WO1983002174A1

WO1983002174A1 - Process for preparing silver halide emulsion

Info

Publication number: WO1983002174A1
Application number: PCT/JP1982/000471
Authority: WO
Inventors: Ltd. Konishiroku Photo Industry Co.
Original assignee: Takiguchi, Hideki; Iijima, Toshifumi
Priority date: 1981-12-19
Filing date: 1982-12-20
Publication date: 1983-06-23
Also published as: GB8322389D0; EP0097720A1; EP0097720B1; DE3274500D1; GB2125981B; GB2125981A; JPH0353619B2; JPS58126526A; EP0097720A4

Abstract

A process for preparing a silver halide emulsion containing core/shell type silver halide grains, which comprises using silver halide grains of octahedral or tetradecahedral crystals having a (1 1 1) face substantially comprising silver bromoiodide and having a variation coefficient of particle size distribution of 0.18 or less, and subjecting them to gold-sulfur sensitization or gold-selenium sensitization in the presence of a nitrogen-containing heterocyclic compound capable of forming a complex with silver or its ion. This emulsion shows a remarkably high photographic sensitivity and less reciprocity law failure in high illuminance region, and undergoes less fogging, thus being suitable as a silver halide photographic light-sensitive material.

Description

Details

Method for producing silver halide emulsion

〔 Technical field 〕

The present invention relates to a photosensitive silver halide photographic emulsion, and more particularly to a silver halide emulsion containing silver halide grains mainly or silver iodobromide. The present invention relates to a sensitizing method and a silver halide photographic emulsion sensed by the method.

[Background technology]

Conventionally, silver halides such as silver chloride, silver bromide, silver chlorobromide, silver bromoiodide, and silver chloroiodobromide have been used as photographic silver halides.

However, silver iodobromide has been used as a high-sensitivity photographic silver halide for obtaining high-sensitivity emulsions.

In recent years, the demand for high-sensitivity photographic silver halide emulsions has been increasing.

15 There is an ever-higher demand for photographic performance, such as more stringent, high sensitivity, excellent graininess, high sharpness, low fog, and sufficiently high optical power. .

At the same time, the depletion of silver resources is being sought, and there is a strong demand for the development of low silver content photosensitive materials. I think these seemingly different

20 The demands also depend on the technology for producing silver halide emulsions with low sensitivity and high sensitivity.]? ? It is an exaggeration to say that the development of a low-capacity, high-sensitivity silver iodide silver halide emulsion is the greatest challenge in the industry.

High sensitivity, low fog as described above]?

25 Most Proper Guns to Achieve True Performance は Silver Halide

O PI IPO Is to improve the quantum efficiency. For this purpose, knowledge of solid state physics has been actively adopted. This quantum劾率theoretically calculated, study discussed the Kagekyo of particle size distribution, for example, 1980 on the progress of photos Tokyo Thin port Jiyu over-time of the ^proceedings, Lee te over La click Shea Yo lens * BIT WIN * LIGHT AND ♦ MATERIALS FOR FOOTGRAPHICS, ABRICTIONS * (Interactions

Be -ween Light and Materials for Photographic

Applications) on page 91. According to this study, it is predicted that narrowing the particle size distribution and making a monodisperse emulsion will be effective in improving the quantity efficiency. In addition, silver halide emulsions Monodispersed emulsions would be advantageous in order to achieve high sensitivity efficiently while maintaining low fog in a process called chemical perception to alter the sensitization of the emulsion. The theory is considered reasonable O

However, in actual emulsion systems, only a single or mixed monodisperse emulsion is used, and there is no negative high-sensitivity emulsion. The reason for this is that, even if a monodisperse emulsion is prepared by a commonly known method and subjected to a regular chemical sensitization, the sensation can be achieved. Emulsions] 5 are also widely known in the art to have inferior results.

In order to industrially produce a monodisperse emulsion, as described in JP-A-54-48521, strict pAg and

, OMFI bets the control of pH is also controlled and sufficient撩拌conditions feed rate to the reaction system of Gin'i on determined theoretically and C ⁵³ gain down I on-are required. The silver halide emulsions produced under these conditions are cubic, octahedral and decahedral composed of so-called normal crystal grains having various proportions of (100) and (111) faces. It has a tetrahedral shape.

On the other hand, in the field of emulsion grain production technology, octahedral, tetradecahedral or 棱 -shaped crystal grains having a (111) plane are usually produced under conditions of low silver density, and thus latent images are usually produced. It is known that silver nuclei, which are known as nuclei or helmets, have the advantage of being small.

However, in the field of chemical sensitization technology, the chemical sensitization reaction has a large crystal dependence, and for example, in a normal method,

Since the sulfur sensitization nuclei are more numerous on the (111) plane than on the (100) plane, the latent image formation is dispersive.] 3 It is known that the efficiency is low, and hence the sensitization efficiency is low. Therefore, it has been considered disadvantageous or difficult to put silver halide particles having the (111) plane into practical use as described above.

For such features of octahedral particles, see Journal of Photographic Science, Vol. 14, P * 181-184 (1966). ), Vol. 16: B 102-113 (1968), Photo ograpM che Korr e spondena j Vol. 106, P. 149-160 1970) and the journal of the Photographic Society of Japan, Vol. 42, p. 112-: 121 (1979). it can. From the above report, it is expected that the progress of the chemical texture of the tetradecahedral particles will be dominated by the (111) plane, and the tetradecahedron has the same characteristics as the octahedron. However, in fact, our research shows that it has octahedral similarity ft.

On the other hand, hydroxyazaindene compounds have been conventionally used as stabilizers for photographic emulsions in the industry because they have the property of inhibiting chemical ripening due to sulfur-containing yellowing. It is well known 1), it is added for the purpose of terminating the sulfur sensation reaction and for preventing the generation of fog or during the manufacturing process, during storage, or during development. This compound is also known to have the effect of increasing photographic sensitivity. For example, in British Patent 1,315,755, a silver halide emulsion is prepared by adding azaindene prior to sulfur sensation and simultaneously or simultaneously. It is stated that the addition of a monovalent gold complex chloride containing sulfur followed by ripening increases the intrinsic sensitivity of silver halide as compared to the conventional method. However, it is not possible to obtain a sufficient effect simply by applying this sensitivity method to a silver halide emulsion.

In addition, Japanese Patent Application Laid-Open No. 50-63914 and German Patent Application (OLS) 2, 419, 798 disclose the monodisperse pores of cubic particles having a silver bromide-containing mole ratio of 80 or more. It is described that the sensitivity is increased by adding a hydroquinone tetrazindene compound after sulfur sensitization of a silver genide grain emulsion. However, this publication discloses crystal forms outside the cube, for example,

_O PI _ It is also noted that the sensitivity of octahedral particles and plate-like particles in the form of particles surrounded by (1 1 1) planes is rather small even if the sensitivity is rather small or increased.

JP-A-51-77223 and U.S. Pat. No. 4,078,937 disclose a sulfur-sensitized silver halide photographic emulsion containing silver halide grains having an average grain size of silver halide grains. It has been described that when the size exceeds 0.5 m, the sensitivity is increased when a certain type of hydroxytetrazindene compound is contained.

Certainly, as shown in the examples of this publication, after the sulfur sensitization was performed, the compound was coated with the hydroxycitrazinedene compound, and the coating was not added at all. In some cases, the I & A may have slightly higher sensitivity than the case of applying to the skin. However, the industry has traditionally added hydroxyzite lazanden compounds as stabilizers after chemical ripening, with or without impeachment. The method described in Japanese Patent Application Laid-Open No. 51-77223 and U.S. Pat. No. 4,073,937 is higher than the conventional method. It has not provided a new sensitization method for realizing high-sensitivity emulsions.

[Disclosure of the Invention]

First, the object of the present invention is to produce almost a monodisperse emulsion containing silver halide grains of octahedral or tetradecahedral crystal having (11 1) plane]}. To provide a method of significantly sensitizing] 9, and secondly, a high-sensitivity silver halide photographic emulsion obtained by such a chemical sensitization method. Offer

OMPI WIPO— To provide.

The other objects and features of the present invention can be understood from the following description.

An object of the present invention is to provide a silver-halogenated emulsion containing core z-shell silver halide grains with a gold sensitizer and a sulfur sensitizer or a selenium sensitizer. In the method for producing a silver halide emulsion in which the silver halide grains are sensitive to gold or selenium, the silver halide grains are octahedral crystals or dodecahedral crystals having a (111) plane. The silver halide constituting the grains is substantially different from silver iodide! ), The halogenation (the number of fluctuations in the particle size distribution of the particles is 0.18 or less)), and gold-sulfur in the presence of a nitrogen-containing complex compound that forms a complex with silver or silver ion. It is altered by the method of manufacturing silver halide emulsions, which are characterized by the sensation or sensitization of gold-selenium.

According to the present invention, the halogenated ^ grains contained in the silver halide emulsion are converted from an octahedral or tetradecahedral crystal having a (111) face.

Monodisperse core-shell silver iodobromide particles, and a selenium sensitizer and gold are added in the presence of a nitrogen-containing heterocyclic compound which forms a complex with silver in an amount sufficient to cover the particles. It is based on the discovery that if the ratio between the sensitizer and the ratio between the sulfur sensitizer and the gold sensitizer j is controlled within a certain range, markedly higher sensitivity can be achieved. The effect of the present invention is that when a known gold-sulfur sensitization method or gold-selenium sensitization method is applied to octahedral or tetradecahedral silver iodide grains, the (111) face is sulfided. (4) A large number of photosensitive nuclei are formed on a single silver iodobromide grain because the nuclei are easily formed, and the quantum efficiency does not increase.

O PI _ V, ' ^iFO Therefore, the effect of the present invention is that the silver iodobromide grains are converted to a coanoshell type in a monodisperse emulsion, and a complex is formed with silver or silver ion. This was obtained by intentionally controlling the photonucleation reaction on the (111) plane in the presence of a nitrogen-containing heterocyclic compound. However, when the cubic crystal is used instead of the octahedral crystal or the tetradecahedral crystal in the present invention, the effect of the present invention cannot be obtained. Cubic silver halide grains have each vertex of the cube at each (100) plane.] 3 Photosensitive nuclei are easily generated, and the photosensitive nuclei are selectively apexed without special attention. Because it is generated.

Even when the method of the present invention is applied to a monodispersed octahedral or 14-sided silver iodobromide emulsion having a core / shell structure, the sensitizing effect is large, and The mono-dispersed octahedral or tetradecahedral silver iodobromide emulsion of the anochel type may be subjected to gold-sulfur sensitization or gold-selenium sensitization in the absence of a nitrogen-containing heterocyclic compound. The fruit is small.

Inclusion of iodine in silver bromide grains increases quantum efficiency and increases gold-sulfur sensitization or gold-selenium sensitization sensitivity, but contains iodine.] 3 lattice defect And the interstitial silver ion increases accordingly. In addition, iodine atoms present on the crystal surface suppress gold-sulfur sensitization or gold-selenium sensitization reaction.

Known monodisperse octahedral or tetradecahedral silver iodobromide emulsions have a gold-sulfur or gold-selenium sensation.

_ OMFI Because of these effects and the crystal habit dependence of the chemical sensitization reaction described above, many photosensitive nuclei are present on the (111) plane in octahedral and tetradecahedral silver halide particles. The inventors and others have determined that it has been formed. The effect of iodine atoms on the surface in the presence of nitrogen-containing extrinsic ring compounds on chemical sensitization can be reduced by co-shelling to reduce the surface silver iodide content. However, an effect can be expected on an increase in lattice defects and an increase in interstitial silver ions, and the dependence of the chemical sensitization reaction on the crystal habit can be controlled. The nitrogen-containing heterocyclic compound forms a complex with silver ion on the surface to reduce the amount of interstitial silver ion to the amount required for the chemical sensitization reaction and to enhance the chemical sensitivity reaction. It seems that this contributes to the generation of a small number of effective photosensitive nuclei, but does not prevent the iodine atom on the surface from suppressing the chemical sensitization reaction. From these facts, good results can be obtained by sensitizing a core-shell octahedral or tetradecahedral silver iodobromide emulsion to gold-sulfur or gold-selenium sensitization in the presence of a nitrogen-containing heterocyclic compound. However, the degree of sensitization obtained was more remarkable than expected.] 3, it seems that a synergistic effect other than that predicted by the inventors was obtained.

The present invention controls the reaction of forming a chemically sensitized nucleus by adopting the above-mentioned technical constitution, and uses a combination of gold-sulfur or gold-selenium sensitization. Conventionally, the effect is markedly manifested.] On the other hand, it is described in Japanese Patent Application Laid-Open No. 50-S3914 and West German Patent Application (OLS) 2, 419, 798. The sensitization method used is that at the end of yellow sensitization, the nitrogen-containing heterocyclic compound OMH, ΛΥΠ'Ο From this fact, the improvement of the latent image formation efficiency by controlling the silver ion and the like in the vicinity of the silver iodide grain surface and in the vicinity thereof. It is presumed that the invention was aimed at, and both are different skill bites.

In addition, Makikai No. 51-77223 and U.S. Pat. No. 4,078,937 disclose that a silver halide emulsion having an average grain size of more than 0.5 m is sensitive to sulfur. There is disclosed a method for increasing the sensitivity of a silver halide emulsion containing a loxacitrazinden compound. However, the publication does not completely disclose the constitution and effect of the present invention, and in particular, all of the examples are prepared by adding hydroxycitrazaindene compound after completion of chemical ripening. For that reason, the sensitizing effect of the method depends on the average grain size, and the crystal habit of the silver halide grains is a technique different from the present invention, such as selection.

In addition, British Patent No. 1,315,755 discloses a method of adding gold-sulfur by adding an azaindene compound and then adding a sulfur-containing monovalent gold complex chloride as described above. However, the crystal habit, core / shell structure, and the like of the silver halide grains are not mentioned, and the present invention cannot be predicted from the literature.

Hereinafter, the present invention will be specifically described.

Halogenated octahedral or tetradecahedral crystals of the present invention have a halogenated composition of 0.5 to 15 mol silver iodide. It is preferable that the substance substantially consists of silver chloride, but even if silver chloride is contained within a range that does not impair the effect of the present invention, it is possible to obtain the same effect.

Ο ΡΙ

Α an eh ^.

The form of the silver halide grains is substantially an octahedron formed by the (111) plane, or a tetrahedron formed by the (111 :) plane and the (100 :) plane. . Their particle size is determined.

Although the ratio of the (111) plane to the (100) plane of the surface of the tetradecahedral silver halide grains used in the present invention is not limited to a specific one, at least the total of the grains is not limited. 5 of surface area

^ The upper part has the (111) plane], and the larger the ratio of the (111) plane, the greater the sensitizing effect of the method of the present invention.] Preferably, the (111 :) plane Is 40 or more.

Further, in the emulsion of the present invention, the effect of the present invention increases as the percentage of the silver halide particles of the present invention out of the silver halide particles contained in the emulsion increases. The ratio is 50

^ The top is preferred, and the 70 is more preferred, and the emulsion in which silver halide grains are substantially composed of the haguchi genated 钹 grains of the present invention is most preferred.

In the present invention, a so-called monodispersed emulsion in which the variation coefficient of the particle size distribution of silver halide particles contained in the silver halide emulsion is 0.18 ° or less is used.

According to the method of the present invention, the halogenated surface is treated with a nitrogen-containing heterocyclic compound capable of forming a complex with silver or silver ion to form a gold-selenium sensitization reaction or gold. -Controls the sensitization reaction, but polydisperse emulsions have more variation in surface area between grains! ? Efficient application of particle surface

OMFI · It seems that ΐ becomes difficult.

The average particle size of the halo-danned particles contained in the silver halide emulsion is calculated by dividing the standard difference S of the particle size distribution represented by the following formula (1) by the average particle size 7. Value, the coefficient of variation of the particle size distribution

(Hereinafter referred to as the degree of dispersion). (1) τ ~ τι j ni

S (2) The average particle size referred to here is the average value of the diameter when a projected image of a silver halide particle is a circular image of the same area ^ 渙渙. When the diameter is ri]? And its number is ni, by the following formula? Is defined.

Σηϊ ri

(3) The particle size of the above IS can be measured by various methods used for killing in the technical field for the above purpose. A typical method is the Lapland's “Particle Size Analysis Method”, ST-1 Symposium, On • Light Microscoby, 1955, pp. 94-122. It is also described in Chapter 2 of The Photographic Process Theory, co-authored by Mice and James, Third Edition, published by McMillan (1966).

^ In the description below, an emulsion having a dispersity of 0.18 or less is called a monodispersed emulsion.

― O PI ' (10) The silver halide emulsion of the present invention is

(P. Glafkides), Chimie et Phyeique Photograph i que

(Paul Monte 1 published 1967); Photographic Emulsion Chemistry, Photographic Emulsion Chemistry, written by GF Duiiin ) (e Focal Press ϊΡΙ 1966); co-authored by Buoy 'El Zelikman (VL Ze 1 ikman), etc., MAKING AND * COTING, PHOTOGRAPH Firta, Emarjion

(Making and Coating Photograph ic Emulsion (The Focal Press, 1964)), such as the neutral method, the neutral method, and the ammonia method. The method of reacting the soluble ^ salt with the soluble halogen salt may be any of the injection mixing method, the simultaneous mixing method, and any combination thereof. o

One method of the double jet method is to use a method in which the pAg in the liquid phase in which silver halide is formed is kept constant, i.e., the so-called control * double jet method. The core Z-shell type halogenated silver halide grains according to the present invention can be composed of two layers having different silver iodide contents and a layered structure composed of two layers. ]), And the iodide content in the vicinity of the surface of the two or more layers is preferably lower. Here, the vicinity of the surface refers to a portion having a thickness of 0.001 to 0.1 from the surface. Near the surface and it

O PI W ^LPO D It is preferable that the difference in the silver iodide content contained in the inside be 5 m or more.

In the present invention, the lower the silver iodide content in the vicinity of the surface, the more desirable, and it is preferable that the silver iodide is substantially composed of silver bromide. Emulsions containing such silver halide grains have high sensitizing efficiency and are particularly suitable for obtaining surface latent image type emulsions.

In the core Z-shell type c-pi-danide grains of the present invention, the inclination caused by the difference in the silver iodide content from the higher layer to the lower layer is low. It may have a sharp border, or it may be a clear and continuous change.

The distribution state of silver iodide in the silver halide grains described above can be detected by the physical measurement method of each S. For example, the Photographic Society of Japan, Annual Meeting of 1982 As described in the abstract. ¾ Luminescence at low temperatures can also be checked.

In a preferred embodiment of the silver halide grains of the present invention, silver iodide is contained in the vicinity of the surface of the grains in an amount of 0 to 4 mol ^, and iodide is contained inside. It is silver halide containing 2 to 15 moles of silver. In the present invention, the silver halide composition other than the above-mentioned iodide is mainly silver bromide, but the silver halide may be included in D as long as the effect of the present invention is not impaired. In fact, the limit is about less than one mole.

The silver halide emulsion according to the present invention may be a mixture of octahedral and tetradecahedral grains.

O PI

Non

ί ^ΡΟ , The silver halide emulsion having the coz shell type silver halide silver halide emulsion of the present invention comprises monodisperse silver halide particles as cores, which are coated with shells. By doing so, it can be manufactured.

In order to produce monodisperse silver halide particles of the above-mentioned core, it is possible to obtain particles of a desired size by a double jet method while keeping pAg constant. For example, for a monodisperse silver halide emulsion, the method described in JP-A-54-48521 can be applied. For example, an iodine-imaging reammable gelatin solution and an ammonium silver nitrate aqueous solution are added to a gelatin solution containing silver halide iodide particles, and the acceleration is a function of time. It is manufactured by a method in which the amount is changed and added. By appropriately changing the time function of the addition rate, pH, pAg, temperature, etc.] 3, highly monodisperse halogenated particles can be obtained.

Regarding the method for producing the core-shell silver halide grains described above, for example, Japanese Patent No. 1,169,290, British Patent No. 1,027,146, and Japanese Patent Publication No. References can be made to the descriptions in JP-B-57-154232 and JP-B-51-1417.

In the present invention, in the production process of the halogenated particles according to the present invention, for example, a potassium salt, a zinc salt, a calcium salt, a thallium salt, an iridium salt or These complex salts, rhodium salts or their salts may coexist.

In the nitrogen-containing S ring compound used in the present invention, examples of the nitrogen-containing heterocycle include a virazole ring and a bilimidine. Ring, 1,2,4—triazole ring, 1,2,3-triazole ring, 1,3,4—thiadiazol ring, 1,2,3—thiadiazol ring, 1,2,4-thiadiazole ring, 1,2,5-thiadiazole ring, 1, 2, 3, 4 — tetrazole ring, pyridazine ring, 1,2, 3 — Triazine ring, 1, 2, 4 — Triazine ring, 1,3,5 — Triazine ring, benzotriazole ring, benzoimidazo Ring, benzothiazole ring, quinoline ring, benzoxazole ring, benzoselenazole ring, naphthothiazol ring, naphthol Imidazole ring, loadan ring, thiocyanine ring, thiazole ring, thiazole ring, thiazazole ring, serene ring Azole ring, naphthoxazole ring, oxazoline ring Riazotriazole ring, azaindene ring (for example, diazaindene ring, triazaindene ring, tetrazindene ring, Ring, phthalazine ring, and indazole ring.

Preferred among these are compounds having an azazine den ring.] ?, and azazine den compounds having a hydroxy group as a substituent, for example, hydroxyzide More preferred are rearazine den, tetrahydroxyazadinden, and hydroxypentazanedenide compounds.

The heterocyclic ring may have a substituent other than the π-pixy group. Examples of the substituent include an alkyl group, an alkylthio group, an amino group, a hydroxyamino group, an alkylamino group, a dialkylamino group, Arylamino group, calpoxy group, alkoxycarbonyl group, halogen atom, acylamino Group, cyano group, and mercapto group.

Ν

The following is a list of specific examples of the nitrogen-containing heterocyclic compound of the present invention ⁵ , which is not limited thereto.

Ν-1 2,4 — Dihydroxy 6 — Methyl — 1,3a, 7 Triazine

Ν-2 2,5 -Dimethyl — 7 — Hydroxy 1,4,7a

Ν-3 5 — Amino 7 — Hydroxy 2 — Methyl — 1,4,7a — Triazan den

Ν-4 4 — Hydroxy 1 6 — methyl 1,3,3a, 7-tetrazide den

Ν-5 4 — Hydroxy l, 3, 3a, 7 — TetraZine

Den

Ν-6 4 ー Hydroxy 6 — Ferrule 1,3,3a, 7

ー Tetra Zain Den

Ν 7 4-Methyl-6 — Hydroxy — 1,3, 3a, 7-tetrazide den

Ν 8 2,6 — Dimethyl 4-Hydroxy l, 3,3a, 7 — Tetrazaindene

9 4-Hydroxy 5-methyl 1 6-methyl 1

1,3,3a, 7 ー Tetra the den

Ν-0 2,6 — Dimethylino 4 —Hydroxy 5 —

Rules _{3 3} 3a 3 7 Tetra the den

Ν 1 — Hydroxy 1 5, 6 — Dimethyl-1,3, 3a, 7 — Tetrazaindene

O? I

, "", 7)

N-2 2,5,6-Trimethyl -41 Hydroxy-1,3,3a, 7-Tetrazaindene

N-11 3 2 — Methyl 4 — Hydroxy 6 — Phenyl

Five

One 1,3,3a, 7 — Tetra the den

N 4 4 1 Hydroxy 6 — Methyl 1,2,3a, 7 1

Tetra The Inden

N 4-Hydroxy 1-6-ethyl-1,2,3a, 7-tetrazindene

N-6 4-Hydroxy 1-6-Feel-1,2,3a, 7-Tetrazandende

N 1 7 4 1 Hydroxy 1, 2, 3a, 7 ーラ

7 "N

N 1 8 4 ― Methyl 1 6 ― Hydroxy l, 2, 3a, 7 1

Tetra The Inden

N-1 9 7 — Hydroxy 1 5 — Methyl 1,2,3,4,6 —Pentazin den

N 2 0 5 One Hydroxy — 7 — Methyl 1,2,3,4,6 — Ventazaden

N-25, 7 1 Hydroxy 1,2,3,4,6 — Pentazaindene

N-2 2 7 —Hydroxy 5 —Methyl 1 2 —Fer — 1,2,3,4,6 — Pentazandene

-2 3 5 — Dimethyl amino 7 — Hydroxy — 2 — Ferrules 1, 2 j 3, 4, 6 — Pentazin den

N-2 4 1 — Fuel 1 5 — Melt 1 1,2,3,4 — Tetrasol

N 2 5 6 — Amino Brine N 2 6 benzotriazole

N 2 7 6 —-Benzimidazole N 2 8 3 — Methyl — 2 — Methyl Penzozia Zolium p-Trudinsurone

N 291 N-methyl quinoline N 30 Benzothiazole

N 3 1

N 3 2 Penzo-selener N 3 3 Benzimiter, N 3 4 Naphthochiazole

N 3 δ Naphtho serena Zole

N 3 6 Naft imidazol

N 3 7 o 1 Danin N 3 8 2 1 year old Hydantoin N 3 92 2 1 year old 2,4 — Oxazolidinedion

N 4 0 3 1 Benzine 1 — Melkabutopenzinzimidazole

N-4 2 One-melt helmet — 1 — Metilben Zochiazole

N 4 2 5 1 ( _m- tu π-phenyl) Tetrasol N 4 3 2 ₅ 4 1

N 4 4 Methyl-5------------------------------------------------?

, One OM? I

IPO 1

N-4 6 1 1 ethyl — 5 — Melcaptotetrasol

N-4 7 5 1 Methylbenzotriazole

N-4 8 5 — Fertetrasol

N-4 9 1-Methyl-2-Melkabute 1-Benzolamino 1,3,5-Triasol

N-501 1 Benzyl 1 21 Melt 1 5 — acetylamino-1,3,5 -triazole

N-5 1 2 — Melkabuter 1 – 3 Real 1 – 4 — Methyl

— 6 — Hydroxypyridine

-5 2 2, 1 dimethyl; ^

N-5 3 1-Methyl-5-phenol

N-5 4 2 — Ethyl — ^ — Naphtho

N-5 5 2 — Melkabute — 5-1 Aminosia diazole

N-5 6 2 — Melkabutone 51 Aminoxaziazol

N-57 2 — Melkabuterone 5 — Aminoserenadiazole — The amount of nitrogen-containing complex compound added depends on the size, composition and ripening conditions of the silver halide grains. Varies over a wide range depending on the temperature, but from the monomolecular layer on the surface of the silver halide grains.

It is necessary to add an amount capable of forming 10 molecular layers. This addition amount can be added by a control in an adsorption equilibrium state due to a change in pH and temperature during maturation or temperature change.

OMPI

, V / JFO '' m The nitrogen-containing heterocyclic compound can be used in combination with a sensitizing dye for the gold-sulfur or gold-selenium sensitization of the present invention. In this case, the total amount of the nitrogen-containing purifying ring compound and the dye-sensitive dye added is such that a total of 10 molecular layers is formed from a monomolecular layer on the surface of the silver halide particles. Preferably, the sensitizing dye is added in an amount exceeding 70, which is an amount capable of forming a single molecular layer on the surface of the silver halide grains.

The amount of addition required to form a monolayer can be determined by creating an adsorption isotherm. For example, the grain surface of a silver iodobromide emulsion consisting of 0.6 octahedral grains can be determined to be 41-hydrogen. When coating with xixi-methyl-1,3,3a, 7-tetrazandene, the required addition amount is about 210 ^ / A mol] 9, therefore , occupied area that by this compound ^ is one molecule those 3 to about 3 0 1 ^2. As a guide, particles having different particle diameters may be added in proportion to the area based on the above example.

The nitrogen-containing heterocyclic compound of the present invention is preferably a colorless compound. -The method of adding the nitrogen-containing heterocyclic compound of the present invention to an emulsion is carried out by dissolving in a suitable solvent (for example, a permanent or alkaline solution) which does not adversely affect the photoemulsion to form a solution. Can be added with The compound may be present at the time of gold-sulfur sensitization or gold-selenium sensitization, but it may be added when a sulfur sensitizer or a selenium sensitizer is added to the emulsion. Or Sir is preferred. The gold sensitizer may be added during or at the end of the ripening for sensitization of Ryuhyo or Selenium.

O. PI 4 ' ^{ν ΐΓ0} ~ In the present invention, the term “complex” means a bond of two or more compounds or ions.

In the present invention, known sulfur sensitizers can be used. For example, sulphate sulphate, sulphate sulphate, sulphate sulphate, sulphate sulphate, sulphate sulphate , Loadan, and the like. In addition, U.S. Pat.

2,410,689, 2,278,947, 2,728,668, 3,501,313, 3,656,955, German Patent 1,422,869, Japanese Patent No. 56-24937, Japanese Patent

Sulfur sensitizers described in, for example, JP-A-55-45016 can also be used. The addition amount of the sulfur sensitizer may be an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions, such as the amount of the nitrogen-containing nitrogen-containing compound added, pH, temperature, and the size of the silver halide grains. Is 14 halogen silver halide equivalent]?

¹⁰ "τ molar to about 10 ¹ mode about Le is Shi preferred.

In the present invention, a selenium sensitizer can be used in place of the sulfur sensitizer, but the selenium sensitizer is aryluso celenosinate. Aliphatic isoselenocynates, selenoureas, selenoketones, selenoamides, selenocarbons and esters Serenides such as tellurium, serenophosphites, getylserenide, and getyldiselenide can be used. Examples of U.S. Pat.Nos. 1,574,944, 1,602,592, and 1,623,499

ΟΜΡΙ

VvIPO ' It is recorded in the details.

Addition amount Suruga vary over a wide range like the sulfur增感agent, is a guideline, c b gate Nkagin 1 molar equivalent]) about 10 · ^tau mole or al 10- ¹ model about Le is preferred And

In the present invention, as the gold sensitizer, gold compounds having an oxidation number of +1 or +3 and various kinds of gold compounds may be used. Typical examples are gold chloride, potassium black mouth oleate, smart trick chloride, and potassium molybdenum. , California oleate, tetrasino liquefied acid, ummo-momo thiosipate, pyridyl tri cros And so on.

The addition amount of the gold增惑agent Shi preferred range of in is but by D Ru different in a variety of conditions as a guide Ha Russia gain Nkagin 1 molar equivalent]? About 10 moles or, et al. ΚΓ ¹ molar or .

When gold sensitization is used in combination with sulfur sensitization or selenium sensitization, gold nuclei and silver sulfide gold nuclei or silver selenide gold nuclei are formed as photosensitive nuclei. The composition of silver sulfide nuclei or silver selenide gold nuclei has a significant effect on electron trapping or imageability. The ratio of the gold sensitizer to the sulfur sensitizer or selenium sensitizer greatly affects the sensitizing effect. Therefore, in order to effectively increase the sensitivity of the emulsion depending on the ripening conditions, it is necessary to use sulfur. The addition ratio of the sensitizer or selenium sensitizer and gold sensitizer depends on the number of sulfur atoms that form silver sulfide with silver ion among the sulfur atoms contained in the sulfur sensitizer Or selenium atoms contained in the selenium sensitizer

OMPI The number of gold atoms must be in the range of 12 to 1Z200 for the number of selenium atoms that produce silver selenide.

For example, when sodium thiosulfate is used as the sulfur sensitizer and sodium chloroaurate is used as the gold sensitizer, the latter is reduced by about 1 / Add in the range of 200.

The pAg of the emulsion to be subjected to the gold-cyan yellow sensitization or the gold selenium sensitization in the present invention is preferably in the range of 7.5 to 10.0, and the pH is preferably in the range of 5.0 to 9.0.

The sensitization method of the present invention can be used in combination with a sensitization method using another noble metal, for example, a noble metal such as platinum, palladium, iridium, or rhodium or a salt thereof. .

In the present invention, a reduction sensation can be further used in combination. The reducing agent is not particularly limited, and examples thereof include known stannous chloride, thiourea dioxide, hydrazine derivatives, and silane compounds.

It is preferable to carry out the reduction sensation during the growth of the silver halide grains or after the end of the sulfur sensation and the gold sensation.

As described above, the sensitizing method of the present invention is a remarkable spectral sensitizing method in which a sensitizing dye is used in combination with the gold-sulfur sensitization or the gold-selenium sensitization of the present invention. ] 3 Here, the "sensitizing dye" means a dye that extends the photosensitive region of silver halide to the electromagnetic wave outside the intrinsic photosensitive wavelength range. Specifically, the sensitizing dyes useful in the present invention include sianin-based, melocyanin-based, hemocyanin-based quinolone-based, and hemidine-based sensitizing dyes. Sonor And complex melocyan-based dyes, such as those described by F. Ham · Hamer in 'The' Fan '* Din' And '' Related Cont ' By The Cyan i ηβ Dye and Related Compaunds and CT James, 'The Celli-Ob' The * Photographic Process, Forth Ed. Jon '(The Theory of the Photographic Process Four h Edition), pages 194 to 234, etc.3.

Among these, particularly preferred dyes used in the present invention are represented by the following general formula [I]. [I]

,,.,

ゝ,

One fe-N- R,

In the formula, and represent an alkyl group (eg, a methyl group, an ethyl group, a propyl group, a pentyl group, a chloroethyl group, a hydroxyethyl group, a methoxyethyl group, Ethoxy, carboxymethyl, carboxyethyl, ethoxycarbyl, sulfoethyl, sulphobrovir, sulhoptyl, ^ (1) Hydroxy r-Sulfobrovir group, sulfate bromo group, aryl group, benzyl group, phenyl group, etc.), aryl group ( For example, represents a group selected from a phenyl group, a carboxyl phenyl group, a sulfophenyl group, etc .; Li, and: each represent a methine group (eg, One CH = group, one C (C¾) = group, -C

O PI (C, ¾) - group, one C (C¾COOH) = group, -C (C¾ ~ ^>) - group, one C (C _e ¾) - group, -C (C _e ¾COOH) - group or the like) represents : And ¾ represent a 5- or 6-membered heterocyclic nucleus, for example, a thiazoline nucleus (for example, thiazoline, 4-methylthiazole, 41-fluorothiazole). Zozolin), oxazoline nucleus (eg, oxazoline, 4-methylisoxazoline, etc.), serenazolin nucleus (serenazolin, 4-methylselenazo) Phosphorus), thiazole nuclei (for example, thiazol, 4-methylthiazole, 41-fu) = ruthiazole, 5 — methylthiazole,

4.5—Dimethyl thiazole, 4,5—Difluorothiazole, etc., Serenazole nucleus (for example, Serenazol, 41 methyl selenazole, etc.), Oxazol nucleus ( For example, 4-year-old oxazole, 4-methyl-year-old oxazole, 5,5-dimethyl-year-old oxazole, 5-ethyl-year-old oxazole, 5—four-year-old oxazole, penzothia, etc. Zole nucleus (eg, Penzothiazole, 41-mole Penzothiazole, 5—Methylpenzothiazole, 6—Methoxybenzothiazole,

5.6 — dimethoxyxenzothiazole, 5 — hydroxyzinzothiazole, 5 — carboxy shechilbenzoziazol, 6-sulhopenzothiazol, etc.), penzoxazole Nuclei (eg, benzoxazole, benzoxazole, 5-black benzoxazole, 6-methyl benzoxazole, 5-hydroxyxenzoxazole, 4,5-dimethyl Chil-Penzo-Senazol, etc.), Benzo-Senenazol-Zone nucleus (eg, Penzose-Lenazol, 5—Cross-open Penzose-Lenazol, 5

O PI 2-METOSIPEN ZOSELLENAZOLE, 5-HYDROXYSPEN ZOSELLENAZOLE, TETRAHYDROVENZOSENAZOLE, etc.), PENTZIMI Dazol nuclei (for example, Benzimidazole, 31-ethylbenzimidazole, 11-Fe-zul 5,6—Dichloropentzimidazol, etc. ), Indrain nucleus (eg, 3,3—dimethylindrain, 3,3—ethylindrain, 3,3,7—trimethylinline) ), Naphtho thiazol nucleus (for example, naphtho [2,1-d] thiazol, naphtho [1,2-d] thiazol, 5-meth Kinesin (2,3-d) thiazole, etc.), naphthoxazole core (for example, naphtho [2,1—d] oxazole, naphtho [1,2—d) ] ), Naphtho-selenazole nuclei (for example, naphtho [2,1-d] serenazole, naphtho [1,2-d] serenazole, etc. ), Thienothiazole nuclei, pyridine nuclei (for example, 2-pyridin, 5-methyl-2-pyridine, 4- pyridine, 3-methyl-4-pyridine) Etc.), quinoline nuclei (eg, 2-quinoline, 3—methyl-2—quinoline, 6—chloro-2—quinoline, 8-hydroxyl-2 —Quinoline, 4-quinoline, 6 — methoxy 4-quinoline, 1-isoquinoline, 3,4 — dihydro 11-isoquino , 3-isoquinoline, etc.) represent the atoms or groups of atoms required to complete the like; mi and represent 0 or 1; ni represent 0, 1 or 2 X is an acid ion group (eg, If, C, Br, I, C 0 4,, C¾ SO *,

It represents a C _s ¾S0 _4, etc.); represents 1 or 2. However, when the compound forms an inner salt, represents 1.

Below, typical examples of the 12- 姣 sensitive dye represented by the formula [I] * used in the present invention * Specific examples are shown, but the compounds that can be used in the present invention are not limited to these.

D-I C H- ₊

C¾C CHSO,

D-1

D-3

D-1 4

D-1 5

C¾C¾CHSOi

I

CH.

Ct¾

CH-C-CH

D-1 10 (CH * iSO,

D-1 12

D-13

D-14

Q

U3 i

(3D

OCHi

t¾),

-2 CH

D-1 25

D-1 27

OMPI For the silver halide emulsion prepared by the method of the present invention, the processing method is not particularly limited, and any processing method can be applied. For example, a typical example thereof is After color development, bleach-fix processing is performed and then water washing and stabilization processing are performed as necessary.Or, after color development, white and fixing are separated and further water washing and stabilization processing are performed as needed. It is possible to apply the operation method.

The silver halide photographic emulsion produced by the method of the present invention has a remarkable and high photographic sensitivity, and has a high illuminance failure and a small force prep. Applied to silver halide photographic materials and optical materials.

For example, it can be effectively applied to photosensitive materials for various uses such as general black and white, X-ray, color, infrared, micro mouth, silver bleaching, reversal, and diffusion transfer. be able to. [Best Mode for Carrying Out the Invention]

Hereinafter, the present invention will be described specifically with reference to Examples, but it should be understood that the present invention is by no means restricted to such specific Examples.

Example 1 1

An octahedral monodispersed pigment having an average grain size of 0.9 * Λ and having a core of silver iodobromide containing 56 mol of silver iodide and a shell of silver bromide having an average thickness of 0.016 Am was prepared. According to the method described in JP-A-54-48521, the double jet method in which pAg and pH are controlled is prepared (this emulsion is prepared as follows). Emulsion (1)). In the emulsion, the particle size distribution of silver halide grains was 0.15. In the usual way 1? After desalination, this milk Divided into 9 parts, and as shown in Table 1, a predetermined amount of 4-human, lip-^-6-methyl-1, 3,3a, 7-tetrazide den ( Compound (I)) was added, and if necessary, the mixture was adjusted to a predetermined pH with an aqueous solution of hydroxylated hydration.

Each of the thus-adjusted powders is adjusted at a ripening temperature of 55 ° C. so that the ripening time is adjusted as low as possible and a high sensation is obtained. Sulfur sensation was applied. After completion of ripening, the above compound (I) was added to each emulsion in a constant amount (1.4 ^ / mol AgX). Further, to each of these emulsions, a spreading agent, a thickening agent, a hardening agent, etc.—a general copying additive—are added, and then the polyethylene telephone is extracted. Samples f * Ll to 9 were prepared by coating and drying on a rate film paste so that the amount of Ag was 50 dnf.

Sensitometry of these samples was performed as follows. Exposure is performed using a tungsten lamp (color temperature 5,400

¹ ) Exposure through an optical knives was performed using ¹ ) and exposure was performed for 10 ^-6 seconds using a xenon flash. The image was run for 10 minutes at 20 in the following developer.

Sulfur-drum-ρ-methyl 2 min.5 9 azcolbinum 10.0 9 sodium metaborate2 dihydrate 44 f

Bromide-Calium 1.0

Add water 1

The results are shown in Table 1. Sensitivity is obtained with a coupling + 0.1

OMPI

προ The reciprocal of the amount of exposure for the sample 6 and the relative sensitivity of sample 6 as 100.

_ ΟΜΠ CJ1

Compound (III) Na-sulfate sodium Chloroauric acid Relative sensitivity REAME (57k (tetrahydrate)

Addition amount PH Turnip D

Salt) Addition amount Addition amount

Molar AgrX Molar AgX Molar AgX Ho Second exposure 10 ¹⁶ second exposure (con α) 3.5 0.8 5 6.0 0.01 100 100

2 (this invention) 210 14 3.3 6 6.5 0,01 200 520

3 (η) 210 14 1.1 3 6.5 0.02 398 1200

4 (^) 210 14 0.5 6 6.5 0.02 500 1580

5 (η) 850 28 0.8 5 5.5 0.03 630 2510

6 f control) 1 1.0 1 5.5 0.01 100 100

7 (= 3 control) 1 55 1.0 5.5 0.01 16 50

8 (:! Control) 1.0 0,4 5.5 0.02 158 63

9 (this invention) 1 55 1.0 0.4 5.5 0.02 794 3160

It is clear from the comparison of the samples al to 5 in Table 1 that an increase in the sensitivity of the sample obtained by using the method of the present invention was observed, and the increase in the sensitivity was particularly remarkable during short-time exposure.

In addition, comparison of samples NH 6 and 7 shows that when only the sulfur sensitization is performed and compound (I) is added, the compound is desensitized rather than sensitized. On the other hand, the sample Να 6,

From the comparison between 8 and 9, it can be seen that when gold sensitization is used in combination with sulfur sensitization, a remarkable sensitizing effect can be obtained by the presence of compound (I).

Example 1 2

Emulsion (1) obtained in Example 11 was divided into two emulsions, and these emulsions were added with pancro-sensitivity cumulative hydro-3,3'- ヅ-(3-sulfur (Prop.) 1 5,5'- ヅ Cro 0-9 ーーカポン-ンをををををを 4 4 4 Five minutes after the addition, Compound (I) was added to 21 OwZ mol AgX to one emulsion, and the pH was adjusted to 6.5. Each of these emulsions was subjected to ripening at a ripening temperature of 53 ° C., and a gold-sulfuric acid was increased by adjusting the ripening time so that a high sensitivity S was obtained. After ripening, compound (I) was further added so that each emulsion had a constant content (1,4 mol AgX :).

For these emulsions, 1-phenyl-5-mercaptotetrazole (hereinafter, referred to as compound (B)) and the following coupler solutions, and other commonly used emulsions After adding photo-forming additives such as spreading agents and hardening agents, the amount of silver on the triacetate

O PI Was applied so as to be 20 ZdW, and dried to prepare Samples Να 12 and 13.

Coupler dispersion 1-Hyd axy-N- {r- (2,4-di-tert-yl-mil-enoxyp pil)}-2—Naphthamide Of the ^^ is completely dissolved in a mixture of 100% of triglycerol phosphate and 50% of ethyl sulphate, and furthermore, Sorbitan monolaurate. 2 was added. This solution was added to 1 of a 10 weight / weight aqueous solution of gelatin containing 2,5 f of dodecyl benzene sulphonic acid, followed by high-speed stirring and further ultrasonic stirring. What was emulsified and dispersed after use was used.

After subjecting the above sample to wet exposure in the same manner as in Example 11, the sample was subjected to color development for 38 TC for 3 minutes using a color developing solution having the following composition.

Color developer composition

4-Rinomino-3-methyl-N-ethyl-N- (β-hydroxylethyl) yl-Rin-Ryu

m

Anhydrous sodium sulfite

Hydroxylamine

Sulfuric acid

Anhydrous carbon dioxide rim

Anhydrous hydrogen carbonate power

Anhydrous sulfurous acid reamers

Potassium bromide

Sodium chloride Ditrilotrionic acid3 sodium salt

(1 hydrate) 1 · 20 f potassium hydroxide 1.48 f Add water to make 1.

Table 1 shows the results. As can be seen from Table 12, a sample obtained by further adding a sensitizing dye to the promising heterocyclic compound of the present invention when performing the gold-sulfur sensitization of the present invention. The sensitivity is remarkably high.

OMPI Table 1 2

Compound (I) NaOH Sulfate Chloroauric acid Relative sensitivity

Lium (5 water (4 water salt)

Addition amount pH turnip ??

Salt) Addition amount 漦

/ Mol AgX »VZ mol AffX» ¾ »Z mol A & X ¾ ₀ seconds exposure 10 over ⁶ seconds ¾ light

10 (control α) 3.5 0.8 5 6.0 0.02 100 100

11 (this invention) 210 1 4 1.7 0 6.5 0.02 625 1120

Example 1 3

In the same manner as in Example 11, the core and average thickness of silver iodide containing 2 mol of silver iodide were determined by a controlled double-jet method of pAg and pH. A tetrahedral monodisperse emulsion (hereinafter referred to as an emulsion ^) having a silver shell of 16 and an average particle diameter of 0.9 was prepared. The dispersion box of the particle size distribution of silver halide particles in the emulsion (2) was 0.14. After desalting, the solution is divided into three parts, one of which is used as a control, and the other amount of the compound shown in Table 13 is added. Made. Each of the emulsions thus prepared was subjected to gold-sulfur sensitization which was considered to be optimal. After the completion of ripening, compound (1) was added so that the content of each emulsion became constant (1.4 mol AgX :). Each of these emulsions was evaluated in the same manner as in Example 11. Table 1 shows the results.

OMPI 8 I—CXI

-3

Compound (I)

Lithium (5-water (4-hydrate) Relative sensitivity Addition amount pH)

Salt) Addition amount Addition amount

/ Mol AffX mol AffX mol AgrX i¾0 seconds exposure 10 over ⁶ seconds Hikiri light

12 (= r control) 4.0 0.7 5 6,0 0.03 100 100

13 (the present invention) 210 1 4 0.5 0 6.0 0.02 410 1250

14 (f) 850 2 8 0.7 6 5.5 0.02 505 1460

From Table 13, it can be seen that the material according to the present invention is remarkably highly sensitive to tetragonal silver halide grains. Reference example

In Example 1, in contrast to emulsion (1), the average grain size of the emulsion (1) (the octahedral grains and the same body) was a shell-type silver iodobromide grain (core silver iodide 2 mol *). Emulsion (hereinafter referred to as Emulsion (3); dispersity: 0.15) from silver iodobromide, silver bromide having an average thickness of 0.02 Jtm, and conventional products. Example 1 was carried out using an emulsion composed of irregularly-shaped twinned silver iodobromide grains (containing 2 mol of silver iodide) (hereinafter referred to as “Emulsion (4). Dispersion degree: 0.14”). Chemical amplification was attempted in the same manner as in Example 1, and Samples Να15 to 17 using ¾ ¾ and 及び αΐ 8 to 20 using Emulsion (4) were prepared. These samples were evaluated in the same manner as in Example 11. ₀ The results are shown in Table one 4

O PI 01

Table 1 4

However, in the case of the above reference example, the use of sodium thiocyanate and chloroauric acid alone as the sensitizers is extremely poor in sensitizing leather. 0 to 50 WZ AgX added.

As is evident from Table 1, in the case of an emulsion composed of cubic grains and irregular twin grains, chemical ripening was performed in the presence of a hidden π-xitite lazyndene compound. You can see that they are going to perish.

Example 1 4

Emulsion (1) obtained in Example 1 was replaced with 1,1 -'- phenylthiourea (sensitizer A) instead of sodium sulfate instead of sulfuric acid. A comparative experiment similar to that of Example 11 was performed using N-ethyl-Ν'-4-thiozirylthiourea (sensitizer Β). The results are shown in Table 1-5.

OMPI I—cn Table I 5

As is evident from Table 1-5, regardless of the type of sulfur sensitizer, the thiourine violet derivative alone can provide the same sensitizing effect as sodium thiosulfate. .

Example 1 5

In the same manner as in Example 11, two kinds of core / shell octahedral silver iodide emulsions having a dispersity of 0.20 and 0.10.

The Agl content was 8 mol, the average grain size was 0.65 m, the core was silver iodobromide, the shell was silver bromide, and the shell thickness was 0.015μτιι :). To each emulsion was added 5 mol AgX of the following sensitizing dye 、, 40 «? Z mol AgX of sensitizing dye B and 90 ^ / mol AgX of compound (I), and further sodium thiosulfate. Then, ammonium chloroauric acid, ammonium thiocyanate 5QwZmol AgX was added, and the same palm as in Example 11 was subjected to chemical sensitization and spectral sensitization.

(However, the control emulsion was subjected to heat ripening without adding the compound (I).)

To each of the emulsions obtained above, the following stabilizers, color coupler dispersions, commonly used hardeners and coating aids were added, and the triacetate film was added. Samples α26 and 28 were obtained by coating and drying on a paper support.

(Sensitizing dye)

Θ

_{(C¾) * S0 3 (CH2} ) 4SOsNa

OMPI

v WIPO [B]

[Coupler]

1-Hydroxy 2-[3-1 (2,4--tert-mil-enoxy) 1-n-butyl] Naphthamide

[Stabilizer)

(a) Compound (I)

(b) Compound (H) ^ Each sample above was treated in the same manner as in Example 1-2, and sensitometry was performed. Table 6 shows the results.

OMPI WIFO >-*

Οί o

Table--6 compounds (I sodium thiosulfate chloroauric acid

Lium (5 water (4 types) Relative sensitivity Dispersion Addition amount Turnip!)

Salt) Addition amount Addition amount (1 second exposure)

«? / Mol AgjX

26 0.20 nt o 110 5.3 2.8 0.04 100

28 0.10 Present invention 110 5.3 2.8 0.03 209

From Table 1, it can be seen that when the emulsion having a small dispersity, that is, a good monodispersity was sensitized with gold-sulfur in the presence of the nitrogen-containing heterocyclic compound of the present invention, the sensitizing effect was remarkably large. And. Example 1 6

In the same manner as in Example 11, a silver iodobromide refining agent containing octahedral crystals having an average grain size of 0.65 βη (silver iodide content: 6 mol *, dispersion 2), wherein the content of silver iodide is uniformly distributed in the silver iodide (hereinafter referred to as “agent (5)”) and the average grain size is 0.6. A silver iodobromide emulsion (silver iodide content: 8 mol, dispersity: 0 * 1 2) consisting of 5 μνι-octahedral crystal silver phosphide, with a thickness of 0.016 / i « A silver-coated silver iodide emulsion (hereinafter referred to as “Eon, Emulsion (6)”) coated with a silver shell was prepared from the above emulsions (5) and (6). After adding compound (I) to each of the compounds in an amount of 220 mol / mol AgX, two kinds of sensitizations of sulfur sensitization and gold-sulfur sensitization were performed in the same manner as in Example 11. As a chemical enhancer, sodium sulfate sodium (pentahydrate) mol AgX chloroauric acid (tetrahydrate) 0.62 «^ / mol AgX, thiosulfone ammonium- Room 50> ¥ / mole AgX was used. Next, in the same manner as in Example 11, various photographic additives were added to each emulsion to prepare Samples N0L29 to 32, and evaluation was performed in the same manner as in Example 11, and Table 7 shows the maggots. The sensitivities were expressed as relative sensitivities based on the sensitivities at the o-second exposure of the sample obtained by subjecting the emulsion (5) to the sulfur enhancement only (100). 63) Table 1 7

From Table 7, it can be seen that a remarkable sensitizing effect can be obtained only in the case of the present invention in which the gold / sulfur emulsion was added to the emulsion / shell emulsion (sample Να32 :).

Example 1 7

In the same manner as in Example 11, the following emulsions (7), (8), (9) and (10) were prepared by the double jet method.

Emulsion (7) = silver iodobromide polydisperse bi-crystalline emulsion with an average particle size of 0.65 in (dispersion degree 0,34, silver iodide content 8 mols) Emulsions (8), (9) and CO): Monodisperse core Z-shell silver iodobromide powder (Silver iodide shell with average grain size of 0.65 A «, silver iodide content of 8 mol, 0.016) Emulsion (8) is a cubic crystal, Emulsion (9) is an octahedral crystal, and Emulsion is a fourteen-sided crystal. From body crystals.

In each of these emulsions (8), (9) and α, sodium thiosulfate (pentahydrate) was added with mol AgX and chloroauric acid (4 water).

O PI Salt) 1.13 w and Z mol AgX were simultaneously added, and gold-sulfur sensitization was performed in the same manner as in Example 11. However, when compound (I) 222 mol AgX was added (5 minutes before the addition of the chemical sensitizer) and when it was added) (30 minutes after the addition of the chemical sensitizer), addition time ^ (chemical addition) After the end of the feeling). Further, in the same manner as in Example 1: I, various photographic additives were added to each emulsion to prepare Samples 3α33 to 44, and evaluation was performed in the same manner as in Example 11; : See Table 1-8. The relative sensitivities in the table are based on the case where the sensitivity at ¹ Z _50- second exposure was _{100 when} chemical sensitization was performed by adding compound (I) to each of the agents at the time of addition (3). Is the relative value of

Table 1 8

Comparison of Samples Να 39,40 and 41 and Sample Να 42, 43 and 44 shows that Compound (I) can exert the effects of the present invention even when added after completion of the chemical reaction. I understand. Also, from the results of the materials NtL 33 to 38, it was found that the emulsions of the present invention composed of octahedral silver halide grains and the emulsions composed of tetradecahedral silver halide grains were used. Conversely, it can be seen that adding sensitization after chemical sensitization has a greater sensitizing effect. Therefore, it can be seen that the addition time of the compound (I) is unpredictable in the method of the present invention.

Example 1 8

The core of silver iodide containing 10 mol of silver iodide 56 and the average thickness of 0.0 were obtained by the controlled double jet method of pA and ρΗ as in Example 11. A tetrahedral monodispersed emulsion having a silver bromide shell of 16 βτη. And an average particle size of 0.9 <«and a dispersity of 0.15 was prepared. After desalting, this emulsion was divided into nine parts, three of which were used as controls, and the other amount of the compound shown in Table 9 was added to make the desired ρΗ and pAg did. The emulsion thus prepared was subjected to gold-sulfur sensitization and dye sensitization in the same manner as in Example 12. Further, the same photographic additive as in Example 12 was added, and the mixture was applied and dried to prepare Samples NDL 45 to 53. These samples were evaluated in the same manner as in Example 12, and the results are shown below.

ΟΜΡΙ r 01 Table 1 9

(Note) Compound on) is 2-mercaptobenzoyl

• (2) The sensitizing dye is the following j? O

Sensitized purple

(A): 3, 3,--(3-Surho 7 ° π building) 1, 4, 5,

4 ', 5'- ヅ Penzothiocyanin hydroxide

(B ^ i: 5,5'-decyl-3,3'-di-sul-hop-n-pill)

(C ^: 5, 5, _ ヅ--9----9--

(3-Sulfo: ° pi pill)

(D) Γ 9-tool-3, 3 '-s ^-(3-sur hop pill

One, five, six, five ', six' — dipenza

(E): Ash α-5,5'- ヅ Cross mouth -3,3 '-' Source hop pill 9-Echiruchi Doxy

(F): End pi -9 -Ethyl -3,3'--(3 -Sulhopropyl) -4,5,4 ', 5'- End of postcard

As can be seen from Table 9, the sample obtained according to the present invention has less rash and high sensitivity. In addition, it can be seen that the sample of the present invention is improved while the comparative sample has a large high illuminance sensitivity failure.

Example 1 9

In Example 12 as well, in the same manner as in Example 12 except that benzotriazole was added instead of compound (I).

_ OMPI The effect was obtained.

Example 1 10

In Example 12, when benzothiazole was added in place of compound (I), a good sensitizing effect was obtained as in Example 12.

Example 1 1 1

In Example 12, even when penzimidazole was added instead of compound (I), a good sensitizing effect was obtained as in Example 12.

OMPI

Claims

The scope of the claims

1. A silver halide emulsion containing silver / shell silver halide grains is subjected to gold-sulfur sensitization or gold sensitization with a gold sensitizer and a sulfur sensitizer or a selenium sensitizer. A method for producing a silver halide sensitizer which sensitizes to gold and selenium, wherein the silver halide halide is an octahedral crystal or a tetradecahedral crystal having a (111) plane. The silver borohydride constituting the grains is substantially different from silver iodobromide, and the coefficient of variation of the grain size distribution of the π-silver halide grains is large.

0.18 or less! ), Silver or Gin'i on-gold one sulfur增感or in the presence of the complex Ru bovine forming nitrogen-containing heterocyclic compounds, c ¹³ Da emissions of which a call to Toku徵to gold Ichise les down增感Method of producing silver emulsion.

2. The method according to claim 1, wherein the amount of the nitrogen-containing bi-purple ring compound is an amount necessary to cover the surface of the silver phosphide particles with a monomolecular layer or a 10-molecular layer. The method for producing a silver halide emulsion according to the above item.

3. Among the sulfur atoms contained in the sulfur sensitizer, the number of sulfur atoms that can react with silver ion to form silver sulfide or the number of sulfur atoms contained in the sensitizer. In contrast, the number of selenium atoms that react with silver ion to form silver selenide is within the range of ^ "to Production of the hanned emulsion according to claim 1

4. The enantiomer compound is a Zindene ring, a Trizol ring, a Tetrazol ring, a Thiolzol ring, a Penzotizazo ring

(OMPI

^WIPO Ring, naphtho thiazole ring, genuine kisazoru ring, zenzo genuine kisazor ring, naphtho genuine kisazor ring, pentzimidazo Claims which is a compound containing a thiol ring, a naphthoimidazole ring, a thiol end sol ring, an oxal end sol ring or a serenazole ring. 2. The method for producing a silver lon emulsion according to item 1.

5. The process for producing a silver halide emulsion according to claim 4, wherein said double-ring compound of aspirin is a compound containing an azandene ring.

6. The claimed compound is a π-conjugated compound having 3 to 5 nitrogen atoms in the azindene ring. 6. The method for producing a π-silver danide emulsion according to Item 5.

7. The method according to claim 1, wherein the silver iodide content of the silver iodide is 0.5 to 15 mol.

& In the core / shell type, in the silver iodide content distribution, the area near the surface of the silver pi-danide grains is the interior! 5. The method for producing a silver halide emulsion according to claim 1 or 2, wherein

9. The method according to claim 1, wherein the silver halide emulsion further contains at least one plant of a sensitizing dye represented by the following general formula [I]. Item 6. The method for producing a silver halide emulsion according to Item 5.

General formula [I] One OM "PI" Ichiichi Zi--.Ichi -Z%-,

Ε,-Ν CH— CH — 1 ^ one L _s C- CH = CH¾ N-Rt

[Wherein, Ri and 112 «: each represent an alkyl group or a benzyl group; Li, L ₂ and La each represent a methine group; Zi and ZJJ represent Each represents an atom or group of atoms required to complete a 5- or 6-membered heterocyclic ring; and m ₂ represents 0 or 1; ni represents 0, 1 or 2; X represents an acid-on group; represents 1 or 2. However, when the compound forms an inner salt, represents 1. ]

10. The method for producing a silver halide emulsion according to claim 1, wherein said nitrogen-containing heterocyclic compound is a transparent substance.