JPH0792597A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To efficiently desalt without lowering a chemical sensitizing and color sensitizing by coagurating, settling, desalting and redispersing a silver halide emulsion prepared in the presence of a polymer containing an anionic group using gelatin as a settling agent. CONSTITUTION:The silver halide emulsion prepared in the presence of a polymer compd. containing an anionic group, and obtained by adding at least 1g to at most 5200g gelatin in which an amino group is not subjected to a chemical modification is added per 6.02X10<23> anionic group, being coagulated settled, desalted and redispersed, is incorporated in an emulsion layer. In the gelatin to be used as the settling agent, any gelatin except the gelatin whose amino group is subjected to the chemical modification such as gelatin phthalate may be used, but a deionized inert gelatin is preferable. And in the mol.wt. of the gelatin, the gelatin having larger mol.wt. is capable of settling with lower usage, but it is capable of selecting arbitrary by the silver halide emulsion.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material prepared by coagulating, precipitating, desalting and redispersing a silver halide emulsion prepared in the presence of a polymer containing an anionic group, using gelatin as a precipitating agent. Regarding

[0002]

[Prior art]

1. Protective Colloid Gelatin has been used for a long time as a protective colloid used in silver halide photographic emulsions used for image formation of photographic light-sensitive materials, and has been used up to now. The first reason is
Secondly, it has a large protective colloid property, and secondly, it is easy to convert into a sol-gel and easy to handle and can be applied. However, gelatin is easily spoiled by bacteria and fungi, and the quality of the gelatin varies because it is derived from living organisms. To address this difficulty, it is already known to use synthetic polymers instead of gelatin. For example, US Pat.
No. 358836, No. 2484456, No. 254147
No. 4, No. 3511818, No. 3000741 and No. 3
No. 479189, No. 2976156, and No. 328420.
No. 7 and No. 3615624 are listed.

When gelatin is used as a protective colloid, even deionized gelatin is not truly inactive and has impurities regardless of whether it is inorganic or organic, which has an unintended effect on photographic properties. There is. Moreover, while recognizing the existence of impurities, it is very difficult to further raise the purity of gelatin. Japanese Patent Laid-Open No. 4-235546
JP-A-5-5968 describes that the above-mentioned drawbacks of gelatin can be overcome by substituting synthetic polymers. However, some of these synthetic polymers were inferior to the gelatin emulsion particularly in efficiency in the desalting step after grain formation.

2. Coagulation, precipitation and desalting method of silver halide emulsion prepared in the presence of a polymer containing anionic group Precipitation and desalting method of silver halide emulsion prepared in the presence of a polymer containing anionic sulfoxy group Law is US Patent No. 3
A method of using a polymer of a primary amine as described in JP-A-679425 as a coagulant for an emulsion is known. Other known methods include salting-out method, addition of phthalated gelatin, spontaneous precipitation method and centrifugation method. Furthermore, when the anionic group is a weak acid such as carboxylic acid, a cationic group is used. In the case of a polymer without a polymer, an isoelectric point coagulation method is well known in which the pH is lowered to eliminate the water solubility of the polymer and the polymer is precipitated. Further, a desalting method that does not cause precipitation of the silver halide emulsion, such as an ultrafiltration method, is also known.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to efficiently desalt halogenated silver halide emulsion prepared in the presence of a polymer having an anionic group without impairing chemical sensitization or color sensitization. It is to provide a silver halide photographic light-sensitive material containing a silver halide emulsion.

[0006]

The above object is to provide a silver halide photographic light-sensitive material in which at least one silver halide emulsion layer is provided on a support, and the emulsion layer contains a heavy salt containing an anionic group. A silver halide emulsion prepared in the presence of a coalescing compound and having an anionic group of 6.02 × 1.
At least 1 g and at most 5200 g of gelatin whose amino groups have not been chemically modified per 0 ²³ grains are added to cause solidification, precipitation, desalting, and redispersion of the silver halide emulsion. It was achieved by using a silver halide photographic light-sensitive material.

The components of the present invention will be described in detail below. 1. Polymer containing anionic group The polymer containing anionic group described in the present invention may be a strong acid or a weak acid as long as the compound has water solubility in the anionic group, and examples of strong acid include Examples thereof include vinylsulfonic acid-based strong acids such as sodium 2-acrylamido-2-methylpropanesulfonate, and weak acids such as acrylic acid and methacrylic acid. Further, in order to enable the formation of silver halide emulsion grains, JP-A-4-235 is known.
546, a copolymer with a monomer having a repeating unit derived from an ethylenically unsaturated monomer having at least one thioether structure in its side chain,
In addition to a copolymer with a monomer having an imidazole group such as histidine, a copolymer with the following functional groups is preferable.

For example, A. Copolymer with acrylamide type monomer such as acrylamide and methacrylamide B. Copolymer with vinyl alcohol C. Copolymer with vinylpyrrolidone D. Copolymer with vinyl styrene E. Copolymer with vinyl pyridine F. Copolymer with azaindene group-containing monomer G. Examples thereof include a copolymer with a quinoline group-containing monomer, but the copolymer is not limited to the above as long as it can form silver halide emulsion grains, and the copolymerization ratio can be arbitrarily selected. The copolymerization ratio of the above-mentioned functional group and anionic group is 0.1 / 99.9 to 99.9 / 0.1.
The range of (weight ratio) is good, preferably 0.5 / 9
Those of 9.5 to 70/30 (weight ratio) are often used,
Those having a molecular weight of 5,000 to 150,000, preferably about 7,000 to 100,000 are often used.
Further, a copolymer having two or more kinds of the above functional groups and anionic groups can also be used.

Specific examples of the compound that can be used in the present invention are shown below, but needless to say, the present invention is not limited thereto. (P-1) 3-thiapentyl acrylate / acrylic acid copolymer (5.2 / 94.8 weight ratio) (P-2) 3-thiapentyl acrylate / acrylic acid copolymer (10.5 / 89. 5 weight ratio) (P-3) 3-thiapentyl acrylate / acrylic acid copolymer (21/79 weight ratio) (P-4) 3-thiapentyl acrylate / 2-acrylamido-2-methylpropanesulfonate sodium co Polymer (10.5 / 89.5 weight ratio) (P-5) 3-thiapentyl acrylate / acrylic acid / 2-acrylamido-2-methylpropanesulfonate sodium copolymer (10.5 / 31/58. (5 weight ratio) (P-6) 3-thiapentyl acrylate / vinylpyrrolidone / 2-acrylamido-2-methylpropanesulfonate sodium copolymer (4 5/5 / 89.5 weight ratio)

(P-7) 3-thiapentyl acrylate / 2-vinylimidazole / 2-acrylamido-2-
Sodium methyl propane sulfonate copolymer (4.5
/5/89.5 weight ratio) (P-8) N-vinylimidazole / acrylic acid copolymer (5.2 / 94.8 weight ratio) (P-9) N-vinylimidazole / acrylic acid copolymer (10.5 / 89.5 weight ratio) (P-10) N-vinylimidazole / acrylic acid copolymer (21/79 weight ratio) (P-11) N-vinylimidazole / 2-acrylamido-2-methyl Sodium propane sulfonate copolymer (10.5 / 89.5 weight ratio) (P-12) N-vinyl imidazole / acrylic acid / 2-
Acrylamide-2-methylpropanesulfonate sodium copolymer (10.5 / 31 / 58.5 weight ratio) (P-13) N-vinylimidazole / vinylpyrrolidone / 2-acrylamido-2-methylpropanesulfonate sodium copolymer Polymer (4.5 / 5 / 89.5 weight ratio) (P-14) N-vinylimidazole / acrylamide /
2-Acrylamido-2-methylpropanesulfonic acid sodium copolymer (4.5 / 5 / 89.5 weight ratio)

(P-15) Acrylamide / acrylic acid copolymer (50/50 weight ratio) (P-16) Acrylamide / methacrylamide / 2-acrylamido-2-methylpropanesulfonic acid sodium copolymer (15/45) (/ 40 weight ratio) (P-17) vinyl alcohol / acrylic acid copolymer (7
(0/30 weight ratio) (P-18) vinyl alcohol / vinyl pyrrolidone / 2-
Sodium acrylamido-2-methylpropanesulfonate copolymer (15/45/40 weight ratio) (P-19) Vinylstyrene / 4-vinylimidazole /
Methacrylic acid copolymer (1/30/69 copolymerization ratio) (P-20) vinylpyridine / 4-vinylimidazole /
Methacrylic acid copolymer (1/30/69 copolymerization ratio) (P-21) Vinylquinoline / acrylic acid copolymer (5 /
95 weight ratio) (P-22) methyl-7-hydroxy-1,2,4-triazolo [1,5-a] pyrimidine / 2-acrylamido-2-methylpropanesulfonate sodium copolymer (10/90 weight) ratio)

The amount of the copolymer used may be any amount capable of maintaining the protective colloid property, and depends on the grain shape, size and composition of the silver halide, and also on the type, molecular weight and copolymerization ratio of the copolymer. Is in the range of 0.1 g to 150 g per mol of silver per copolymer, preferably 0.3 to 100
It is preferable to use it in the range of g, more preferably in the range of 0.5 to 75 g, and it is also possible to use two or more copolymers in combination within this range.
The position of addition of the copolymer is usually preferably pre-existing as an aqueous solution in a container for particle formation,
If necessary, the same or different kind of the above-mentioned copolymer may be added at any time during the grain formation.

2. Gelatin used as a precipitating agent As gelatin which can be used as a precipitating agent, any gelatin can be used as long as it is not gelatin chemically modified with an amino group such as phthalated gelatin, but deionized inert gelatin is preferable. The molecular weight of gelatin can be from a low molecular weight gelatin of about 10,000 to a gelatin of about 100,000, but a higher molecular weight gelatin can be precipitated with a smaller amount, but can be arbitrarily selected depending on the silver halide emulsion. The amount used varies depending on the size of the silver halide emulsion grains and the type of the anionic group-containing copolymer compound used for grain formation, but from 1 g per 6.02 × 10 ²³ anionic groups in the copolymer compound. At most 52
It can be used in the range of 00 g, but is preferably 2 g to 45
It is preferably used in the range of 00 g, and more preferably in the range of 10 g to 2500 g, and in this range, two or more kinds of gelatin can be used in combination.

When gelatin is used as a precipitating agent, it can be added in the form of powder or granules, but it is preferable to add water to swell it in advance, and it is more preferable to dissolve it in a solution state or in a solid state by once cooling the solution. It is preferable to add it. The temperature at which the silver halide emulsion is settled by adding gelatin is at a temperature above the temperature at which gelatin does not solidify.
However, depending on the conditions of the silver halide emulsion, it is 30
In the range of ℃ to 80 ℃, preferably 30 ℃ to 55 ℃,
It is more preferable to settle in the range of 30 ° C to 45 ° C.

After adding the precipitating agent, the silver halide emulsion can be precipitated by adjusting the pH. In many cases, the pH at the time of precipitation may be set to the isoelectric point of the used gelatin or lower, and it depends on the type of gelatin, the amount used, and the conditions of the silver halide emulsion, but for example, silver bromide having a side length of 0.6 μm. When deionized gelatin having a molecular weight of 100,000 is used for a cubic emulsion, it can be precipitated at a pH of about 2.0 to 4.8. Generally, precipitation is possible in the range of pH 5.0 or less, but this is not the only case. For esterified gelatin chemically modified with a carboxyl group, etc., depending on the situation, the pH may be increased to precipitate silver halide emulsions. There is also. The emulsion once precipitated in the present invention can be precipitated without adding gelatin for precipitation by adding water and stirring to adjust the pH to the above value. By repeating this, desalting can be performed up to the target conductivity. it can. Depending on the prepared silver halide emulsion, desalting can be carried out by any combination of the present invention and the above-mentioned known desalting method. The silver halide emulsion is usually coagulated and settled after grain formation and before chemical sensitization, but it may be during grain formation or after chemical sensitization or color sensitization depending on the emulsion conditions. It can be carried out.

After desalting the silver halide emulsion to a target conductivity, water can be added to raise the pH and redispersion can be carried out. At the time of redispersion, not only water but also the polymer compound, acid, alkali, etc. used at the time of gelatin or particle formation depending on the purpose.
Various compounds other than halogen may be added. The pH at the time of redispersion varies depending on the silver halide emulsion and the gelatin used for precipitation, but as a guide, it is preferable to redisperse at a pH of 5 to 9 at 40 ° C. The temperature at the time of redispersion also varies depending on the silver halide emulsion, and it is preferable to redisperse in the range of 30 ° C. to 80 ° C., preferably 32 ° C. to 78 ° C., and more preferably 35 ° C. to 75 ° C.

3. Formation of Silver Halide Emulsion Grains The shapes of silver halide emulsion grains include normal crystal without twin planes, single twin with one twin plane, and parallel multiple twin with two or more parallel twin planes. Crystal, and non-parallel multiple twins containing two or more non-parallel twin planes. The shape of the silver halide grains is normal crystal without twin planes, single twin with one twin plane, parallel multiple twin with two or more parallel twin planes, non-parallel twin planes. There are non-parallel multiple twins containing two or more. These shapes are described on page 163, edited by The Photographic Society of Japan, Fundamentals of Photographic Industries-Silver Salt Photograph (Corona Publishing Co.). In the case of normal crystals, a cube consisting of (100) plane,
Octahedral grains having (111) faces or dodecahedron grains having (110) faces can be used. The dodecahedral grains are described in JP-B-55-42737 and JP-A-60-222842. In addition, Jo
urnal of Imaging Science 30: 247 (198
6). (Hll) plane, (hhl) plane,
(Hko) plane particles and (hkl) plane particles can also be used according to the purpose. 1 having (111) plane and (100) plane
Tetrahedral particles and grains having (111) and (110) faces can also be used. If necessary, polyhedral grains such as 38-faced, rhomboidal 24-faced, 46-faced, and 68-faced grains can also be used.

The grain size of the silver halide grains may be any grain size from 0.1 μm or less to large size grains having a projected area diameter of more than 10 μm. Monodisperse emulsions having a narrow grain size distribution may be used. Monodisperse emulsions can be prepared, for example, by the number of particles or the weight
It is a silver halide emulsion having a grain size distribution such that 80% or more of all grains fall within 30%. Polydisperse emulsions having a wide grain size distribution may be used. Further, for the purpose of adjusting gradation, two or more kinds of monodisperse silver halide emulsions having substantially the same color sensitivity and different grain sizes may be used in combination. Two or more emulsions may be mixed in the same layer or may be formed in different layers. It is also possible to use two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions.

The method for preparing a silver halide emulsion is described in "Graphics and Chemistry of Photography" by Graphide, published by Paul Montel (P.Gl.
afkides, Chimie et Physique Photographique Paul Mo
ntel, 1967) "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsio
n Chemistry (Focal Press, 1966), "Production and coating of photographic emulsions" by Zelikmann et al., published by Focal Press.
(VL Zelikman et al. Making and Coating Photogra
phic Emulsion. Focal Press, 1964). The preparation method may be any of the acidic method, the neutral method and the ammonia method. As a method of reacting the soluble silver salt and the soluble halogen salt, a one-sided mixing method, a simultaneous mixing method, or a combination thereof can be used. It is also possible to use a method of forming grains in the state of excess silver ions (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid layer in which silver halide is formed,
That is, the so-called controlled double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal system and a substantially uniform grain size can be obtained.

In the preparation of silver halide emulsion, it is preferable to adjust pAg and pH during grain formation. pAg
For adjusting pH and pH, see Photographic Science and Engineering.
and Engineering) Volume 6, 159-165 (196
2); Journal of Photographic Science, Volume 12, 24
2 to 251 (1964), U.S. Pat. No. 3,655,394 and British Patent No. 1413748. The halogen composition of the silver halide grains may be any of silver bromide, silver chloride, silver iodide, silver chloroiodide and silver chlorobromoiodide.

In the present invention, when particles are formed at a low temperature in the presence of gels, the particles may be formed at a temperature not lower than the melting point of the compound, and the temperature is about 100 ° C. so that the particles do not decompose or gel due to heat or the like. Particles can be formed within the range of. In addition, if gelation does not occur even at low temperatures, it is possible to form particles in a wide range from the temperature before freezing of the aqueous solution to the boiling point of the solution if it does not decompose or gel due to heat, but particle formation in the range of 4 ° C to 100 ° C. It is preferable to form particles in the range of 30 ° C. to 80 ° C. In the grain formation, in addition to the temperature and the above-mentioned pH and pAg, it is preferable to appropriately adjust the conditions such as the kind and amount of the silver halide solvent, the addition rate and the addition concentration of the silver salt or the halogen salt used for grain formation. .

Examples of silver halide solvents include thiocyanates (US Pat. Nos. 2,222,264 and 2,448,531).
No. 4, No. 3320069), thioether compound (US Pat. No. 3,271,157, No. 357462)
No. 8, No. 3704130, No. 4297439, No. 4276347, each description), a thione compound (JP-A Nos. 53-144319, 53-82408 and 5).
5-77737) and amine compounds (described in JP-A-54-100717). Ammonia can also be used in combination with the silver halide solvent as long as it does not have any adverse effect. In the process of grain formation or physical ripening of silver halide, a metal salt (including complex salt) may also be present. Examples of metal salts include cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof and iron salts or iron complex salts.

When silver halide grains are formed, the addition rate, addition amount or concentration of the silver salt solution (eg AgNO ₃ aqueous solution) and the halogen compound solution (eg KBr aqueous solution) to be added are increased to accelerate the grain formation rate. Good. Thus, the method of rapidly forming silver halide grains is
British Patent No. 1335925, United States Patent No. 3672900
Nos. 3,650,757 and 4,242,445, JP-A-55-142329 and JP-A-55-15812.
No. 4, No. 58-113927, No. 58-113928.
No. 58-111934 and No. 58-111936.

4. Chemical Sensitization In the present invention, various kinds of chemical sensitizers that are commonly used can be used. The chemical sensitizers used for chemical sensitization include chalcogen sensitization. Examples of chalcogen sensitizers include sulfur sensitizers, selenium sensitizers, and tellurium sensitizers, and known ones such as those mentioned below can be mentioned. An unstable sulfur compound is used as the sulfur sensitizer, and specifically, thiosulfates (for example, hypo), thioureas (for example, diphenylthiourea, triethylthiourea, allylthiourea, etc.), allylisourea. Well-known sulfur compounds such as thiocyanate, cystine, p-toluenethiosulfonate, rhodanines and mercaptos may be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. Appropriate amounts include pH, temperature, compatibility with other sensitizers, size of silver halide grains, etc. Although it varies depending on various conditions, as a guide, it is preferable to use it in the range of 10 ^-9 to 10 ^-1 mol per mol of silver halide.

In the selenium sensitization, a known unstable selenium compound is used. Specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, N, N-diethylselenourea, etc.) are used. ), Selenoketones, selenoamides, aliphatic isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenocarboxylic acids and esters, selenophosates, diethyl selenides, diethyl diselenides and other selenides. Can be used. The addition amount varies depending on various conditions like the sulfur sensitizer, but as a guide, it is preferable to use it in the range of 10 ^-10 to 10 ^-1 mol per mol of silver halide.

In the present invention, in addition to the above chalcogen sensitization, sensitization with a noble metal can also be performed. First, in gold sensitization, the valence of gold may be +1 or +3,
Various gold compounds are used. Typical examples are chloroauric acid, potassium chloroaurate, auric trichloride, potassium aurithiocyanate, potassium iodoaurate, tetraoric acid, ammonium aurothiacyanate, pyridyl trichlorogold,
Examples include gold sulfide, gold selenide, gold telluride, and the like. The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is preferably used within the range of 10 ^-10 to 10 ^-1 mol per mol of silver halide. The gold sensitizer may be added at the same time as sulfur sensitization, selenium sensitization, tellurium sensitization, during or before the sulfur, selenium, tellurium sensitization step, or after the gold sensitizer is used alone. It is also possible to use. The pAg and pH of the emulsion to be sulfur-sensitized, selenium-sensitized or tellurium-sensitized or gold-sensitized in the present invention are not particularly limited, but it is preferable to use pAg in the range of 5-11 and pH in the range of 3-10. . Noble metals other than gold can be used as the chemical sensitizer in the present invention. As the noble metal other than gold, for example, a sensitizer using a metal salt such as platinum, palladium, iridium or rhodium or a complex salt thereof can be used.

In the present invention, reduction sensitization can be further carried out. As the reduction sensitizer used in the present invention, ascorbic acid, stannous salt, amines and polyamines,
Hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds and the like are known. In the present invention,
One of these known compounds can be selected and used,
Further, two or more kinds of compounds can be used in combination. As the reduction sensitizer, stannous chloride, thiourea dioxide, dimethylamine borane, L-ascorbic acid and aminoiminomethanesulfinic acid are preferable compounds. Since the addition amount of the reduction sensitizer depends on the emulsion conditions, it is necessary to select the addition amount, but the range of 10 ^-9 to 10 ^-2 mol per mol of silver halide is suitable. In addition to the method of adding the above-mentioned reduction sensitizer, growth or aging in a low pAg atmosphere of pAg1 to 7 called silver ripening, growth in a high pH atmosphere of pH 8 to 11 called high pH ripening, Alternatively, a method of aging, a method of passing hydrogen gas or a method of reduction sensitization by hydrogen in the nascent stage by electrolysis can be selected. Furthermore, two or more methods can be used together. This reduction sensitization can be used alone,
It can also be used in combination with the above chalcogen sensitization or precious metal sensitization.

5. Spectral Sensitization The emulsion of the present invention may be spectrally sensitized by the nuclei of methine dyes. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes,
Included are styryl dyes and hemioxonol dyes.
Particularly useful dyes are cyanine dyes, merocyanine dyes,
And a dye belonging to the complex merocyanine dye. Any of the dyes generally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like;
A nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; benzindolenine nuclei, indole nuclei, benzoxadol nuclei,
A naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms. The merocyanine dye or the complex merocyanine dye includes a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, and a rhodanin nucleus as a nucleus having a ketomethylene structure. , 5 to 6-membered heterocyclic nuclei such as thiobarbituric acid nuclei can be applied.

The dye may be added to the emulsion at any stage of emulsion preparation. Most commonly, it is carried out after the completion of chemical sensitization and before application, but it is added at the same time as the chemical sensitizer as described in US Pat. Nos. 3,628,969 and 4,225,666. It is also possible to perform spectral sensitization at the same time as chemical sensitization.
It can also be carried out prior to the chemical sensitization as described in JP-A-8-113928. It is also possible to start the spectral sensitization by adding the silver halide grains before completion of precipitation formation. Furthermore, as taught in U.S. Pat. No. 4,225,666, it is possible to add these said compounds separately, i.e. to add some of these compounds prior to the chemical sensitization and the rest to the chemical sensitization. Can be added later and can be at any time during silver halide grain formation, including the method taught in U.S. Pat. No. 4,183,756. The addition amount can be 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol of silver halide.

The silver halide emulsion prepared according to the present invention can be used in both color photographic light-sensitive materials and black-and-white photographic light-sensitive materials. The color photographic light-sensitive material is particularly used for color paper, color photographic film, color reversal film, and the black-and-white photographic light-sensitive material includes X-ray film, general photographic film, printing light-sensitive film and the like. However, it can be preferably used especially for color paper, color photographing film and color reversal film.

There are no particular restrictions on other additives to the photographic light-sensitive material to which the emulsion of the present invention is applied, and examples thereof include Research Disclosure (Reaarch Dis).
Closure) Volume 176, Item 17643 (RD
-17643), the same volume 187, item 18716 (R
D-18716) and Volume 307, Item 3071.
The description such as 05 can be referred to.

RD-17643 and RD-18716
The places where the various additives are described are listed below. Additive type RD17643 RD18716 1 Chemical sensitizer, page 23, page 648, right column 2 Sensitivity enhancer, same as above 3 Spectral sensitizer, pages 23 to 24, page 648, right column to supersensitizer, page 649, right column 4, whitening agent, page 24 5 Antifoggant 24 to 25 pages 649 right column and stabilizer 6 Light absorber, pages 25 to 26 page 649 right column to filter dye 650 page left column Infrared absorber 7 Stain inhibitor 25 page right column 650 page Left to right column 8 Dye image stabilizer page 25 9 Hardener page 26 page 651 Left column 10 Binder page 26 Same as above 11 Plasticizer, lubricant 27 pages 650 Right column 12 Coating aid, Interfaces 26 to 27 Same as above Active Agent 13 Antistatic agent Page 27 Same as above

Among the above additives, antifoggants and stabilizers are azoles (eg, benzothiazolium salt,
Nitroimidazoles, nitrobenzimidazoles,
Chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles,
Aminotriazoles, etc.); Mercapto compounds (eg, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole and its derivatives), mercapto) Pyrimidines, mercaptotriazines, etc .; thioketo compounds such as oxadrinethione; azaindenes {eg, triazaindenes, tetraazaindenes (especially 4-hydroxy-6-methyl (1,3,3a, 7) Tetraazaindene), pentaazaindenes and the like}; benzenethiosulfones; benzenesulfinic acid; benzenesulfonic acid amide and the like can be preferably used.

The color coupler is preferably a non-diffusible one having a hydrophobic group called a ballast group in the molecule, or a polymerized one. The coupler may be either 4-equivalent or 2-equivalent with respect to silver ion.
Further, a colored coupler having a color correction effect or a coupler releasing a development inhibitor with development (so-called DIR coupler) may be contained. The product of the coupling reaction may also be colorless and may include a colorless DIR coupling compound that releases a development inhibitor. For example, as a magenta coupler, a 5-pyrazolone coupler, a pyrazolobenzimidazole coupler, a pyrazolotriazole coupler, a pyrazolotetrazole coupler,
There are cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc., and yellow couplers include acylacetamide couplers (eg, benzoylacetanilides, pivaloylacetanilides), etc.,
Examples of cyan couplers include naphthol couplers and phenol couplers. As cyan couplers, U.S. Pat. Nos. 3,772,002, 2,772,162, and 375.
No. 8308, No. 4126396, No. 4334011
No. 4327173, No. 3446622, No. 43
No. 33999, No. 4451559, No. 4427767
Nos. 4,968,697, and 5,6-diacylamino-substituted phenolic couplers having an ethyl group at the meta position of the phenol nucleus, phenols having a phenylureido group at the 2-position and an acylamino group at the 5-position. Preferred are couplers and couplers in which the 5-position of naphthol is substituted with sulfonamide, amide or the like because the image fastness is excellent. The above couplers and the like can be used in combination in two or more kinds in the same layer in order to satisfy the characteristics required for the light-sensitive material, and it is of course possible to add the same compound in two or more different layers.

Hydroquinone, 6 as an anti-fading agent
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, p-alkoxyphenols, hindered phenols centering on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and silylated phenolic hydroxyl groups of these compounds, Representative examples are alkylated ether or ester derivatives. Further, a metal complex represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Photographic processing of a light-sensitive material using the present invention includes
Any known method can be used, and a known processing solution can be used. The treatment temperature is usually selected from 18 ° C to 50 ° C, but it may be lower than 18 ° C or higher than 50 ° C. Depending on the purpose, either development processing for forming a silver image (black and white photographic processing) or color photographic processing including development processing for forming a dye image can be applied. Black and white developers include dihydroxybenzenes (eg hydroquinone) and 3-pyrazolidones (eg 1-phenyl-
3-pyrazolidone), aminophenols (eg N-
Known developing agents such as methyl-p-aminophenol) can be used alone or in combination. The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. Color developing agents are known general aromatic amine developers such as phenylenediamines (eg 4-amino-).
N, N-diethylaniline, 3-methyl-4-amino-
N, N-diethylaniline, 4-amino-N-ethyl-
N-β-hydroxyethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 4-amino-3-
Methyl-N-ethyl-N-β-methoxyethylaniline and the like) can be used. In addition, L. F. A. 226, published by Focal Press (1966), "Photographic Processing Chemistry" by Meson.
229, U.S. Pat. Nos. 2,193,015 and 259,236.
Those described in each specification of No. 4, JP-A-48-64993, etc. may be used.

The developer may be a development inhibitor such as a pH buffering agent such as an alkali metal sulfite, a carbonate, a borate and a phosphate, a bromide, an iodide, or an organic antifoggant. Antifoggants and the like can be included. If necessary, a water softener, a preservative such as hydroxylamine, an organic solvent such as benzyl alcohol or diethylene glycol, a polyethylene glycol, a quaternary ammonium salt, a development accelerator such as amines, a dye-forming coupler. , Competing couplers, foggants such as sodium borohydride, co-developers such as 1-phenyl-3-pyrazolidone, tackifiers, US Pat.
The polycarboxylic acid type chelating agent described in the specification of 083723, the antioxidant described in West German publication (OLS) 2622950, etc. may be included.

When color photographic processing is performed, the photographic light-sensitive material after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process or may be performed individually. Examples of bleaching agents include iron (III) and cobalt (III)
Compounds of polyvalent metals such as chromium, chromium (IV), and copper (II), peracids, quinones, and nitroso compounds are used. For example,
Organic complex salts of phenylicyanide, dichromate, iron (III) or cobalt (III) (for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid or citric acid) , Complex salts of organic acids such as tartaric acid and malic acid), persulfates, permanganates, nitrosophenols, etc. can be used. Of these, potassium ferricyanide, sodium ethylenediaminetetraacetate (III) acetate and ammonium ethylenediaminetetraacetate (III) acetate are particularly useful. The ethylenediaminetetraacetic acid iron (III) complex salt is useful both in a stand-alone bleaching solution and in a one-bath bleach-fixing solution. For bleaching or bleach-fixing solutions, US Pat.
Nos. 520 and 3241966, Japanese Patent Publication No. 45-
Various additives can be added in addition to the bleaching accelerators described in JP-B No. 8506 and JP-B-45-8836, the thiol compound described in JP-A-53-65732, and the like. Further, after bleaching or bleach-fixing, washing treatment may be carried out, or only stabilizing bath treatment may be carried out.

[0039]

The following examples show the process time and efficiency when the emulsion is precipitated with gelatin as in the present invention, and the superiority of the photographic property of the emulsion of the present invention, but the present invention is not limited to this. It is not something that will be done. Example 1 (Invention) 890 ml of water, 0.25 g of potassium bromide and 2 g of the compound (1) described below (containing 4.71 × 10 ⁻¹ anionic groups)
Were mixed to form a solution having a pH of 5.00 at 40 ° C. Next, this solution was heated to 75 ° C. and stirred, and an aqueous solution of silver nitrate and an aqueous solution of potassium bromide were added at a precision constant flow rate of 3.6 ml /
Min (corresponding to 0.05 g / min of silver nitrate) was simultaneously added for 10 minutes, and then 25.2 ml / min was simultaneously added for 7 minutes to perform nucleation. The pBr was constant during this addition. The grain size of the silver bromide grains at this point was 0.17 μm (side length). Continuing to set the silver potential to +160 mV and set 1 for nucleation.
When a silver nitrate aqueous solution was added for 100 minutes while accelerating (primary) the silver nitrate aqueous solution and the potassium bromide aqueous solution having a concentration of 0 times, a 0.6 μm (side length) monodispersed silver bromide cube was obtained. . Next, after cooling the emulsion to 35 ° C.,
1) 2 g of deionized gelatin dissolved in 300 ml of water was added, 5 minutes later, the pH was lowered to 3.1 using phosphoric acid, and stirring was stopped after 3 minutes. After 2-3 minutes, the silver halide grains were completely settled. 2) After removing the supernatant liquid, 25
Add 00 ml of water, stir, add phosphoric acid again and adjust pH to 3.
It was adjusted to 1 and stirring was stopped after 3 minutes. After 2-3 minutes, the silver halide grains were completely settled. After repeating the procedure of 2) again, the temperature was raised to 40 ° C., 400 ml of water was added, and KBr was added.
With 1N sodium hydroxide, pAg 8.5, pH 6.5
Of the emulsion. The silver halide emulsion was completely redispersed and no emulsion lumps could be confirmed. This silver halide emulsion is designated as Emulsion 1.

[0040]

[Chemical 1]

Comparative Example 1 As a comparative example, an example in which the precipitation of a silver halide emulsion was tried with an amount of gelatin exceeding the range of the present invention will be shown. After preparing 0.6 μm silver bromide cubic emulsion grains in the same manner as in Example 1, 3
The temperature was lowered to 5 ° C., 45 g of deionized gelatin dissolved in 300 ml of water was added, and after 5 minutes, the pH was lowered with phosphoric acid, but even if the pH was lowered to 1, the silver halide emulsion did not precipitate. This emulsion was redispersed in the same manner as in Example 1 after desalting by sedimentation with a commonly used sedimentation agent when grains were formed in the presence of gelatin. This emulsion is designated as emulsion 2.

Comparative Example 2 After preparing silver bromide cubic emulsion grains having a side length of 0.6 μm in the same manner as in Example 1, the temperature was lowered to 35 ° C. and the pH was adjusted to 1, 2, 3, 4, and 4.
It was adjusted to 5, and stirring was stopped. No rapid emulsion settling was observed at any pH. Next, when the silver halide emulsion adjusted to pH 5 was allowed to stand in a cool dark place, the emulsion grains were completely settled after 7 days. The supernatant was removed, 2500 ml of water was added, redispersed and allowed to stand for 7 days, and then the supernatant was removed. After repeating this operation again, 400 ml of water was added to adjust pAg 8.5 and pH 6.5 at 40 ° C. No lumps of silver halide emulsion were observed, and it was completely redispersed, but it took 21 days to desalt to the same conductivity as Emulsion 1. This emulsion is designated as Emulsion 3.

Comparative Example 3 After preparing silver bromide cubic emulsion grains similar to those in Example 1, this emulsion was centrifuged at 8000 rpm for 30 minutes. Most of the emulsions were settled by this operation, but some grains were not completely settled. After removing the supernatant, redispersion was carried out in the same manner as in Example 1, but some particles were aggregated. This emulsion is designated as Emulsion 4.

The emulsions 1 to 4 obtained above are summarized in Table 1. As is clear from Table 1, according to the present invention, the precipitation and desalting of the emulsion in which grains have been formed can be rapidly carried out without agglomeration of emulsion grains.

[0045]

[Table 1]

Example 2 (Chemical Sensitization of Emulsions 1 to 4) Emulsions 1 to 4 were each heated to 60 ° C. and optimally subjected to gold sulfur sensitization for 60 minutes using hypo and chloroauric acid. Next, a stabilizer, a coating aid and a hardening agent were added, the gelatin contents of the emulsions were combined, and the emulsion was coated on a triacetyl cellulose support together with the protective layer by the simultaneous extrusion method to obtain a sample. 1 / each sample
Wedge exposure was performed for 100 seconds using a BPN-42 filter, and 5 times at 20 ° C. with Kodak D-19 developer.
Development was carried out for a minute, ordinary stopping, fixing, washing with water and drying were carried out, and the density was measured with white light. The results in Table 2 were obtained.

[0047]

[Table 2]

However, the relative sensitivity in Table 2 is the fog value + 0.
It is represented by the relative value of the reciprocal of the exposure amount required to obtain an optical density of 1. Emulsion 3 had a sensitivity of 100. From Table 2, the emulsion of the present invention had no adverse effect on the chemical sensitization by gelatin used for precipitation, and had the same sensitivity and fog as those of the natural precipitation emulsion. In Emulsion 4, the apparent grain size was increased due to the aggregation of grains and the sensitivity was increased.

Example 3 (Spectral Sensitization) Emulsions 1 to 4 were each heated to 60 ° C. and optimally chemically sensitized with hypo and chloroauric acid for 60 minutes. Then 4 emulsions
The temperature was lowered to 0 ° C., the sensitizing dyes shown below were added, the mixture was allowed to stand for 40 minutes, and then coated in the same manner as in Example 2 to obtain a sample.

[0050]

[Chemical 2]

Wedge exposure of each sample was performed for 1/100 second using an SC-50 filter, and Kodak D-19 was used.
It was developed with a developing solution at 20 ° C. for 5 minutes, then stopped, fixed, washed with water and dried, and the density was measured with white light.
The results shown in Table 3 were obtained. However, the relative sensitivity in Table 3 is fog +
It was expressed as a relative value of the reciprocal of the exposure amount required to obtain an optical density of 0.1. Emulsion 3 had a relative sensitivity of 100.

[0052]

[Table 3]

As is clear from Table 3, the silver halide emulsion of the present invention has the same sensitivity and fog as Emulsion 3 without being adversely affected by gelatin used for sedimentation even in spectral sensitization. When a gelatin amount exceeding the range of the present invention was used at the time of sedimentation, the spectral sensitization sensitivity was low and the fog was high.

Example 4 Stirred in 2400 ml of an aqueous solution of pH 3.0 in which 6.9 g of sodium chloride kept at 60 ° C. and 6 g of the compound (1) (containing 1.41 × 10 ²² anionic groups) were dissolved. Meanwhile, aqueous silver nitrate solution (1440m by adding water to 360g of silver nitrate)
l) and sodium chloride aqueous solution (sodium chloride 126g
Water was added to 1440 ml) at the same time to obtain a monodisperse cube having a side length of 0.95 μm. This emulsion was divided into three to obtain Emulsion 5, Emulsion 6 and Emulsion 7, which were respectively precipitated, desalted and redispersed by the following methods.

(Emulsion 5) The temperature of the silver halide emulsion was lowered to 35 ° C. with stirring, and 2 g of deionized gelatin dissolved in 300 ml of water (8 per 6.02 × 10 ²³ anionic groups) was used.
5.4 g) of the solution was added to adjust the pH to 3.2, and then the stirring was stopped. Silver halide emulsion grains from 1 minute 30 seconds to 2
It completely settled in 30 minutes. After gently removing the supernatant, 2400 ml of water was added, and the mixture was stirred again to adjust the pH to 3.
It was adjusted to 2, and stirring was stopped. The silver halide emulsion grains completely settled in 1 to 2 minutes. After removing the supernatant liquid and repeating the above operation, this time, instead of adding 2400 ml of water, 400 ml of water was added, the temperature was raised to 40 ° C., sodium chloride and sodium hydroxide were added, and pAg 7.5,
The pH was adjusted to 6.2 and redispersion was performed. No aggregation was observed in the silver halide emulsion.

(Emulsion 6) In the same manner as in Emulsion 5, except that 2 g of phthalated gelatin was used in place of deionized gelatin and the pH was lowered to 2.1 to precipitate and desalt the silver halide emulsion. It was It took 50 to 60 minutes for one settling. This silver halide emulsion was precipitated the same number of times as Emulsion 5,
After repeating desalting, redispersion was performed in the same manner as in Emulsion 5.

(Emulsion 7) Same as Emulsion 5, except that 35 g of phthalated gelatin was used in place of deionized gelatin and the pH was adjusted to 3.9 to precipitate and desalt the silver halide emulsion. 5 was repeated the same number of times and redispersed in the same manner as Emulsion 5. The average settling time per run was 25-30 minutes. Also, the same method as described above is used, except that an emulsion prepared by natural sedimentation, desalted, and redispersed is referred to as Emulsion 8. Next, each of the above emulsions 5 to 8 was heated to 60 ° C., optimally chemically sensitized with hypo and chloroauric acid, and coated in the same manner as in Example 6 to obtain a sample. Each sample was subjected to wedge exposure for 1/10 seconds, developed with the developers described in Table 4 below for 10 minutes, then subjected to normal stop, fixing, washing with water and drying, and the density was measured with white light. I got the result.

[0058]

[Table 4]

[0059]

[Table 5]

However, the relative sensitivity in Table 5 is fog +0.1.
It was expressed as a relative value of the reciprocal of the exposure amount required to obtain the optical density of. Emulsion 5 had a relative sensitivity of 100. As is clear from Table 5, when phthalated gelatin is used for sedimentation, it takes a long time to sediment a silver halide emulsion, the reaching sensitivity is low, and the fog is high, whereas in the present invention, the sedimentation time is very short. In addition, it can be seen that it has the same sensitivity and fog as those of the spontaneous precipitation emulsion.

Example 5 2580 ml of water, 0.75 g of potassium bromide and 4.5 g of the compound (2) described below (containing 3.37 × 10 ²² anionic groups) were mixed, and the pH was adjusted to 4.5 at 40 ° C. Solution. Next, this solution is heated to 75 ° C., and an aqueous solution of silver nitrate and an aqueous solution of potassium bromide are stirred with a precision constant flow rate pump while stirring 3.
Nucleation was carried out by simultaneous addition of 6 ml / min (corresponding to 0.05 g / min of silver nitrate) for 10 minutes, and then simultaneous addition of 25.2 ml / min for 7 minutes. The pBr was constant during this addition. The grain size of the silver bromide grains at this point was 0.15 μm in terms of side length. Subsequently, the silver potential was set to +75 mV, and the silver nitrate aqueous solution and the potassium bromide aqueous solution having a concentration 10 times as high as that at the time of nucleation were added for 100 minutes while accelerating (primary) the silver nitrate aqueous solution, and the side length was about 0.6 μm. A monodisperse silver bromide cube of was obtained. This emulsion is divided into three parts and the following emulsion 9 to
11 was adjusted.

[0062]

[Chemical 3]

(Emulsion 9) 1) The temperature of the silver halide emulsion was set to 35 ° C. and 48 g of a 10% deionized gelatin aqueous solution was added.
(85.7 g per 6.02 × 10 ²³ anionic groups)
Was added to lower the pH to 3.0, and then the stirring was stopped.
The silver halide emulsion all settled after 3 minutes and 30 seconds.
2) After removing the supernatant liquid, 2400 ml of water was added and stirred to adjust the pH to 3.0, and then the stirring was stopped again. All the silver halide emulsions settled after 4 minutes, and the supernatant was gently removed. 3) After repeating the procedure of 2) again, 400 ml
Water was added and stirred, and the temperature was raised to 40 ° C. to adjust the pH to 6.5,
The pAg was adjusted to 8.5.

(Emulsion 10) The temperature of the silver halide emulsion was set to 3
After the temperature was lowered to 5 ° C. and the pH was lowered to 3.0, stirring was stopped.
The silver halide emulsion grains started to settle slowly and completely settled after 7 minutes. After removing the supernatant liquid, 2400 ml of water was added and the pH was adjusted to 2.7 with stirring, and then the stirring was stopped. The silver halide emulsion grains started to settle slowly, and completely settled after 9 minutes, and the supernatant was gently removed.
Next, add 2400 ml of water and stir to adjust the pH to 2.4.
After adjusting to 5, stirring was stopped. The silver halide emulsion grains started to settle slowly and completely settled after 10 minutes. After removing the supernatant, add 400 ml of water and stir,
The temperature was raised to 40 ° C. to adjust the pH to 6.5 and pAg to 8.5.

(Emulsion 11) The silver halide emulsion was stored in a cool and dark place to spontaneously precipitate emulsion grains. After 7 days, all silver halide emulsion grains had settled. After completely removing the supernatant liquid, water was added so that the same volume as that of Emulsion 9 was obtained.
H and pAg were also silver halide emulsions which were adapted to Emulsion 9.

The emulsions 9 to 11 were chemically sensitized and coated as in Example 2 to obtain samples. Each sample was subjected to wedge exposure for 1/10 seconds using a BPN-42 filter and treated with Kodak D-19 developer in the same manner as in Example 5 to obtain the results shown in Table 6. However, the relative sensitivity in Table 6 is represented by the relative value of the reciprocal of the exposure amount required to obtain an optical density of fogging + 0.1. Emulsion 6 had a relative sensitivity of 100.

[0067]

[Table 6]

As is clear from Table 6, the silver halide emulsion of the present invention has the same sensitivity and fog as those of the naturally precipitated emulsion 11 without being adversely affected by the gelatin used for precipitation.
Moreover, the time required for sedimentation and redispersion was shorter than that of the pH operation alone and the natural sedimentation method, and the desalting could be efficiently performed.

Example 6 1000 ml of an aqueous solution containing 143 g of potassium bromide and 1
1000 ml of an aqueous solution containing 70 g of silver nitrate was mixed with 4 g of potassium bromide and 2.2 g of the above compound (1) (anionic group 5.
18 × 10 ²¹ containing) 100 pH aqueous solution containing 100
The mixture was mixed in 0 ml with vigorous stirring at 75 ° C. for 60 minutes to obtain silver bromide octahedral emulsion grains having a spherical equivalent diameter of 0.8 μm. 1 mol of silver nitrate in this emulsion
Chemical sensitization was carried out by adding 6 mg of sodium thiosulfate per 1 mol and 3 mg of chloroauric acid per 1 mol of silver nitrate and aging at 75 ° C. for 80 minutes. Next, this silver halide emulsion was desalted by an ultrafiltration method, and the volume, pH and pAg were adjusted to the values immediately before grain formation and before desalting, and the silver halide emulsion grains were potassium bromide as described above. And an aqueous solution of silver nitrate were simultaneously mixed for 60 minutes to prepare a silver bromide octahedral internal latent image type core / shell emulsion having an average equivalent spherical diameter of 1.4 μm. Next, 0.4 mg of sodium thiosulfate per mol of silver nitrate and 20 mg of poly- (N-vinylpyrrolidone) per mol of silver nitrate were added to this silver halide emulsion and ripened at 60 DEG C. for 60 minutes for chemical sensitization. . Next, this emulsion was allowed to stand in a cool and dark place for 7 days, and it was confirmed that the silver halide emulsion grains had completely settled. Then, the supernatant was gently removed, water was added and the mixture was stirred at 40 ° C.
The emulsion was H6.5 and pAg8.5. This emulsion is designated as Emulsion 12. Same as Emulsion 12 above, but after shell chemical sensitization, deionized gelatin 4 at 35 ° C instead of spontaneous sedimentation.
g (464.9 per 6.02 × 10 ²³ anionic groups)
g) was added to precipitate silver halide emulsion grains to 40 ° C.
When the emulsion 13 adjusted to the same pH and pAg as described above and the amount of deionized gelatin used in the precipitation of 49 g (5696.2 g per 6.02 × 10 ²³ anionic groups) were added, the pH alone was used. Emulsion 14 which did not settle and was treated in the same manner as Emulsion 2 of Example 1 was prepared.

To each of the above emulsions 12 to 14 was added 1 mg of 1-formyl-2- [4- {3- (3-phenylthioureido) benzamido} phenyl] hydrazide per mol of silver nitrate, and the mixture was mixed at 40 ° C. for 10 minutes. , Gelatin content is combined and coated on a film support at 240 μg / cm ² ,
It was exposed for 1/100 seconds with a Xe flash sensitometer manufactured by EGG Co., Ltd. and processed in a developer shown in Table 7 at 20 ° C. for 8 minutes.

[0071]

[Table 7]

[0072]

[Table 8]

The results shown in Table 8 were obtained. The sensitivity is represented by the relative value of the reciprocal of the exposure amount at the optical density of D = 0.7. Emulsion 12 has a sensitivity of 100. As is clear from Table 8, the silver halide emulsion of the present invention was capable of rapid desalting and redispersion processing without impairing the sensitivity and fog of the naturally precipitated emulsion.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material in which at least one silver halide emulsion layer is provided on a support, and the halogen prepared in the presence of a polymer compound containing an anionic group in the emulsion layer. It is a silver halide emulsion and is prepared by adding at least 1 g to at most 5200 g of gelatin not chemically modified with amino groups per 6.02 × 10 ²³ anionic groups, coagulating, precipitating, desalting and redispersing. A silver halide photographic light-sensitive material characterized by containing a certain silver halide emulsion.