JPS60138538A - Production of silver halide emulsion - Google Patents

Abstract

PURPOSE:To obtain a titled emulsion having high sensitivity and excellent granular characteristic at high gamma by growing a shell which is low in the content of silver iodide on the core of the silver halide particles which are octahedron and have a high content of silver iodide under the conditions under which the octahedral crystal is formed. CONSTITUTION:The particles which are monodisperse silver halide particles of an octahedral crystal and consist of silver iobromide or silver chloroiobromide contg. >=8mol% silver iodide and <=10mol% silver chloride are prepd. as core particles. The shell consisting substantially of silver iobromide contg. mol% or under of silver iodide, silver chloroiobromide or silver bromide is grown on such core particles. The silver halide crystal to be formed is so grown that the equil. crystal habit thereof is made substantially octahedral by controlling pAg, pH, temp., the concn. of the silver halide solvent and the compsn. of halogen, etc., by which the intended silver halide emulsion is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing a silver halogenide emulsion, and more specifically to a silver halogenide emulsion having high sensitivity, high gamma, and improved graininess. This invention relates to a method for producing an emulsion.

(Prior Art) In recent years, color negative films have become highly sensitive and small format, and demands for high image quality of silver halide photographic materials have become extremely severe. In particular, many improvement techniques have been proposed regarding graininess, which is completely incompatible with the demand for higher sensitivity.

The above improved technologies can be classified as (1) layer structure technology, (2)
) technology for sensitizing silver halide grains; (3) technology for the use of DIR compounds that can react with oxidized forms of developing agents to release development-inhibiting compounds; and (4) techniques for reacting with oxidized forms of developing agents to form color images. It can be broadly divided into techniques for forming couplers.

Among the above-mentioned improved techniques, methods for sensitizing silver halide grains include, for example, JP-A Nos. 58-28743 and 5B-148.
As seen in publications such as No. 29 and No. 58-100847, the technology using emulsions consisting of monodisperse silver halogenide grains is rapidly developing.

Journal of the Photographic Society of Japan, Volume 31, Pages A-O (1968) K
As reported in It was technically difficult to cover with a shell having a shell thickness.

In other words, in the above method, the device ion distribution differs between grains, and when developed after exposure, the ratio of undeveloped grains (dead grains) is high, resulting in poor sensitivity.

The degree of improvement in graininess could not be said to be sufficient.

Furthermore, Japanese Patent Publication No. 49-21657 discloses a method for producing an improved silver halide emulsion, which is believed to be based on a technical concept similar to that of core/shell type emulsions. Silver halide grains have a size,
The final emulsions obtained are irregular in shape and, as described in the examples, are silver halide with a low ionic content with a final emulsion ion content of 4 to 5 molt, It is presumed that a halogen ion exchange (conversion) reaction occurs during the process, and that the halogen composition is becoming more uniform.

Further, JP-A-55-161229 discloses a hybrid silver halide emulsion in which silver halide containing silver iodide of less than 10 mol/c is epitaxially bonded onto silver iodobromide grains having a high silver iodide content. However, there is still no known method for growing a uniform shell on silver iodobromide grains with a high silver iodide content.

(Objective of the Invention) Therefore, the object of the present invention is to provide a silver halide emulsion with a small amount of dead grains, high sensitivity, high gamma, and improved graininess. Another object of the present invention is to provide a method for producing a silver halide emulsion having high sensitivity, high gamma, and improved graininess, and another object of the present invention is to provide a method for producing a silver halide emulsion having high sensitivity, high gamma, and improved graininess. An object of the present invention is to provide a method for producing a shell-type silver halide emulsion.

(Structure of the Invention) The object of the present invention is to provide monodispersed silver halide grains having octahedral crystals, and having a silver iodide content of 8 moles or more and a silver chloride content of 10 moles or less. or a grain consisting essentially of silver chloroiodobromide as a core, and a grain consisting essentially of silver iodobromide\silver chloroiodobromide or silver bromide with a silver iodide content of 5 molt or less on the core. A method for producing a silver halide emulsion including a step of growing a shell, wherein the production of a silver halide emulsion is carried out under conditions in which the equilibrium crystal habit of the silver halide crystals produced in the step is substantially octahedral. This can be achieved by a method.

The monodisperse core/shell type silver halide emulsion according to the present invention (hereinafter simply referred to as 1 emulsion according to the present invention) produced under the conditions specified above according to the present invention can be used after chemical sensitization. It has high sensitivity and gamma, has an extremely low ratio of so-called dead duplexes that do not contribute to development, can achieve an IO of less than 1, and has a remarkable effect of improving graininess.

In other words, the emulsion according to the present invention has excellent monodispersity) and is free from irregularities in grain shape, and is particularly free from gouges caused by elution of crystal faces that tend to occur during the manufacturing process under other conditions, and from specific irregularities at the corners of grains. The appearance rate of irregularly shaped particles that appear to have grown is extremely low. It is presumed that this results in improved particle homogeneity, leading to the above-mentioned excellent photographic properties.

Next, regarding the monodisperse silver halide grains of the present invention, the particle size distribution of the monodisperse core grains is defined by the following formula according to the present invention: The divided value is o, is, or less.

Formula (A) 12160.15 The average grain size here refers to the diameter in the case of spherical /% Iff silver germide grains, and the diameter in the case of grains with shapes other than cubic or spherical. The average value of the diameter when the projected image is converted into a circular image with the same area, and when the individual grain size is ri and the number of grains is ni, it is calculated by the following formula - "Cr
is defined.

-Σn龜Renewal 1 The above particle size can be measured by various methods commonly used in the art for the above purpose. A typical method is Loveland's particle size analysis method JA, S.

T.M., Symposium on Auto-Light Microbiography, 1955, pp. 94-122, or in chapter 2 of [The Theory of Photographic Processes], co-authored by Mies and James, 3rd edition 1, Macmillan Publishing Co., Ltd. (1966). has been done. The particle size can be measured using the projected area or approximate diameter of the particle.

If the particles are of substantially uniform shape, the particle size distribution can be expressed fairly accurately as diameter or projected area.

The relationship between grain size distribution is described in "Empirical relationship between sensitometric distribution and grain size distribution in photographic emulsions" The Photographic Journal z LXXIX! , (1949) 3
This can be determined using the method described in the article by Trivelli and Smith on page 30,338.

The monodisperse core particles according to the present invention as described above are substantially octahedral crystals. In the present invention, "substantially octahedral crystal" means that the volume ratio of octahedral particles to the total volume of the particles is 80 or more.

In addition, the octahedral core particle referred to in the present invention is a core consisting of a 14-hedral crystal in which the vertices of the octahedral crystal are slightly removed (the appearance is hexagonal and quadrilateral. However, the hexagonal and quadrilateral have rounded corners. ), but the most effective core is an octahedral crystal.

The monodisperse core grains according to the present invention are silver iodobromide having a silver iodide content of 8 molt or more. The above core particle is 1
Although it may contain silver chloride at a molar ratio of 0 or less, it is preferable that it does not contain silver chloride.

Furthermore, if the silver iodide content of the core grains exceeds Seki Morchi, it becomes difficult to obtain a core with a homogeneous halogen composition, making the core grains unsuitable for use in the present invention. If the silver iodide content in the core grains is below the range of the present invention, a core/shell type emulsion with high sensitivity, high gamma, and few dead grains can be obtained without using the production method of the present invention, but graininess However, the improvement is insufficient.

The silver halide composition of the shell portion of the core/shell type monodisperse emulsion according to the present invention is silver iodobromide monochloroiodobromide or pure silver bromide containing 5 moles or less of silver iodide.

When the shell is made of silver chloroiodobromide, the content of silver chloride is preferably 10 mole or less, particularly preferably 1 mole or less. The thickness of the shell is preferably 0.2 to 0.01 μm, particularly preferably 0.1 to 0.054 μm.

When the shell thickness exceeds 0.2 μm, a core/shell type emulsion with high sensitivity, high gamma and little dead grain can be obtained, but the degree of improvement in graininess is small. Furthermore, when the shell thickness is less than o, oiμ, it is difficult to obtain a silver halide emulsion with high sensitivity, high gamma, little dead grain, and improved graininess even by the production method of the present invention.

A feature of the method for producing a silver halide emulsion of the present invention is that in the step of growing a shell having the above-mentioned silver halide composition on the core grains having the above-mentioned characteristics, the halogenation step in which the shell is grown The purpose is to carry out the process under conditions in which the equilibrium crystal habit of the silver crystal becomes substantially octahedral.

The meaning of the above-mentioned substantially octahedral shape has already been described in the explanation regarding the monodisperse core particles. The emulsion consisting of octahedrons produced by the production method of the present invention is
It may have a slight depression or a slight roundness as described in Japanese Patent Application Laid-Open No. 58-106352.

The effect of the present invention is that even if the core particles are monodisperse, the shape of the core is a cube or a tetradecahedron close to a cube (the shape of the core is octagonal and triangular, and triangular and quadrilateral). ), it cannot be obtained, and it can also be obtained when the equilibrium crystal habit of the silver halide crystal at the time of Schelling is substantially cubic or tetradecahedral, and when it is in the twinning region. I can't.

To produce monodisperse core silver halide grains, grains of a desired size can be obtained by a double jet method while keeping pAg constant. In addition, for the production of highly sensitive monodisperse silver halide emulsions, JP-A No. 54-4
The method described in Japanese Patent No. 8521 can be applied. For example, it is produced by a method in which a potassium iodobromide-gelatin aqueous solution and an ammoniacal silver nitrate aqueous solution are added to a gelatin aqueous solution containing silver halide seed particles while changing the addition rate as a function of time. At this time, highly monodisperse silver halide grains can be obtained by appropriately selecting the time function of addition rate + pH + pAg * temperature, etc.

The equilibrium crystal habit of the core grains and core/shell grains of a silver halide emulsion depends on the environment in which the silver halide grains grow, that is, pAg + pH * temperature, presence or absence of a silver halide container1.
and the concentration of the solvent. In addition, the equilibrium crystal habit varies greatly depending on the halogen composition of silver halide.

This is discussed in the Photographic Book Science and Engineering, Vol. 6, p. 159, (1
962), Ibid., Vol. 17, p. 289, (1973), Ibid., Vol. 12, p. 207, (1968), and Jarl Otographik Science, Vol. 1, p. 81 (1968). 1976), vol. 4, p. 47 (1)
979), Vol. 12, p. 242 (1964), etc.

Therefore, the shape of silver halide grains in the present invention is controlled by controlling the pA during precipitation and physical ripening of the silver halide emulsion.
g * plFI + is achieved by controlling the temperature, the concentration of the halogenated trowel solvent, and the silver halide composition.

In the present invention, before the addition of the water-soluble silver salt in the step of adding the core/shell silver halide particles with the pericardial fluid and in the process of adding the aqueous solution of the water-soluble silver salt, the tetrazaindene compound It is preferable for the presence of the above to narrow the particle size distribution of the resulting silver halide grains.

The tetrazaindene compound is preferably a compound represented by the following general formula (I).

R1t Rt and Rs are hydrogen atoms, alkyl groups, amino groups, alkyl group derivatives, amino group derivatives 1-C0
NH-R4 (Ra is water: Jg atom, alkyl group, amino group 1 derivative of alkyl group, derivative of amino group, halogen atom, aryl group, derivative of aryl group)? represent.

Specific examples of the tetrazaindene compound will be shown below.

(1) (2) (3) (4) The substantially monodisperse silver halide grains produced by the present invention can be used in other monodisperse emulsions or polydisperse emulsions having different silver iodide contents and grain sizes. It can also be used in a mixture of 1 and 1.

When the silver halide grains produced according to the present invention are applied to a light-sensitive material, the monodisperse silver halide grains according to the present invention are added to the same silver halide emulsion layer by a total weight of less than or equal to the weight of all grains. It is preferable that it contains. More preferably, it is equal to or higher than Seki Shigechi.

In the process of producing silver halide grains obtained by the 91i production method of the present invention, for example, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or m-salts thereof, rhodium salts or complex salts thereof, etc. are allowed to coexist. Good too.

The silver halide emulsion according to the present invention can be spectrally sensitized using dyes of type 6. Dyes used include polymethine dyes including cyanine-merocyanine, complex cyanine and complex merocyanine (ie, tri-, tetra-, and polynuclear cyanine and merocyanine), oxonol, hemioxonol, styryl, merostyryl, and streptocyanine.

Cyanine spectral sensitizing ♂ elements include quinolinium, pyridinium, inquinolinium, 3H-indolium, pentuindolium, oxacillium, oxazolinium, thiazolium, thiazolinium, imidazolinium, benzoxacillium, benzothiazolium, benzoselenium. Zolium, benzimidazolium naphthoxacillium,
Two basic heterocyclic nuclei connected by a 5-methine bond derived from naphthothiazolium, naphthoselenazolium, thiazolinium, dihydronaphthothiazolium, biryllium and imigzovirazinium quaternary salts. included.

Fio cyanine spectral sensitizing dyes include barbituric acid, 2
-thiobarbic acid, a-danine, hydantoin, 2
-thiohydantoin, 4-thiohydantoin, 2-pyrazolyl-5-one, 2-isooxazolin-5-one,
indan-1,3-dione, 1,3-dioxane-4,
6-dione, pyrazoline-3,5-dione, pentane-
Acidic nuclei such as those derived from 2,4-dione, -alkylsulfonylacetonitrile, malononitrile, isoquinolin-4-one, and chroman-2,4-dione and a cyanine dye-type basic polycyclic nucleus form a methine bond. including those connected by.

Spectral sensitizing dyes useful for sensitizing the silver halide emulsions of the present invention include British Patent Nos. 742,112, 1 U.S. Pat. No. 1.846,302, No. 1,846,303
No. 1.846,304, No. 2.078,23
No. 3, No. 2.089,729, No. 2,165,3
No. 38, No. 2,213,238, No. 2,231,
No. 658, No. 2.493,747, No. 2.493
, No. 748, No. 2,526,632, No. 2,73
No. 9,964, Reissue Patent No. 24,292), Reissue Patent No. 2
, No. 778,823, No. 2.917,516, No. 3,352,857, No. 3.411,916, No. 3,431,111, No. 2.295,276 ,
2,481,698, 2,503,776, i2.68s, s4s, 2,704,714
No. 29.21,067, No. 2.945,76
No. 3, No. 3,282,933, No. 3.397,0
No. 60 1 ken $ 3,660,102, No. 3.660
, No. 103, No. 3.335,010, No. 1, No. 3.35
No. 2,680, No. 3,384,486, No. 3.3
No. 97,931, No. 3.482,978, No. 3.
No. 623,881, No. 3.718,470, and No. 4.025,349. Examples of useful dye combinations, including supersensitizing dye combinations, are provided in U.S. Pat.
．． No. 506,443 and No. 3,672,898. Examples of supersensitizing combinations consisting of spectral sensitizing dyes and non-absorbing additives include U.S. Pat.
805, bis-triazinyl aznostilbene as disclosed in U.S. Pat. No. 2,933.390, and U.S. Pat. 1 using sulfonated aromatic compounds as disclosed in US Pat. No. 3,457,087; ,8
Using iodide as disclosed in No. 26, and using other compounds, including those described in the previously cited Review of Mechanisms Reference by S Supersensitization by Gilman. I can do it. The above-mentioned sensitizing dyes may be added at any time such as at the beginning of chemical ripening (also called second ripening) of the silver silver emulsion, during ripening, after the end of ripening, or at an appropriate time prior to emulsion coating. But it doesn't matter.

In addition, the method for adding the sensitizing dye to the photographic emulsion is as follows:
The fgk method that has been proposed in the past can be applied. For example, as described in U.S. Pat. No. 3,469,987, a sensitizing dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and this dispersion is added to an emulsion. Good too. Furthermore, the sensitizing dye of the present invention is
Individually dissolved in the same or iE, jx le medium, these solutions can be mixed or added separately before being added to the emulsion.

As the solvent for the dye when the sensitizing dye is added to the silver halide emulsion, water-miscible organic solvents such as methyl alcohol, ethyl alcohol, and acetone are preferably used.

When the sensitizing dye is added to the silver halide emulsion, the amount added is 1X10-' mol to 2.5x10-'' mol, preferably 1.0X10-4 mol to 1 mol per mol of silver halide. .OX 10"-" mole.

The silver halide grains according to the present invention can be subjected to various commonly used chemical sensitization methods. i.e. active gelatin;
Noble metal sensitizers such as water-soluble gold salts, water-soluble platinum salts, water-soluble palladium salts, water-soluble rhodium salts, and water-soluble iridium salts;
Chemical sensitization can also be carried out using chemical sensitizers such as sulfur sensitizers; selenium sensitizers; polyamines, reduction sensitizers such as stannous chloride, etc. alone or in combination.

As the sulfur sensitizer, known ones can be used. Examples include thiosulfate, allylthiocarbamide thiourea, allyl isothiacyanate, cystine, p-toluenethiosulfonate, and rhodanine. Other U.S. Patents No. 1,574°944, U.S. Patent No. 2,410,
No. 689, No. 2,278,947, No. 2,728
．． No. 668, No. 3,501,313, No. 3.65
6,955 specifications, German Patent No. 1.422,86
No. 9, Japanese Patent No. 56-24937 1 Japanese Patent Publication No. 55-4
Sulfur sensitizers described in Publication No. 5016 can also be used. The amount of sulfur sensitizer added may be sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range depending on various conditions such as pH, temperature, silver halide grain size, etc., but as a guide, it is about 10-7 mol to about 10-1 mol per mol of silver halide. preferable.

Selenium sensitization can be used instead of sulfur sensitization, and selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenoamides, selenocarboxylic acids and esters. and selenides such as selenophosphate@1 diethylselenide, specific examples of which are described in U.S. Pat. Nos. 1,574,944 and 1,6
No. 02,592, Specification No. 1,623,499, etc.

As with the sulfur sensitizer, the amount added varies over a wide range, but a rough guideline is approximately 10-7 per 81 moles of halogenide.
The amount is preferably about 1 mol to 10 mol.

As the gold sensitizer (in the present invention), various kinds of gold compounds can be used, regardless of whether the oxidation number of gold is +1 or +3. Typical examples include chloroauric acid salt, potassium auric thiocyanate, auric trichloride monopotassium auric thiocyanate, potassium iodoaurate, tetracyano auric acid, ammonium aurothiocyanate, pyridyl trichlorogold, and the like.

The amount of gold sensitizer added varies depending on various conditions, but as a guide, it is approximately 10-7 to 10-7 mol per mol of silver halide.
A range of up to 1 mol is preferred.

The method for sensitizing silver halide grains in the present invention can also be carried out in combination with a method for sensitizing silver halide grains using other noble metals, such as platinum, palladium, iridium, rhodium, or salts thereof.

In the present invention, it is also possible to further use reduction sensitization. The reducing agent is not particularly limited, but includes known stannous chloride, thiourea dioxide, and hydrazine derivative-1 silane compounds.

It is preferable to perform reduction sensitization during the growth of silver halide grains or after completion of sulfur sensitization and gold sensitization.

A known halogenated #solvent can be used at any point in the production process of the silver halide emulsion according to the present invention. For example, (a) U.S. Patent No. 3,271゜157, U.S. Patent No. 3,531,289, U.S. Pat.
(b) thiourea derivatives described in JP-A-53-82408, JP-A-55-77737 and JP-A-55-29829; (,) Japanese Patent Publication No. 53-1
Silver halide il agent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in Japanese Patent Publication No. 44319, (d) imidazole a) described in Japanese Patent Application Laid-Open No. 100717/1983 e) Sulfite [, (f)
thiocyanane), (g) ammonia, (h) JP-A-1973
Hydroxyalkyl-substituted ethylenediamines described in JP 7-196228, (f) JP-A-57-202
Examples include the mercaptotetrazole anticonductor described in Japanese Patent Publication No. 531, and (j) the benzimidazole derivative described in Japanese Patent Application Laid-Open No. 58-54333.

The silver halide grains according to the present invention include a manufacturing process thereof,
Various compounds may be added at the end of chemical ripening for the purpose of preventing fog from occurring during storage or development, or for stabilizing photographic performance.

For example, anurs 1, such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles 1, etc.
Lobenzimidazoles, promobenzicardial dazoles, mercaptothiazoles 1 mercaptobenzimitazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (special IC 1-7 z-nyl-5-mercaptotetrazole) ), as well as mercaptopyrimidines, mercaptotriazines, thioketo compounds such as oxazolinthione, as well as benzenethiosulfinic acid, benzenesulfinic acid, benzenesulfonic acid amide, hydroquinone derivatives, aponophenol derivatives, gallic acid derivatives. A number of compounds known as antifoggants or stabilizers can be added, such as 1 ascorbic acid derivatives and the like.

These chemicals are preferably added during chemical ripening or before coating.

Various hydrophilic colloids including gelatin are used as binders for silver halide emulsions. Gelatin includes not only gelatin but also derivative gelatin.
Derivative gelatin includes a reaction product with gelatin anhydride, a reaction product between gelatin and isocyanate, a reaction product between gelatin and a compound having an active halogen atom, and the like. The acid anhydrides used in the reaction with gelatin include, for example, maleic anhydride, 7-talic anhydride, benzoic anhydride, acetic anhydride, isatoic anhydride, succinic anhydride, etc., and the isocyanate compounds include, for example, phenyl anhydride. isocyanate, p-prosophenyl isocyanate, p-chlorophaer isocyanate), p
-) Lylisocyanate, p-nitrophenyl isocyanate, naphthylisocyanate, and the like.

Furthermore, examples of compounds having an active nitrogen atom include Irf, benzenesulfonyl chloride, p-methoxybenzenesulfonyl chloride, p-phenoxybenzenesulfonyl chloride, p-bromobenzenesulfonyl chloride, p-toluenesulfonyl chloride, m
-nitrobenzenesulfonyl chloride, m-sulfobenzoyl dichloride, naphthalene-β-sulfonyl chloride, p-chlorobenzenesulfonyl chloride,
3-Nitro-4-aminobenzenesulfonyl chloride, 2-carboxy-4-bromobenzenesulfonyl chloride, m-carboxybenzenesulfonyl chloride, 2-amino-5-methylbenzenesulfonyl chloride, 7thalyl a-ride, p-nitropenzoyl Included are chloride, pensoyl chloride, ethyl chlorocarbonate, furoyl chloride, and the like.

In addition to the above-mentioned derivative gelatin and ordinary photographic gelatin, as Kl aqueous colloid for preparing a silver halide emulsion, colloidal albumin, agar, gum arabic, dextran 1 alginic acid, for example, acetyl content 19 to Types of cellulose acetate hydrolyzed to 2B% K Cellulose derivatives 1 Polyacrylamide, imidized polyacrylamide, casein, vinyl alcohol polymers containing urethane carboxylic acid groups or cyanoacetyl groups, such as vinyl alcohol vinyl cyanoacetate copolymers, polyvinyl Use of algylene polyvinyl pyrrolidone, hydrolyzed polyvinyl acetate, polymers obtained by polymerizing proteins or saturated acylated proteins with monomers having vinyl groups, polyvinylpyridine, polyvinylamine, polyaminoethyl methacrylate, polyethyleneimine, etc. You can also do it.

Furthermore, silver halide emulsions contain various known interfaces for various purposes such as coating aids, antistatic agents, improving slipperiness, emulsification and dispersion, preventing adhesion, and improving photographic properties (for example, accelerating development, increasing contrast, and sensitizing). It may also contain an activator.

Namely, U.S. Pat. Nos. 2,240,472 and 2,38
1゜766 No. 1, No. 3.158,414, No. 3, 2
No. 10,191, No. 3.294,540, No. 3,
507,6601 British Patent No. 1.0124,951
U.S. Patent No. 1.022,878, U.S. Patent No. 1.179,2901, U.S. Patent No. 1,198,450, U.S. Patent No. 2.739,
No. 891, No. 2,823,123, No. 1.179
No. 290, No. 1,198,450, No. 2,739
, No. 891.

No. 2,823,123, No. 3,068,101, No. 3,415,649, No. 3,666,478
No. 3,756°828, British Patent No. 1,397
, No. 218, No. 3,113゜816, No. 3,4
No. 11,413, No. 3,473.174, No. 3.
No. 345,974, No. 3,726,683, No. 3
．． No. 483,368 1 Belgian Patent No. 731,126, British Patent No. 1.138,514, Belgian Patent No. 1.15 g
, No. 825, No. 1,374,780 1 U.S. Patent No. 2
, 271,623, 2.288,226, 2,944,900, 3,235.919, 3,671.247, 3,772,021 ,
No. 3,589,906, No. 3,666,478, No. 3,754,924 1 West German Patent No. 1M OL8
1,961,683 description and JP-A-117-1983
No. 414 No. 50-59025, Special Publication No. 40-378
No. 1 No. 40-379 and No. 43-13822.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensate, polyethylene glycol alkyl or alkylaryl ether polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol/l /furkylamines or amides, silicone polyethylene oxide adducts), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), li! Ii Fatty acid esters of alcohols, alkyl esters of sugars, nonionic surfactants such as urethanes or ethers, triterpenoid saponins 1-alkyl carboxylates 1-alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates esters, alkyl phosphates) N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers 1 polyoxyethylene alkyl phosphates, carboxy, sulfo groups such as nano, Anionic surfactants containing acidic groups such as phospho groups, sulfate ester groups, phosphate ester groups, etc.
Ampholytic surfactants such as mitotic acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkyl betaines, amine imides, amine oxides, alkyl amine salts, aliphatic or aromatic quaternary ammonium Cationic surfactants such as salts, heterocyclic quaternary ammonium salts such as viridicum, imidazolium, and sulfonium or sulfonium salts containing aliphatic or heterocycles can be used.

In the silver halide emulsion according to the present invention, in addition to the above-mentioned surfactant as a development accelerator,
No. 2,002,871, No. 2,445,611, No. 2,360,878, British Patent No. 1,352,19
It may contain imidazoles, thioethers, selenoethers, etc. described in the specification described in No. 6.

In order to apply the matahalide button emulsion to color light-sensitive materials, magenta, silver halide emulsion adjusted to green sensitivity, red sensitivity and blue sensitivity according to the present invention, magenta,
It is sufficient to apply the methods and materials used for color photosensitive materials, such as incorporating a combination of cyan and yellow couplers. Preferably, the couplers are non-diffusible and have a hydrophobic group called a pallast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ions. It may also include a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). As a good yellow color-forming coupler, a known open-chain ketomethylene coupler can be used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow couplers that can be used include U.S. Pat. No. 2,875°057.
No. 1, No. 3,265,506) No. 3,408,19
No. 4, No. 3,551,155, No. 3.582,3
22 No. 1 No. 3.725.07\2, No. 3,891
, 445, West German Patent No. 1.547,868, West German Patent Application (OLS) No. 2,213.461 No. 1, No. 2, 2
No. 19,917, No. 2,261,361, No. 2,
No. 414,006, No. 2,263,875, etc.

As the magenta coloring coupler, pyrazolone compounds, indacylon compounds, cyanoacetyl compounds, etc. can be used, and patented pyrazolone compounds are advantageous.

Specific examples of magenta color-forming couplers that can be used include U.S. Pat. No. 2,600,788, U.S. Pat.
No. 2,311,476, No. 3,419,391 1 No. 3,519,429, No. 3,558,319
No. 3.582,322, No. 3.615,50
No. 6, No. 3,834゜908, No. 3,891,4
45, West German Patent No. 1,810゜464, West German Patent Application (OLS) No. 2,408,665, West German Patent Application No. 2,417
, 945 No. 1 2,418,959, 2.42
No. 4,467, Japanese Patent Publication No. 40-6031, etc.

As the cyan coloring coupler, phenolic compounds, naphthol compounds, etc. can be used. Specific examples include U.S. Patent No. 2,639,929, U.S. Patent No. 2,434,
No. 272, No. 2,474,293, No. 2.521
, No. 908, No. 2,895,826, No. 3,03
4゜892 No. 1 3,311,476, 3,4
No. 58,315, No. 3,476,563, No. 3,
No. 583,971, No. 3,591,383, No. 3
, No. 767,411, West German Patent Application (OLS) 2,4
No. 14,830, No. 2,454,329, Japanese Unexamined Patent Publication No. 4
No. 8-59838.

Brain No. 3,476,560, Brain No. 2,521,908,
No. 3.034,892, Special Publication No. 44-2016,
No. 38-22335, No. 42-11304, No. 44
-No. 32461, 7F! 9Ml1i'(49-9846
9th light! '! t, 50-118021 @Mei IVI11
8. Those described in West German Patent Application (OLS) No. 2,418°959 can be used.

DIrL couplers include, for example, U.S. Pat.
No. 7,554, No. 3.617,291, No. 3.7
No. 01゜783, No. 3,790,384, No. 3,
No. 632,345, West German patent application (OLS) 2,41
No. 4,006 1 No. 2,454゜301, No. 2,4
No. 54,329, British Patent No. 9.53゜454, Japanese Patent Application Publication No. 154234/1983, Japanese Patent Publication No. 28690/1983,
JP 54-145135, JP 57-151944, JP 52-82424, U.S. Patent No. 2.327,55
No. 4, No. 3.958,993, Japanese Unexamined Patent Publication No. 1983-145
Those described in the above-1 publication of No. 135 Fathom can be used.

In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor upon development, and those described in West German Patent Application (OT, S) No. 2,417.914 can be used. Others JP-A-55-85549, JP-A-57-94752, JP-A-56-65134, JP-A-56-
No. 135841, No. 54-130716, No. 56-1
No. 33734 to No. 56-135841, U.S. Patent No. 4
, 310,618, British Patent No. 2,083,640, Research Disclosure, 18360 (19
1979) 414850 (1980), A 190
33 (1980), 19146 (1980)
, 420525 (1981), 421728 (
Couplers described in 1982) can also be used.

Two or more of the above couplers may be contained in the same layer. Further, the same compound may be contained in two or more different layers.

The coupler can be introduced into the silver halide emulsion layer using known methods, such as the method described in US Pat. No. 2,322,027. For example, phthalic acid alkyl esters (dibutyl 7 talate, dibutyl 7 talate, etc.),
Phosphate esters (diphenyl phosphate, triphenyl 7-mole 7-ate, tricresyl 7-othate, dioctyl pudyl phos-7ate), citric acid esters (
Examples include acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl lacrylamide), etc., and boiling points of 30°C.
Organic solvent at 150°C to 150°C, such as lower alkyl acetate such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol A methyl isobutyl ketone, β
- After being dissolved in methoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid.

The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used.

When the coupler has a carboxylic acid or sulfonic acid group, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

These couplers are generally added from 2X10-' moles to 5X10-' moles, preferably from 1X10-2 moles to 5X10-' moles, per mole of silver in the silver halide emulsion layer. The materials are 1hydrodroginone derivatives, aminophenol fat conductors, and antifogging agents.
It may contain gallic acid derivatives, ascorbic acid derivatives, etc., specific examples of which are given in U.S. Patent No. 2,360,29.
No. 0, No. 2,336,327, No. 2.403,7
No. 21, No. 2.41.8,613, No. 2,675
゜314, same No. 2,701,197, same No. 2.70
No. 4,713, No. 2,728,659, No. 2,7
No. 32,300, No. 2.735,765, Japanese Unexamined Patent Publication No. 1973
No. 0-92988, No. 50-92989, No. 50-9
No. 3928, No. 50-110337, Special Publication No. 50-2
3813 etc.).

As the antistatic agent, diacetyl cellulose, styrene perfluoroalkyl rhidium freate copolymer, alkali salt of a reaction product of styrene-maleic anhydride copolymer and p-aminobenzenesulfonic acid, etc. are effective. Examples of matting agents include methyl methacrylate, polystyrene, and alkali-soluble polymers. Furthermore, it is also possible to use colloidal silicon oxide. Further, examples of the latex added to improve the physical properties of the film include copolymers of acrylic esters, vinyl esters, etc., and other monomers having ethylene groups. Examples of gelatin plasticizers include glycerin and glycol compounds, and examples of thickeners include styrene-sodium maleate copolymers and alkyl vinyl needle-maleic acid copolymers.

Supports for photosensitive materials made using the silver halide emulsion prepared as described above include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass paper, cellulose acetate, cellulose nitrate, polyvinyl Examples include acetal 1 polypropylene, polyester films such as polyethylene terephthalate, polystyrene, and the like, and these supports are appropriately selected depending on the purpose of use of each photosensitive material.

These supports are subjected to undercoat processing, if necessary.

After exposure, a photosensitive material made using the silver halide emulsion according to the present invention can be developed by a commonly used known method.

The black and white developer is an alkaline solution containing developing agents such as hydroxybenzenes, aminophenols, and aminobenzenes, as well as sulfites, carbonates, and other alkali metal salts.
May include bisulfites, bromides, iodides, and the like.

In addition, when the light-sensitive material is for color use, color development can be carried out by a commonly used color development method.In the zero reversal method, the material is first developed with a black negative developer, and then exposed to white light or in a bath containing a fogging agent. , and further color development is performed using an alkaline developer containing a color developing agent. There are no particular restrictions on the processing method, and any processing method can be applied, but typical examples include a color development method, a method in which a bleach-fixing treatment is performed, and if necessary, further washing with water and a stabilization treatment, or a color development method. After development, bleaching and fixing are performed separately, and if necessary, further water washing and stabilization treatment are performed.5.
The formula can be applied.

It is preferably applied to many photosensitive materials because it has low fog and low fog.

For example, the photosensitive material according to the present invention may be used for general black and white use, for X-ray use,
It can be effectively applied to photosensitive materials for various uses such as color, infrared, micro, silver dye bleaching, reversal, and diffusion transfer.

Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 0.079 mol equivalent of a monodisperse silver iodobromide emulsion with an average grain size of 0.3 μ containing 2 mol of silver iodide was added as seed grains to an aqueous solution (A-1) having the following composition at 40°C. In addition, pH and p
Ag was prepared using acetic acid and an aqueous potassium bromide solution. This solution was vigorously stirred, and while controlling the pH and pAg, aqueous solutions (B-1) and (C-1) with the following composition were added by the double jet method, and then in the same manner as above, an aqueous solution (D-1) with the following composition was added. 1) and (E-1) added
Next, the pH of the above solution was adjusted to 6.0 and the pAg to 10.3, and the solution was washed with demineralized water using a conventional method to obtain (Em -1) to (Em -s ) of a monodisperse emulsion sample with an average grain size of 0.8.
was created.

Aqueous solution (A-t) Aqueous solution (B-1) Aqueous solution (C-1) Aqueous solution (D-t) ' Aqueous solution (E-1) Above aqueous solution (B-1) r (C-1) , (D -1
) and (E-1) and the results of observation using an electron microscope of the obtained emulsions are shown in Table 1 below. The core/shell type silver halide grains contained in emulsions (E-3) and (E-s) have an extremely low contamination rate of irregularly shaped grains compared to silver halide grains obtained by production methods other than the present invention. I understand that.

Example 2 The emulsion samples (F-1) to (E-8) prepared in the above example were divided into silver halide contents equivalent to 0.35 mol, and each portion was divided into two parts: ammonium thiocyanate, ammonium thiocyanate,
Chemical sensitization was performed using sodium thiosulfate and chloroauric acid, and anhydro 5.5'-
Dichloro-9-ethyl-3,3'-di(3-sulfopropyl)oxacarbocyanine hydroxide: Ambidrow 5,5'-diphenyl-9-ethyl-3,3'-di(3-sulfopropyl)oxacarbo Cyanine: Anhydro-9-ethyl-3,3'-di(3-sulfopropyl)-5,6°5',6'-dibenzoxacarbocyanine hydroxide was added at 20 Iv each, and further 4-hydroxy-6- Methyl-113,3m
+ Added 7-chitrazaindene and 5-phenyl-1-mercaptotetrazole. Next, a dispersion with the following composition (
M-1) at 1200 m/2, saponin and 1,2-bisvinylsulfonylethane were added to a cellulose triacetate paste support with a silver content of 15 vv/d11?
A sample having a stable coating film was obtained by applying the coating and drying it once. This sample was used as sample 1%1 to 16. Dispersion (M-1) 1-(2,4,6-)dichlorophenyl)-3-(3-(2,4-di-tcrt- amylphenoxyacetamide)-penzamide-5-
Using 8 xio"" moles of pyrazolone per mole of halogenation, 2-(1-7 ale-5
-tetrazolylthio)-4-octadecylsuccinimide-1-indanone was used.

This was mixed with tricresyl phosphate in an amount of 1 times the weight of the coupler as a high-boiling organic acid, and ethyl acetate was added to the mixture and heated to 60° C. to completely dissolve it. A 10% aqueous solution of Alkanol B (registered trademark DuPont alkylnaphthalene sulfonate)
The mixture was mixed with an aqueous solution of 700 g of gelatin and 10 g of gelatin, and dispersed using a colloid mill. These samples and comparative samples were exposed to white light using a #KS-1 type sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd.) according to the JIS method, and then subjected to the following color development treatment.

[Processing process] (37.8℃) Processing time 1, color development 3 minutes 15 seconds 2, bleaching 6 minutes 15 seconds 3, washing with water 3 minutes 15 seconds 4, fixing 6 minutes 5 seconds, Washing with water 3 minutes 15 seconds 6, stabilization 1 minute (9) seconds 7, drying Color developer composition: Bleach composition Fixer composition: Too V & ammonium acid 175.0. ! Composition of il stabilizing liquid: The sensitometric results obtained by sniffing are shown in Table 2 below. Here, the sensitivity is expressed as a relative value of the reciprocal of the exposure amount that gives a fog of +0.1.

In addition, graininess is defined as 100% of the standard deviation of the variation in elegance value that occurs when a dye image with a dye image density of 1J + 0.7 is scanned by a microdensitometer with a circular scanning aperture of 5μ.
Control sample with 0 times value 100 Procedural amendment November 29, 1980 Mr. Manabu Shiga, Commissioner of the Patent Office 1.711 indications 1982 Patent Application No. 248625 26 Name of invention Method for producing silver halide emulsion 3 , Relationship with the case of the person making the amendment Patent applicant address Higashig'lnI 1-26-2 Nishi-Shinjuku, Shinjuku-ku Name (127) Konishiroku Photo Industry Co., Ltd. 4, Agent 〒
191 Address: 1 Sakura-cho, Hino-shi, Tokyo, Japan 6. From the results of the above table in the "Detailed Description of the Invention" of the specification subject to amendment, core/shell type monodisperse obtained by the manufacturing method of the present invention. Emulsion sample containing halogenated sushi grains (
Samples/I63.8.11 and 16) have higher sensitivity and higher gamma than emulsions prepared by other manufacturing methods using the same halogen composition, and they were obtained by adding a DIR compound to the emulsion. It can be seen that even when they are aligned, the sensitivity is high and the graininess is significantly improved. At the same time, it was also found that the number of dead grains during development was small and dead grain was improved.

(Effects of the Invention) The emulsion containing core/shell type monodisperse silver halide grains obtained by the production method of the present invention has high sensitivity, high gamma, and improved graininess, and has the characteristics of low dead drain during development. It comes to have.

Agent Yoshimi Kuwahara

Claims (1)

[Claims] Monodispersed silver iodobromide grains of octahedral crystals, with a silver iodide content of 8 mol or more and a silver chloride content of 10 mol or less, or itm iodobromide sushikar, etc. A step of growing a shell consisting essentially of silver iodobromide, silver chloroiodobromide, or silver bromide having a silver iodide content of 5 molt or less on the core. A method for producing a silver oxide emulsion), characterized in that the step is carried out under conditions in which the equilibrium crystal habit of the silver oxide crystals formed is substantially octahedral. A method for producing a chlorogenated steel emulsion.