JPS6114630A - Preparation of silver halide emulsion - Google Patents

Abstract

PURPOSE:To obtain a monodispersed silver halide emulsion consisting essentially of twins and high in sensitivity and superior in graininess by growing multiple twin grains or spherical grains obtained from the multiple twins as seed crystals in the range of specified pBr in the presence of a tetraazaindene compd. CONSTITUTION:The silver halide emulsion having a high content of AgI is prepared by growing the multiple twin grains or spherical grains obtained from the multiple twins as seed crystals in a pBr of -0.8-4.0 in the presence of one of compds. represented by formulae I -IV or having repeating units, each represented by formula V in which R5 is H or 1-6C alkyl; J is a bivalent linking bond; X is one of formulae I -IV; and R1-R3 are each H, halogen, optionally substd. amino, alkyl, cycloalkyl, or optionally substd. aryl, or the like. The use of a photosensitive layer contg. this emulsion permits a photosensitive material to have high sensitivity and superior graininess and to be used for black-and-white, X-ray, and color photosensitive materials, etc.

Description

[Detailed description of the invention]

(1) Purpose of the invention (industrial application field) The present invention relates to a method for producing a halogenated halogen emulsion, and more specifically, it is a highly sensitive and granular emulsion with a relatively high silver iodide content (mainly composed of twin grains). This invention relates to a method for producing a silver halide emulsion that is particularly suitable for producing a silver halide emulsion with excellent properties. (Prior art) In recent years, color negative films have become more sensitive and small-formant, and silver halide photographic materials have become more and more highly sensitive. The demands for improved image quality are becoming increasingly strict.In response to these demands, research has been carried out with a focus on improving silver halide emulsions. In particular, we are concerned with the control technology of the size and size distribution of silver halide grains, the single structure of halogen grains inside the grains, and the crystal shape.

[
7, using monodisperse normal crystals (+)) ``IP has been carried out. On the other hand, H1 Kankawa' from Yumto: Lj@- Silver chloride emulsion suitable for film and C polydisperse. Silver iodobromide emulsions with a relatively high silver iodide content consisting of twinned grains of It was recognized that crystals played an important role in the copying process, and were widely used.Although it has these characteristics, there is no sufficient explanation regarding the generation and growth mechanisms of twins. It must be said that the control technology for size, size distribution, halide complex composition structure inside the grain, crystal shape, etc. is extremely incomplete compared to the technology for normal crystals. A technique for growing twinned emulsions with relatively high monodispersity is not yet known. Japanese Patent Publication No. 5R-3FI762 discloses a method for producing twinned emulsions with high monodispersity; The process of growing the emulsion is limited to iodine with a low silver iodide content.
+1 [No. 123] discloses that after forming silver halide crystals containing 90 mol% of silver iodide, a water preparation solution and bromide or a homogenate are added, and a twinned halogen is formed using a convergicin reaction. A method for producing a silver oxide emulsion has not been disclosed 2
) However, in order to effectively cause the IT conversion reaction in Konera's method, it is assumed that the silver iodide content of the halogenated parent grains during growth is low, which is a major constraint. Japanese Patent Publication No. 5F1-142329, 5B-211143
No. 58-209730 discloses an improved method for producing a monodisperse emulsion, but it not only has the drawback that grain growth is limited to cases where the silver iodide content is low. The emulsion obtained by this method contains many normal crystals and can hardly be called a monodisperse twin emulsion. JP-A-5F+-127921 discloses a method for producing planar twin emulsions made of Shinshiro Shigin, but the grain size distribution of the emulsions obtained by this method is wide;
It cannot be said that it is monodisperse. JP-A-58-113927 discloses a tabular twin emulsion with a high silver iodide content in the outer part of the grains, but the grain size distribution of the emulsion that cannot be obtained by this method is wide and monodisperse. I can't say anything about sex. Although various attempts have been made to produce twin emulsions as described above, it is difficult to produce silver halide emulsions that have a high silver iodide content, have good monodispersity, and are mainly composed of twin crystals. The method is still unknown. OBJECTS OF THE INVENTION The first object of the present invention is to provide a method for producing a monodisperse silver genide emulsion consisting mainly of twin crystals. A second object of the present invention is to provide a method for producing a silver iodobromide emulsion, which has a relatively high silver iodide content, is monodisperse, and mainly consists of twin crystals. A third object of the present invention is to provide a method for producing a silver iodobromide twinned emulsion which has a relatively high silver iodide content and is monodisperse, mainly consisting of C1111) planes. A fourth object of the present invention is to provide a method for producing a silver halogenide emulsion suitable for a photographic material having high sensitivity and excellent graininess. (2) Structure of the Invention The object of the present invention is characterized by having a step of growing seed particles, which are multi-twin particles and/or spherical particles that cannot be obtained from multi-twins, in the presence of a tetrazaindene compound. This can be achieved by a method for producing a silver halide emulsion. As the tetrazaindene compound used in the present invention, compounds represented by the following general formulas (I) to (IV) and compounds having a repeating unit represented by the general formula (V) are preferable. In the formula, R1-R1 may be the same or different, and each hydrogen atom: halogen atom, amide group, substituted amino group (e.g. jethyltemino group, etc.); aliphatic residue, e.g. alkyl group (e.g. methyl group, ethyl group, etc.) group, propyl group, pentyl group, hexyl group, octyl group, isopropyl group, 8ee-
Butyl group, t-butyl group, cyclohexyl group, cyclopentylmethyl group, 2-norbornyl group, the above general formula (1
) to (IV), with one hydrogen atom removed and an alkyl group substituted with a monovalent group); an alkyl group substituted with an aromatic residue (e.g. benzyl group, phenethyl group, benzhydryl group, etc.); group, l-naphthylmethyl group, 3-
phenylbutyl group, etc.); alkyl group substituted with an alkoxy group (e.g. methoxymethyl group, 2-methoxyethyl group, 3-ethoxypropyl group, 4-methoxybutyl group)
; a hydrogen atom, a hydroquine group, a carboxyne group, a mercapto group, an alkoxycarbonyl group, a Vi-substituted or unsubstituted amino group, or an argyl group (e.g., monochloronotyl group, didroginmethyl group, 2-hydroxy Methyl group,; U-hydroxybutyl group, methylmercapto group, carboxynemethyl group, 2-carboxyethyl group,
2-(methoxycarbonyl)ethyl group, aminomethyl group, diethylaminomethyl group, etc.); or aromatic residue aryl group (e.g. phenyl group, 1-naphthyl group, etc.):
An aryl group having a substituent (e.g. p-tolyl group, m-
Ethylphenyl group, m-cumenyl group, mesityl &, 2.
3-xylyl group, p-chlorophenyl group, o-bromophenyl group, p-hydroxybutyl group,] -]hydroxy-2-naphthyl group m-methoxyphenyl group, p-ethoxyphenyl group, p-carboxyphenyl M, O- (methoxycarbonyl)phenyl group, m-(,utoquincarbonyl)phenyl group, 4-carboxy-1-naphthyl group, etc. or -LR. (R, has the same meaning as R1 and R7, and 17 represents a divalent linking group, such as -CONH, -). Hail nke1 and it2 again. General formula (V) RI+ (-CH2-C) (1) Length, R5 dihydrogen) 1, I charcoal 1: sand 1 to 6 alkyl group (for example, methyl group, ethyl group, etc.). L represents a divalent linking group. X represents the above general formula (I) - (
IV) represents a monovalent group obtained by removing one hydrogen atom from a compound. Especially preferred as R3 are a hydrogen atom and a methyl group. Although J is a divalent linking group, it is preferable that the total number of carbon atoms is ] -20. Among such linking groups, the following formula (
Those not represented by J-I) or (J-TI) are preferred. (J-1)0 -c-y-z- In the formula, Y is -〇- or -N- (where R6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. z represents an alkylene group ( Preferably, the number of carbon atoms is 10 t. An amide bond, ester bond, or needle bond may be present between the alkylene groups. For example, methylene group, ethylene group, propylene group, -CB, OC
H,-,-CH,CONHCH,-1-CH,CTlI
COOCH2-1-CH,CH,0COCH,-1-C
112N HC (I CH, -, etc.) or arylene group (
Preferably one having 6 to 12 carbon atoms. For example, p-phenylene group, etc.). Particularly preferable divalent linking groups as J include the following. -C0NHCH, -1-C0NHCH, CH, -1-C
0NHCH, 0COCH, -1-C0NHCH2CH,
CH,0COCH,-1-C00CH,-1-C00C
H2CH,-1-C00CH,CH,0COCH,~,
-C00CH,CH,CI,0COCH,-5 Examples of the tetofuzai/thene compound are given below. OH011 +81 +91 (1st place
(171
M O<aII C31)
C)l. H The multi-twinned particles used in the present invention can be obtained by mixing a water-soluble protective colloid solution with a water-soluble silver salt bath solution, or a water-soluble silver salt bath solution and water γ61'F...ride under conditions where pBr is 07 to 200, for example. C can be obtained by adding 7 Jll of compound solution). Multi-twinned grains are dispersed in a water-soluble colloidal dispersion medium and grown as a dispersion, i.e., an emulsion.
A 7j emulsion containing seed grains that can be used for Iv anti-1-4W is hereinafter referred to as a seed emulsion. 4- The seed emulsion containing multiple twinned grains used in the invention (referred to as 1 sotho-quadruple twinned grain emulsion) has a ratio of power-harvesting twins of (9) to the combined grain number τ similar to that of the emulsion. It is preferable that it is 1% or more, and it is favorable for history to be above 1%. Morphology of multiple twins [-Basic scissors and salt photography edition of photographic engineering IP,
1fi3 to 166 (Corona Inc.), and are classified and described in detail, and can be distinguished using an electron microscope. The spherical grain-containing emulsion used in the present invention (hereinafter referred to as spherical seed emulsion) &-1 The emulsion containing multiple twinned grains obtained by the above method is ripened in the presence of a silver halide emulsion. Particularly preferred conditions include ammonia 0.4 to 10 mol/liter and potassium bromide 0.3 to 0.5 mol/liter at a temperature of 35 to 45°C.
) It can be obtained by aging for 5 minutes to -). In the present invention, silver halide emulsions which cannot be obtained by using a spherical seed emulsion than by using a multi-twin seed emulsion or a multi-twin grain and a spherical grain obtained from the multi-twin field emulsion are preferred. Preferable from the viewpoint of monodispersity. The seed emulsion used in the present invention is formed by mixing silver ions and halogen ions and can be transferred to the next mill in the same container. You can also do that. The seed particles contained in the seed emulsion are preferably selected from the above-mentioned seed particles of the present invention. The 1'1' ratio of the seed particles other than the seed particles of the present invention is at most 2 (preferably about 1% by weight). In the method of the present invention, the tetrazaindene compound is It is preferable that the Ki emulsion is present in the range of 10-1 to 10-5 mol per 1 mol of silver halide contained in a dispersion system, that is, an emulsion, in which silver 9-genide grains are dispersed and grow using grains as nuclei. , more preferably 5×
It is in the range of 10 to 10 moles. Note that the tetrazaindene compound is represented by the general formula (V)
In the case of a compound having 14 repeating units, the same number of moles of the tetrazaindene is added. -7-h '7''J (As a method of adding the compound, it is also possible to directly add the seed particles to the &tr water-soluble storage colloid solution, or to dissolve the seed particles in the water-soluble halogen supplement aqueous solution. l) LJ of silver halide grains with seed grains as cores
It can also be added gradually in batches. A preferred embodiment of the production method of the present invention is an embodiment in which the production method is carried out in a kneaded stage V, that is, an embodiment in which the tetrazaindene compound is contained in a dispersion system containing seed particles and the amount of the tetrazaindene compound is increased as the halogenated complex particles grow. is despised. The seed particle growth pBr in the present invention is from 07 to 4.0.
There is a mandatory committee under the following conditions. Outside this range, the monodispersity is markedly reduced and it is difficult to obtain the desired emulsion. A more preferable pBr range is 1.0 to 3.0. In the present invention, a water-soluble etb solution and a water-soluble halide solution are mixed into the seed emulsion to grow seed grains.
If good. In the present invention, the water-soluble silver salt solution or the water-soluble silver salt solution and the water-soluble halide solution in the seed particle growth step are carried out in a range of 1) to 100% of the critical crystal growth rate.
). The critical velocity of a crystal is defined as the -1- limit at which new nuclei are not substantially generated in the process of crystal growth;
The present invention allows the weight of the newly generated crystal nuclei to be less than 10% of the total weight of the total complex. , grow the seed particles, double the average particle size of the seed particles - the average particle size of the halogen iron #
Grain-f to IIv length l? I like to be able to make a lot of cloves (
7. In the 14th step of the growth process of the present invention, the crystal growth method 1f
III! For the purpose of IN, known halogen silver solvents are present (4).
271゜157th edition-1 same No.: (,531,289, 3.574.
・+-+589+7 Is it an organic thioether that is not described in each publication?
No. 77737, No. 55-2 '1829, and Japanese Patent Publication No. 1977-: (N 57 + Thiourea derivatives described in each publication, etc., tc) 4! AgX solvent having an oxygen or sulfur atom and a gold atom which is not described in Japanese Patent Application Laid-Open No. 144319, 'f, f' and a thiocarbonyl group, fat Imidazoles not listed in , (,) 1sulfurous acid 1 salt, fr) thiocyanate, (GL ammonia, FHL JP-A Showa Fi7-1
Hydroquine argyl-substituted ethylenediamines described in 41fi228, fil JP-A-57-20
Examples include mercaptototrazoles, which were not described in Japanese Patent No. 2531, and benzimidazoles, which were described in FJL JP-A-58-54333. Specific examples of silver halide solvents are listed below: HO-(OH7)t-8-(CHt)*-8-(
CHt 12-0HCH, -NHCO-CH9CH,C
0OHCH, -3-CH, CH, SC, H. CH, -NHCO-CH, CH, CH. CH, -3-CH, CM, SCH, CH2C0OH 盈CH. CH, OCH, CH, CI4 = CH. fe) K, So. ffl NH,SCN, KSCNfgl
NH, oH ()II OHI ()l((lH CH. In the present invention, in the step of growing seed particles, the p I-1 of the particle growth atmosphere can be in the range of 2.0 to 130. However, preferably ld7.0 to 12.
It is an l-envelopment of 0. In the present invention, the temperature of the emulsion in the step of forming seed grains can range from 30°C to 80°C, but it is preferably carried out at 35°C to 65°C. 6. As the water-soluble silver salt and water-soluble halide used for the formation of the seed particles and the growth of the seed particles, those not normally used in this field can be used, and the water bath Examples of water-soluble salts include silver nitrate, and examples of water-soluble halides include potassium bromide and hexate-11 bromide.
Examples include ammonium bromide, potassium iodide, and the like. In the silver halide emulsion prepared by the production method B1 of the present invention, the composition distribution of silver iodine within the grains may be localized (unevenly distributed) or may be uniform. An example of the localization of iodine scissors is a core made of iodine tithe with a high silver iodide content and a shell made of iodine tithe or Ii pure silver bromide with a low silver iodide content. Core and/or shell types are preferred. When the silver halide emulsion produced according to the present invention is used in a photographic light-sensitive material, the tortoise-dispersible IJ button emulsion according to the present invention is incorporated into one silver halide emulsion layer. - It is preferable that the IF-11 iron contains 3)% l of gold. It's more preferable than Kanto η%jヅ. In the manufacturing process VC of silver halide emulsions according to the uninvented manufacturing method ζ, for example, cadmium salts, zinc salts,
Lead bottles, thallium fields, iridium bases, complex salts such as iridium salts, rhodium salts, complex salts thereof, etc. can coexist. The halogenated button emulsion 11 according to the present invention can be spectral sensitized using various dyes. Dyes used include K VJ-anine, melon-anine, complex merocyanine, and complex merocyanine (i.e., tri-, terra-, and polynuclear cyanino- and melon-anine), oxonol, hemioglysol, sunaryl. Contains no polymethine dyes such as , merostyryl and histoleftosinol.Nanine spectral sensitizing dyes include 6-j, quinolinium, pyridinium, isoquinolinium, 3) 1-indolium, pentuindolium, ogisazolium, ogyrhizoli: Yuno2, the Ryozolium, thiazolinium, imidazolinium, penzochyrhizolium, benguthiazo-11um, penzoselenazollium, benzimidazoliuno, f
- C#A was not combined by a methine bond that could not be derived from phthoxazolium, naphthothiacyliQ, naphthocetonazolium, thiazolinium, /hydronaphthothiazolium, pyrylium, and imidazopyrazinium quaternary salts. 2
It does not contain two Hanawa-based multi*ring nuclei. Merosia; d1 barbituric acid as a spectral sensitizing dye, 2
- Thiopaf 1 pituric acid, rhodanine, hydantoin,
2-naohydantoin, 4-thiohydantoin/, 2-pyrazolyl-5-one, 2-isooxazolin-5-one, indan-1,3-dione, 1,3-dioxan-4
, 6-dione, birazoline-4,5-dione, pentane-2,4-dione, λrusulfonyl-cetonitol, malononide II, isozanolin-4-one and chroman-? 1. I will visit from 1-2 on. In the present invention, "5 acidic nucleus and noanine ring I element 1 ((1's base element fv element ring nucleus and ζ, connected to methine bond 1゛1 s i)" are also included. In the present invention, Spectral sensitizing dyes useful for producing halogenated-Q emulsions? sensitizing A and V) are described in British Patent No. 742.
．． 112, U.S. Patent No. 1.84fi, 300, -
1 No. 1.8・lFi, :(IN No. 1.Ft46.
3 (No. 12, No. 1.846, No. 03, No. 1.
84fi, No. 404, No. 2, +178, 2
No. 33, No. 2, (No. 189, 729, No. 2.+
65. :(<o No. 2,213,238, No. 2,231,1i58, No. 2,493,747,
Dotej, L', No. 493,748, No. 2,526.6
:I issue, No. 2,7: (9,964-sleeve (Reissue No. 24, No. 292), No. 2,778.82: (No.,
No. 2,917,516, No. 39, U52,2157
No. 3,411.91fi, No. 3.431,
No. 111, No. 2,295.27fi, No. 2,48
1,698-Bow, same No. 2.5 (13,77fi No. 2.6) 11(, fiJfi No. 2.7 (14,7
No. 14, No. 2, ! 12 +, 11fi No. 7,
Same No. 2, 945, 763, Same No.: (, 282, 9
3: No. U, No. 397, No. 0fiO, No. S
, hti (1, l f] No. 2, hti No. 3, fif
ifl, + No. 113, same No.: (, 335, (11
No. 11, No. 3,352.68 (No. 1, No. i,
3) (4, No. 4815, same number; U+ 3!J 7
, 51B No. 1, same No. 3, 4) + 2, ! +
71 (No. 3, fi 2', 'h, 88
No. 1, -Road No. 3,718,470 and No. 4,025,349
It is published in the issue. Examples of useful dye combinations, including supersensitizing dye combinations, are in US patents! 3, 506. No. 443 and No. 3,672,898. An example of a supersensitizing combination consisting of a spectral sensitizing dye and a non-absorbing additive is the use of thiocyanate in the process of spectral sensitization as disclosed in U.S. Pat. No. 2,933,390, using bis-triazinylaminostilbenes, and using sulfonated aromatic compounds as disclosed in U.S. Pat. No. 2,937,089; Patent No. 3,45
No. 7,087 using mercapto-sensitized heterocyclic compounds and iodides as disclosed in British Patent No. 1.413,826. Other compounds can be used, including those described in ``The Mechanism on Supersensitization''. At the beginning (also called second ripening), during ripening h12,
This process may be carried out at an appropriate time, such as after the completion of ripening or prior to coating the emulsion (＼).Also, as a method of adding a sensitizing dye to the above-mentioned silver halide emulsion, no conventional method has been proposed. Various methods can be applied, such as those described in U.S. Pat. It may also be carried out by dispersing and adding this dispersion to an emulsion.
Individually dissolved in the same or different solvents, the kneading solutions can be mixed or added separately before being added to the emulsion. As the solvent for the sensitizing dye, for example, water-miscible organic solvents such as methyl alcohol, ethyl alcohol, and acetone are preferably used. Addition of sensitizing dye, 1xl per mole of silver halide
O mol to 2.5XlO mol, preferably 1.0Xl
O mol to 1. OX 10 mol. The silver halide emulsion produced according to the present invention can be subjected to various chemical sensitization methods that are commonly used. Namely, activated 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; sulfur sensitizers; selenium sensitizers; polyamines, primary chloride It is also possible to sensitize using chemical sensitizers such as reduction sensitizers such as tin alone or in combination. As the sulfur sensitizer, known ones can be used. Examples include thiosulfate, allylthiocarbamide thiourea, allyl isothiacyanate, cystine, p-)luenethiosulfonate, and rhodanine. Other U.S. Patent No. 1.574.944, U.S. Patent No. 2.4 In
, fi89, same no.2゜278.947-, same no.2
, 728.668, same No. 3゜501, , (13-
4+, same number 3.656.9! ') No. 5 specifications, German Patent No. 1.422, + (No. 69, Japanese Patent No. 56-2)
No. 4937, JP-A-55-45FL16, etc. (MeC yellow sensitizer can also be used. The sulfur sensitizer m711111 effectively increases the sensitivity of the agent. For example, pH
Although it varies over a considerable range under various conditions such as temperature and size of silver halide grains, it is preferably about 10 mol to about 10 mol per at mol of halide. 1.Selenium sensitization may be used instead of yellow sensitization, but selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenamides, and selenocarbons. Acids and esters, selenophosphates, selenides such as diethylselenide, etc. can be used, and specific examples thereof are described in U.S. Pat. No. 1,574,4144 and U.S. Pat. It is described in fi02゜592, fi02゜592, fi02゜592, fi02゜592. As with the case of sulfur sensitizers, the amount of addition is variable over a wide range, but as a guideline, it is approximately 10% per mole of silver halide.
The amount is preferably about 1 mol to 10 mol. In the present invention, the gold sensitizer may have an oxidation number of +1 or +3, and a multivalent gold compound is used. Typical examples include chlorauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, hisridyl trichlorogold, and the like. The addition port of the gold sensitizer varies depending on various conditions, but as a rough guide, it is preferably in the range of about 10 mol to tO mol per mol of halogenated #. The sensitization of the halogenated emulsion prepared according to the present invention can also be carried out using other noble metals, such as platinum, palladium, iridium, rhodium, or metals 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, hydrazine crystal conductor, and silane compound. Reduction sensitization can be carried out during the growth of the halogenated trowel particles, and the reduction sensitization can be carried out during the growth of the halogenated trowel particles.
This can be carried out after completion of sulfur sensitization and gold sensitization of the silver rognide emulsion. In the silver halide emulsion produced according to the present invention, it is possible to prevent the occurrence of fog during its production process, storage, or physical development.
Various compounds may be included at the end of chemical ripening for the purpose of stabilizing FL or photographic performance. For example, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzimidazoles, aminotriazoles, benzo]-lyazoles, nitrobenzimidazoles, benzimidazoles, mercaptotetrazoles (% 1-phenyl-5-mercaptotetrazole), etc., mercaptopyrimidines, mercaptotriazines, thioketo compounds such as oxazolinthione, and also benzenethiosulfinic acid, benzenesulfinic acid Many compounds known as antifoggants or stabilizers can be added, such as benzenesulfonic acid amide, hydroquinone fermentation conductor, amino'phenol fermentation conductor, gallic acid fermentation conductor, ascorbic acid vg conductor, and the like. These chemicals are preferably added during chemical ripening or before coating. In the present invention, protective colloids for the seed emulsion and the halogenated image emulsion produced by the method of the present invention can be those commonly used for halogenated complex emulsions, and various hydrophilic colloids including gelatin can be used. I need it. Gelatin includes not only gelatin but also derivative gelatin, and derivative gelatin includes gelatin, a reaction product with gelatinic acid anhydride, a reaction product between gelatin and incyanate, or a reaction product between seratin and a compound having an active halogen atom. Products etc. can be included. Examples of the acid anhydrides used in the reaction with gelatin include maleic anhydride, phthalic anhydride, benzoic anhydride, acetic anhydride, isatoic anhydride, and succinic anhydride, and examples of incyanate compounds include For example, phenyl isocyanate, p-bromophenyl isocyanate, p-chlorophenylinocyanate, p-tolyl isocyanate, p-don 1 trophy i product 7
/isocyanate, naphthyl isocyanate and the like. Furthermore, examples of compounds having active halogen atoms include benzenesulfonyl chloride, p-methquinbenzenesulfonyl chloride, p-phenoxybenzenesulfonyl chloride, p-20mobenzenesulfonyl chloride, p-toluenesulfonyl chloride, m-nitrobenzenesulfonyl chloride, m-sulfobenzoyl dichloride, naphthalene-β-sulfonyl chloride, p-chlorobenzenesulfonyl chloride, 3-nitro-4-aminebenzenesulfonyl chloride, 2-carboxine-4-bromobenzenesulfonyl chloride,
m-carboxybenzenesulfonyl chloride, 2-amino-5-methylbenzenesulfonyl chloride, phthalyl chloride, p-nitrobenzoyl chloride, benzoyl chloride, ethyl chlorocarbonate, 70
Included are yl chloride and the like. In addition to the above-mentioned derivative gelatin and ordinary photographic gelatin, examples of hydrophilic colloids include colloidal albumin, agar, agar, gum arabic, dextran, alginic acid, etc. 1) Hino such as lulose acetate (for use)
- base conductors, polyvinylamines, imidized poly'gammacryl'mide, casein, 1 ruthane carbon lV & f, anoacetyl, M + ((( 'l'
Vinyl alcohol polymer-, polyvinyl f/l-
: l-ruphorinylhyloritone, hydrolyzed polyvinyl hydrolithate, a polymer obtained by polymerizing a proteinaceous polymer or an acylated proteinaceous compound with a vinyl group-containing hexamer;
Polyvinylpyridine, polyvinylamine, polyaminoethyl methacrylate, polyethyleneimine, etc. can also be used. Furthermore, silver halide emulsion GC produced according to the present invention
1d, coating aid, antistatic agent, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g. development acceleration, high contrast,
Various known surfactants may be included for various purposes such as sensitization). That is, U.S. Pat. No. 2,240,472, U.S. Pat. No. 2.3R
l, 7 t; fi issue, fi + era 3, 158, 41
No. 4, same No. 3゜210.1!1149. Same number;(,29
4,540, 3°507.6(i(1), British Patent No.+, o+2.49s, 1.022.F(78
No. 1.179,290, No. 1,1 (18,4
No. 50, U.S. Patent No. 2.739. 81) No. 1, No. 2.82: (, No. 123, No. 1, 1)
79゜290, same No. 1,198.4F10, same No. 2
．． 739. 85th month, same No. 2,823,123, same No. 3. f16
8゜101, same No. 3,415. fi No. 49, No. 3.
666. 478, British Patent No. 3,756,828, British Patent No. 1:497,21s-Q, British Patent No. 3,113.81fi,
Same No. 3゜1, No. 413, No. 3,473,174, No. 345.974, No. 3,726,683
No. 3°483: (fiB, Belgian Patent No. 7
31,126, British Patent No. 1,138,514, British Patent No. 1,159°825, British Patent No. 1,374,780,
U.S. Patent No. 2.271. fi No. 23, No. 2,288,
No. 226, No. 2.944.900, No. 23
No. 5,919, No. 3.671.247, No. 3,7
No. 72,021, No. 3.589.90fi, No. 3
．． 6fi3478, 3,754.9271, West German Patent 10Ls I, 961. No. 683, each specification 1 and JP-A No. 1987-50-++74z-s. 11jl 50-! 'l No. 90241, Tokkosho, i
n-378, same white) -; (79th, same 4; U-
1: (For example, the first example described in each publication No. 822)
; Nian steroids), -r Lukire 7 Oh 1' -
IJ-(do b conductor (e.g. polyethylene glycol, polynylene glycol/polypropylene glycol condensate, polyethylene glycol algyl or goalkylaryl ether polyethylene glycol 1-
chills, polyethylene glycol alcohol chillies, polyalkylene glycol alcohol-1'luminamides, silicone polyethylene
7-ide adducts), glycidol derivatives (e.g. alkenyl succinic acid polyglycerides, alkenyl-root enol polyglycerides), polyhydric alnyi 1- + σ month 1t
T rib acid Nisal 4. Argyl esters of JLlν1,
Similarly, non-imene surfactants such as Q-rethanes or L-thyls, trinalpenoid threads, Zaboan, alkyl carboxylic acids, alkylbenzenesulfones, mt=,
Alkylnaphthalene sulfonic acid base, alkyl merenate esters, alkyl phosphate esters, N-anru N-alkyl taurine jJ1, sulfosuccinic acid esters, sulfoalkylpolyogine ethylene'rlkyl phenyl ether f, t'J, polyogine ethylene / Anionic surfactants containing acidic groups such as carboxy, sulfo, phospho, sulfate, phosphate groups such as argyl phosphates, amino acids, aminoargyl X
Luhon r! J/class, aminoalkyl sulfate or H If
Amphoteric interface agents, alkyl amine groups, aliphatic or aromatic compounds such as esters, alkyl betaines, amine imides, amine oxides, etc., primary ammonium! ! Classes, hyridium, imidazolium, etc. are suitable for primary and primary ammonium and 111 (
Cationic surfactants containing If-containing sulfonium or 11 sulbo121 cum tMm can be used. . In addition to the above-mentioned surfactant as a development accelerator, the silver halide emulsion produced by the present invention contains
OLS)2. t) No. 02,871, same No. 2゜445, l
'il No. 1, No. 2, (fi (1, 878,
It may contain imidazoles, thioethers, selenoethers, etc., which are described in British Patent No. 1.3F12.1qfi. Further, K in which the silver halide emulsion produced according to the present invention is applied to an electrosensitive material of color 411 is the green-sensitive silver halide emulsion according to the present invention, red-sensitive and evening-sensitive KM mode f+
It is only necessary to apply the techniques and materials used for each color photosensitive material, such as incorporating 11 combinations of magenta, cyan, and yellow couplers into a silver halide emulsion, and the couplers are incorporated into the molecule. A non-diffusible substance with a hydrophobic group called a ballast group is...
It can be either 4 hits or 2 hits lit ill' for Kabufu tddjA-n. In addition, nonora-docazolar, which has a color correction effect of 11L, and 4) i, c ・-(311, 1! 4! ('II
'! It A1. l 'a' late I coupler (so-called I) T R coupler) 4" read 411. In history coupler V: t coupling 71 colors, raw IJ74 of course force t (color coupler also A) It is possible to use a known open-chain ketomethylene coupler as a yellow color-forming coupler. Preference is given to compounds of the Kowara uchipenzoylacetanilide series and of the hibaloylacetanilide series. Specific examples of yellow stretch couplers that can be used and U.S. Pat.
No. 4, I8 Co. 1 No. 3,551,155, No. 3, 5
82, :(22, 01; German Patent No. 3.725,072, German Patent No. 3.891,445, West German Patent No. 1,547.
8fi No. 8, West German Patent Application (OLS) 2,213.4f
i1, m2゜219, ! 117 envelopes, No. 2.2
fil, :+61, No. 2゜414.0116, No. 2,263,875, etc. cannot be mentioned. As magenta color couplers, pyrazolone compounds, indacylon compounds, /anoacetyl compounds, etc. can be used.Pyrazolone type compounds for samurai are advantageous. Specific examples include U.S. Patent jA2, fioO, No. 788,
No. IR2,983, fi08-Q, Same No.: (, Ofi
2, fi 53, same No. 3. +2'7.2fig No., same No.;u, 311.47fi No., same No.:(,419,
: No. 391, No. 519, No. 429, No. 429;
U, 558, '319, Same No.', (,582,
No. 322, No. 2 (, I]l 5.5116, No. 5:
(,834,9F18ぢ,Same No. 3,891,11F
Published by West German Patent No. 1.81 (No. 1゜464, West German Patent No. 11'
j, 7'1iJai (OLS) 2.4118.6
No. 65-, same No. 2. Roa, No. 945, No. 2, 41
8,959 shi J1 same No. 2.424.4f Geji! V) described in Japanese Patent Publication No. 40-6031 etc. is pregnant. A phenol compound, a naphthol compound, etc. can be used as a cyan coloring agent or a blur. Specific examples include U.S. Patent No. 216; column 39°029;
．． 4: 4.272°, 2.474°. 2 (No. 13, 2.52+, qns, 2.89
5. No. 826, same No.; U, O: (, 1, 892, same No. 3
, :(l 1. 476, same No. 3,458,315, same No. 3.47f
'i. No. 563, same No.: (,583,971, same No., U, F
l! 11゜; U83, Same No.:l, 7 fi 7
, No. 411, West German Time 11-Out 1+1 (OLS) 2. II
+, 8:<o issue, i'A2, 454, :32
September, Tokukai Akime <h! + 8: (+(interest; shikom)
7'1. Examples of colored couplers include U.S. Patent No. 3,
476, Fl No. 60, Id. No. 2,521.9iIF
No. I, No. 3 o: +4. +92 No. 44-2 (1
16-i-i, same: U8-22: (No. 35, same 42-
No. 113114, No. 44-32/161, Patent Application 1977
-98469 Mei 140 Ca, Mei 50-1l8 (Description 1 of No. 129, West German Patent Application (OLS) 2゜418.959 VC) can be used.゜2
27.554, IEI No. 617,291, IEI No. 3゜7+11,783, IEI No. 3, 790, 3
84S, same No.: 3°632, 345, West German Patent No. m
(OLS) 2,414゜0I) No. 6, same No. 2,454.
: (No. 01, No. 2.4!'14. ; No. 329, British Permit 95: U, = No. 154, Japanese Patent Publication No. 1983-] F14234, Japanese Patent Publication No. 1989-286
No. 90, Japanese Patent Publication No. 54-145135 bow, No. 57-151
No. 944, 10152-) 12424, U.S. Pat.
．． :(27,554 April, 3rd, 9h 8, 99
No. 3, Japanese Patent Application Publication No. 54-14513F1, etc.
Those listed in the official gazette can be used. In addition to the DIR coupler, the light-sensitive material may also contain a compound that releases a development inhibitor along with the dust mound.
79, 529, West German Patent No. 111 (OLS) 2,4
17゜914 can be used with the F4 pin. Others: JP-A No. 55-85549, JP-A No. 57-947S2, JP-A No. 56-('+ 5134, JP-A No. 56-135841,
No. 54-130716, No. 5 ti-1:4373
No. 4, No. 5f'1-135841, U.S. time 11~",
4, :(l 1), No. 618, British Patent No. 2゜083.1i411 Bow, Research Disclosure, No +83f'i0 (1079), No +4
850 (1980), No. 90 :(:((+
! 180 years), Ii 19146 (+4) 80 years),
II2 (1525 (Ro) 81), 21728 (l)
You can also use the j + tano J puller described in +2 years). The couplers mentioned above can also meet in the same layer. (The same compound may be contained in two or more different layers). Coupler 4...1] A silver emulsion layer is formed using the known method, for example, Kida Tokubi 1 No. 2. :(22,
Horn method described in No. 1127 ``, l-: is used J+i) P/lle i-, I'' / Argyl tarrate J block (dino-f-) 1 phthalate-1, dioctyl Futato t 't), Su] / Acid ester (Schiff S nyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), Nisdel citrate (e.g. acetyl tributyl citrate)
, benzoic acid esters (e.g. octyl benzoate), algylamides (e.g. diethyl laurylamide), organic solvents with a boiling point of 30'C to 150°C, such as lower argyl acetates such as ethyl acetate, butyl acetate,
After dissolving in ethyl 1biacetate, secondary butyl alcohol, methyl isobutyl ketone, β-methoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. It may be used in combination with a low boiling point organic solvent.If the coupler has an acid group such as carboxylic acid or sulfonic acid, it will be introduced into the hydrophilic tocolloid as an alkaline aqueous solution.Couplers such as CH are generally halogenated. 2XlO mol to 5 x 10 mol per mol of silver emulsion 1, 1-
) L<KeIXl+) mole to FIXIO mole addition is applied using the present invention! = Ten 1 [Silver emulsion-containing photosensitive material If'iψ As an anti-bleeding agent...Idokino 7e4 body, aminephenol R4 body, gallic acid, 41
[, Ascorbic acid? It may contain form A, etc., and specific examples thereof include US Pat. No. 2.3fiO, 290 and US Pat.
, 3: (No. 6, 327, 13 verses 2,403,721, same writing 2,418,613 art, p, i: 4.675, 3
14, 14 Haya 2, 7 I)l, 197, same No.:, 7:) 4,713, same No. 2.728.659,
Same No. 2,7: (No. 2,300, No. 2.7: (5,76
No. 5, JP-A No. 50-92988, JP-A No. 50-92989
No. 50-93928, No. 5O-11tC (described in No. 37, Koko No. 50-23813, etc.). Maleate copolymers, alkali salts of reaction products of styrene-maleic anhydride copolymers and p-aminebenzenesulfonic acid, etc. are effective.As matting agents, polymethyl methacrylate,
Examples include polystyrene and hyalkali-soluble polymers. Furthermore, it is also possible to use silicon oxide in the form of 21J.Also, as a latex added to improve the physical properties of the film, acrylic esters, vinyl esters, etc. and other ethylene group-containing monomers can be used. Examples of gelatin plasticizers include glycerin and glycol compounds, and thickeners include styrene-maleic acid copolymers and alkyl vinyl ether-maleic acid copolymers. Supports for photosensitive materials made using the silver halide emulsion produced according to the present invention include V, 1, such as baryta paper, polyethylene 411 paper, polypropylene synthetic m, glass paper, cellulose acetate, and cellulose. Polyester films such as nitrate, polyvinyl acetal, polypropylene, polyethylene terephthalate, etc.
Examples include polystyrene, and the dough support is appropriately selected depending on the intended use of each photosensitive material. . These supports are subjected to -CT drawing processing if necessary. After exposure, the light-sensitive material prepared using the silver halide emulsion according to the present invention can be subjected to image processing by a commonly used known method. It is an alkaline solution containing yI image royalties such as black-and-white phenomenon QFi, hydroxybenzenes, aminephenols, and aminebenzenes, and other alkali metal salts such as sulfites, carbonates, bisulfites, bromides, and iodides. can include. When the photosensitive material is for color use, color development can be carried out by the commonly used combination development I# method. In the reversal method, the image is developed with a black iron developer, then exposed to white light or treated with a bath containing a cuffing agent, and then developed with an alkaline developer containing a color developing agent.About the processing method There are no particular restrictions (not all non-processing methods are applicable, but typical examples include color development, bleach-fixing, and if necessary, washing with water,
It is possible to use a method in which stabilization treatment is performed, or a method in which bleaching and fixing are performed separately after color development, and further water washing and stabilization treatment are performed as necessary. The silver halide emulsion prepared according to the present invention can be used for black and white general use, It can be effectively applied to photosensitive materials for various uses. . (Example) Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited by these. Example 1 A solution of the five compounds shown below was prepared, and a monodisperse spherical seed emulsion was prepared as rA. -Sekiichi E, 28%77 Monia water 330
n1eF, 56% acetic acid 511 (l
At 78,540°C, solution B and solution CI were added to the stirred molten g, A1, by a double jet method. (Addition rate per minute at the start of addition: 55ml, per minute at the end of addition)
(Oml and Na 2). Furthermore, pBr was maintained at 1.1 during addition. The time required to complete the addition was Vi 33 minutes. After the addition was completed, the sample was washed with desalinated water using a conventional method. The emulsion consisted of polydisperse grains that were mostly multiply twinned. Next, maintain the temperature at 40°C and add a solution to this emulsion (■)
was added and aged for 1 minute.
-7# If 089 moles 11. The pBr value was 05. Thereafter, a solution was immediately added to neutralize the mixture, and the mixture was washed with demineralized water using rIj and a conventional method. The halogen iron particles included in this ≠7 agent have an average particle size of 0.32 μm, and
They were monodisperse spherical particles7). IiEm this emulsion
Call it -1. Next, catch 7'1. A monodisperse emulsion was prepared according to the method of the present invention using the four yuzu solutions shown below. A silver iodobromide emulsion having a silver iodide content I of 10 mol% was grown by adding molten gB, -+ and C7 to solution A2, which was kept at 40°C and stirred, by the double-jet i method. −
The addition was interrupted when the addition of No. 1 was completed. After adjusting the pBr, continue using the double jet method to prepare solution B2.
-2 and C7 were added to grow silver iodobromide with a silver iodide content of 2 mol %. The pH during addition was controlled as shown in Table 1 by adding pBr, KBr solution and acetic acid solution. The table also shows the rate of addition of Calo liquid. Table -1 1゛:-7 Box □ □□□□□□□□□ After the addition was completed, p) ( was adjusted to 600 using acetic acid and washed with desalinated water using a conventional method. At this time The resulting emulsion is called Em-2. When the silver halide grains of Em-2 were observed using an electron microscope, the average grain size was tl,
A monodisperse emulsion with a particle size distribution of 70 μm and a fluctuation coefficient of 18% and containing 86% twin grains could not be obtained. As the emulsion had a high silver iodide content and consisted mainly of twin crystals, the monodispersity of Vi could not be significantly improved. Comparative Example 1 Seed particles containing multiple twins were prepared using the following three solutions according to the method disclosed in JP-A-55-142329. C3f), 45 M AgN1)3
1', (F+ 41 cC At 40°C, add solution B3 to stirred solution A3 at 35C (7/min),
Solution C8 at 71, 65, 7 min with cooling power nL, respectively ft.
Added for 20 minutes. Desalinated water washing was carried out using the cooling method. This emulsion is called Em-:4. This emulsion contains multiply twinned grains, single-twinned grains and octahedral grains, the proportion of multiply twinned emulsions is about I%, and the average grain size is 0.5%.
27 μm, and the variation coefficient of particle size distribution was 32%. Next, a monodisperse emulsion having a silver iodide content of mol % was prepared using A4j emulsion Em-3 and the following four types of solutions. A monodispersed T and f emulsion containing 63% twin grains could not be obtained. As a result, it is found that an emulsion consisting mainly of twin crystals, which has a relatively high a iodide content and good monodispersity, cannot be obtained by the conventional method. Example 2 Emulsion samples prepared according to Example 1 (E-2, E-
4 and E-5) were divided so that the a halide content was equivalent to 0.35 mol, and each was chemically sensitized using ammonium thiocyanate, thiosulfuric acid (II) and chloroauric acid, and further Anhydro as a green-sensitive sensitizing dye5.
5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)oxacarbocyanine hydroxide; ambient-5,5'-diphenyl-9-ethyl-3,3
/-di(3-sulfopropyl)oxacarpoquanine: anhydro-9-ethyl-3,3'-di(3-sulfoprovir)-5,6,5',l'i'-dibenzoxacarbocyanine hydroxide Add 20μ of each, and then add 4-hydroxy-6-methyl=1+3.3m
, 'y-tetrazaindene and 5-phenyl-1-mercaptotetrazole were added. Next, a dispersion (M-1) having the following composition was deposited on an ecellulose triacetate-based support with 12001/12001/saponin' and 1,2-bisvinylsulfonyl-modified tannin to give a silver content of 15%.
It was coated to give a ratio of 11Q/d7n' and dried to obtain a sample with a stable coating film. Samples M1 to M3
And so. Dispersion (M-1) Halogenated 1-(2,4,61-lichlorophenyl)-5-(3-(2,4-di-tart-amylphenoxyacetamide)-benzamide)-5-pyrazolone as a magenta coupler@ Using 8 x 10 mol per mol, 2-(l-phenyl-5-tetrazolylthio)-4-octadecylsuccinimide-
The gradation was controlled using l-indanone so that the gradation was the same. This was mixed with tricresyl phosphate in an amount of 1 times the weight of the coupler as a high-boiling organic solvent, and ethyl acetate was added to the mixture and heated to 60°C to completely dissolve it. Add this liquid to 10% of Alkanol B (Algirna' ivy L. sulfonate manufactured by Dubo/Need 1).
water bath liquid 5 fl md / bifun 10 s? Horn bath Q700#+7to7111. RL Co. ) After giving a white exposure, the above-mentioned development process was carried out. [Processing step 1 (37, FloC) Processing time 1, color development; 3 minutes 15 seconds 2 # White 6
Minute seconds 3, water washing 3 minutes 15 seconds 4,
Fixing 6 minutes (9) seconds 5, washing with water
3 minutes 15 seconds 6, stabilization 1 minute addition 7 degrees drying ratio Developer composition: Bleach composition Fixer composition: [Ammonium thiosulfate +75.0. ? Table 5 shows the measurement results of the twin ratio and the fluctuation coefficient of grain size distribution in the obtained halogenated complex emulsion. Table 5 As a result, in the various tetrazaindene compounds, the effects of the present invention, i.e., iodobromide scissors with a relatively high silver iodide content, and a monodisperse emulsion with a high ratio of twins can be obtained. It has been confirmed that it is effective. Example 4 Monodisperse emulsion Em-10 was produced by the method of the present invention using the following four types of solutions. By applying the double jet method to the stirred solution A at 40 DEG C., a monodisperse agent (2) containing 93% of twinned particles could not be obtained. As is clear from these results, the present invention significantly improves the monodispersity of an emulsion in which the iodide content is mainly derived from twin crystals. (3) Effects of the Invention By the production method of the present invention, a highly dispersible iodobromide emulsion containing 4 to 40 mol% silver iodide and consisting mainly of twin grains was produced, which had previously been considered impossible. This makes it possible to provide a silver halide emulsion with high sensitivity and excellent graininess. In addition, according to the manufacturing method of the present invention, 2, which was previously impossible,
At a pBr of 0 or less, a monodisperse silver halide emulsion consisting mainly of twins with a high silver iodide content was obtained, and it became possible to increase the ratio of twins to more than 10%. (7) The production method of the present invention is particularly effective in obtaining a monodisperse silver halide emulsion having a relatively high silver iodide content and consisting mainly of twin crystals. A silver oxide emulsion is one in which the coefficient of variation, fi&, which is obtained by dividing the lapel deviation of the grain size distribution by the average grain size, is 5% or less than 4. Spherical grains obtained from multiple twins are used as seed grains. When used, it is also possible to obtain emulsions in which the coefficient of variation of the particle size distribution is less than or equal to 1%.Thus, the parogenized emulsions 1-14 to 14 obtained by the production method of the present invention As an emulsion containing 5 mol% silver iodide and consisting mainly of twin crystals, it has excellent monodispersity.Here, the average grain size refers to the diameter of spherical silver halide grains, and also the diameter of spherical silver halide grains. In the case of particles of other shapes, the average value of the diameter when the projected image is converted into a circular image of the same area, the individual particle size is rl, and the number is 01
When , the average particle size F is defined by the following 2. In addition, the above particle diameter can be measured according to the method pc commonly used in the technical field for the above purpose.1, as a typical method,
1 grain of 7 plants - f Xiang () and i method A, S. T, M, Numbosytum on Light Microscopy, l! 155, 94-122 It 1 Theory of Photographic Process 1 Co-authored by Mies and James, 3rd edition, published by Macmillan (19 Fifi), Chapter 2. Stiffness can be measured using the particle diameter or the approximate diameter of the particle. Agent Patent Attorney No 1) Parent-in-law/Procedural Amendment 1it Illwa6()I'1+1261+ Commissioner of the Patent Office Michibu Uga 1 Display of the case
No. 1:9 1981 Patent Application No. 1358) tl
1. Name of the invention Manufacture of silver halide feather agent Kli, b /), 3. Relationship with the 41 amendments Patent applicant address 26-2, 17'll Nishi-Shinjuku, Shinjuku-ku, Tokyo Sakura, Hino-shi, Tokyo Town 1 Konishiroku Photo Industry Co., Ltd. (Tel: 0425-83-152
1) Patent Department) 5. Column 6 of "Detailed Description of the Invention" of the Specification Subject to Amendment 6 Contents of the Amendment The column of "Detailed Description of the Invention" will be corrected as follows.

Claims (6)

[Claims] (1) A method for producing a silver halide emulsion, which comprises the step of growing multiple twin grains and/or spherical grains obtained from multiple twins as seed grains in the presence of a tetrazaindene compound. (2) The method for producing a silver halide emulsion according to claim 1, wherein the silver halide formed in the growing step has a high silver iodide content. (3) The method for producing a silver halide emulsion according to claim 1 or 2, wherein the silver halide composition of the silver halide emulsion consists essentially of silver iodobromide. (4) pBr in the above growth step is −0.8 to
Claim 1, characterized in that: 4.0;
A method for producing a silver halide emulsion according to item 2 or 3. (5) pBr in the step of forming the above-mentioned multiple twin grains and/or spherical particles obtained from multiple twins is -0.7 to 2
．． 0. A method for producing a silver halide emulsion according to claim 1, 2, 3, or 4, wherein the silver halide emulsion is 0. (6) pH in the above growing step is 2.0 to 13
．． 0. A method for producing a silver halide emulsion according to claim 1, 2, 3, 4 or 5, wherein the silver halide emulsion is 0.