ・ 6 × 10 ^-4 ExC-1 ・ ・ ・ 0.07 ExC-4 ・ ・ ・ 0.05 Solv-1… 0.07 Solv-2… 0.20 Cpd-7… 4.6 × 10 ^-4 Fifth layer (intermediate layer) Gelatin 0.6 UV-4 0.03 UV-5 0.04 Cpd-1… 0.1 Polyethyl acrylate latex… 0.08 Solv-1 ... 0.05 6th layer (low-sensitivity green emulsion layer) Silver iodobromide emulsion (AgI 4 mol% uniform type. Equivalent sphere diameter 0.7μ, variation coefficient of sphere equivalent diameter 37%, plate-like grain, diameter / thickness ratio 2.0)
Silver amount coated 0.18 Gelatin 0.4 ExS-3… 2 × 10 ^-4 ExS-4… 7 × 10 ^-4 ExS-5… 1 × 10 ^-4 ExM-5… 0.11 ExM-7… 0.03 ExY-8… 0.01 Solv -1 0.09 Solv-4 0.01 7th layer (medium speed green emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, core-shell ratio 1: 1 surface height A)
gI type, equivalent sphere diameter 0.5μ, variation coefficient of equivalent sphere diameter 20%, plate-like particles, diameter / thickness ratio 4.0) Silver coating amount 0.27 Gelatin 0.6 ExS-3 2x10 ^-4 ExS- ⁴ 7x 10 ^-4 ExS-5 ・ ・ ・ 1 × 10 ^-4 ExM-5 ・ ・ ・ 0.17 ExM-7 ・ ・ ・ 0.04 ExY-8 ・ ・ ・ 0.02 Solv-1 0.14 Solv-4 0.02 Eighth layer (high sensitivity green emulsion layer) Silver iodobromide Emulsion II (internal high AgI type with 1: 2 core-shell ratio, equivalent sphere diameter 0.75μ, variation coefficient of equivalent sphere diameter 25%) Coating silver amount ... 0.7 Gelatin ... 0.8 ExS-4 ... 5.2 × 10 ^-4 ExS-5 ... 1 x 10 ^-4 ExS-8 ... 0.3 x 10 ^-4 ExM-5 ... 0.1 ExM-6 ... 0.03 ExY-8 ... 0.02 ExC-1 ... 0.02 ExC-4 ... 0.01 Solv-1 ... 0.25 Solv-2 ... 0.06 Solv -4 ... 0.01 Cpd-7 ... 1 x 10 ^-4 9th layer (intermediate layer) Gelatin 0.6 Cpd-1 ... 0.04 Polyethyl acrylate latex ... 0.12 Solv-1 ... 0.02 10th layer (donor of multi-layer effect for red-sensitive layer) Layer) Silver iodobromide emulsion (AgI 6 mol%, core-shell ratio 2: 1) Part High A
gI type, sphere equivalent diameter 0.7μ, variation coefficient of sphere equivalent diameter 25%, plate-shaped grain, diameter / thickness ratio 2.0) Coating silver amount ... 0.68 Silver iodobromide emulsion (AgI 4 mol% uniform type, variation of sphere equivalent diameter) coefficient
37%, plate-shaped particles, diameter / thickness ratio 3.0) Coating silver amount 0.19 Gelatin 1.0 ExS-3 6x10 ^-4 ExM-10 0.19 Solv-1 0.20 11th layer (yellow filter layer) Yellow colloid Silver: 0.06 Gelatin 0.8 Cpd-2: 0.13 Solv-1: 0.13 Cpd-1: 0.07 Cpd-6: 0.002 H-1: 0.13 12th layer (low sensitivity blue emulsion layer) Silver iodobromide emulsion (AgI4.5 Mol%, uniform AgI type, sphere equivalent diameter 0.7
μ, coefficient of variation of spherical equivalent diameter 15%, plate-like particles, diameter / thickness ratio
7.0) Coating silver amount ... 0.3 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, spherical equivalent diameter 0.3
μ, coefficient of variation of equivalent sphere diameter 30%, plate-like particles, diameter / thickness ratio
7.0) Silver coating amount 0.15 Gelatin 1.8 ExS-6 9x10 ^-4 ExC-1 0.06 ExC-4 0.03 ExY-9 0.14 ExY-11 0.88 Solv-1 0.42 13th layer (intermediate layer) Gelatin 0.7 ExY-12… 0.20 Solv-1… 0.34 14th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion III (internal high AgI type with core-shell ratio 1: 2, sphere equivalent diameter 0.75 μ, sphere equivalent diameter Coefficient of variation: 25%) Silver coating amount: 0.5 Gelatin: 0.5 ExS-6: 1 × 10 ^-4 ExY-9: 0.01 ExY-11: 0.20 ExC-1: 0.02 Solv-1: 0.10 15th layer (1st protective layer) ) Fine grain silver bromide emulsion (AgI 2 mol%, uniform AgI type, equivalent spherical diameter)
0.07μ) Silver amount coated 0.12 Gelatin 0.9 UV-4 0.11 UV-5 0.16 Solv-5 0.02 H-1 0.13 Cpd-5 0.10 Polyethyl acrylate latex 0.09 16th layer (2nd protective layer) ) Fine grain silver bromide emulsion (AgI 2 mol%, uniform AgI type, equivalent spherical diameter)
0.07μ) Coating silver amount 0.36 Gelatin 0.55 Polymethylmethacrylate particles (diameter 1.5μ) 0.2 H-1 0.17 In addition to the above components in each layer, emulsion stabilizer Cpd-3
(0.07 g / m ² ) and the surfactant Cpd-4 (0.03 g / m ² ) were added as coating aids.

 Table D shows the structural formulas of the compounds used.

In Em-1 of Example 1, the average equivalent sphere diameter of the seed crystal was set to 0.
The emulsion prepared in the same manner as in Em-1 of Example 1 except that the emulsion had a diameter of 5 μm and thus had an average equivalent spherical diameter of the final grains of 0.75 μm was designated as Em-201.

Emulsions 202 to 207 were prepared by adding the thiosulfonic acid compound and the reduction sensitizer to Em-201 in the same manner as described in Example 1 in the amounts shown in Table 8-1.

The emulsion of the present invention thus prepared and Comparative Examples 201 to 207
Was optimally sulfur-sensitized with sodium thiosulfate and chloroauric acid for each emulsion.

Fourth layer silver iodobromide emulsion I, eighth layer silver iodobromide emulsion
II, samples 801 to 804 were prepared in the same manner except that the silver iodobromide emulsion III of the 14th layer was changed.

These samples were left under conditions of 40 ° C. and 70% relative humidity for 14 hours, and then subjected to sensitometric exposure.
The same color development processing as described above was performed.

The density of the treated sample was measured with a red filter, a green filter and a blue filter. The obtained results are shown in Table 8-2.
Shown in

The results of the photographic performance are shown as relative sensitivities when the sensitivity of the sample 801 is 100, and the sensitivity of each of the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer is 100.

As is clear from Table 8-2, it is understood that the emulsion of the present invention has an effect of sensitization with almost no increase in fog. When this sample was stored for the same period of time as in Example 1, and the photographic performances were compared, Sample 802 showed a marked increase in fog and a decrease in sensitivity. On the other hand, it was found that the samples 803 and 804 of the present invention showed better photographic performance than the comparative examples 801 and 802.

Claims (2)

(57) [Claims] 1. A silver halide grain is ^subjected to reduction sensitization with 5 × 10 ^-5 to 1 × 10 ^-1 mol of ascorbic acid or at least one derivative thereof per mol of silver halide during the growth of silver halide grains. And a method for producing a silver halide emulsion. 2. Reduction sensitization is carried out in the presence of at least one compound represented by the general formula [I], [II] or [III],
A method for producing a silver halide emulsion according to claim 1. [I] RSO in _{2 S-M [II] RSO} 2 S-R 1 [III] RSO 2 S-L m -SSO 2 -R 2 Formula, R, R ^1, also R ² is the same or different Alternatively, it represents an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1. The compounds of the general formulas [I] to [III] may be a polymer containing a divalent group derived from the structure represented by [I] to [III] as a repeating unit.