JPS60150046A - Silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To improve the sensitivity, preservation stability, etc., and to reduce the red light sensitivity, fogging, etc. by sensitizing chemically a silver halide photographic emulsion with a water-soluble metallic compd., an unstable sulfur compd., and a specified selenium compd. CONSTITUTION:(A) 1X10<-9>-1X10<-4>mol water-soluble gold compd. (e.g., chloroauric acid) based on 1mol silver halide, (B) 1X10<-7>-1X10<-3>mol unstable sulfur compd. (e.g., ammonium thiosulfate) based on 1mol silver halide, and (C) a compd. (e.g., formulas II and III) expressed by the formula I [Z is a nonmetallic atom group necessary for forming a nitrogen-contg. heterocyclic ring, R1 and R2 are H, alkyl, etc., and (n) is 0, 1, and 2] are added to a silver halide photographic emulsion to sensitize chemically the emulsion. In addition, the compd. of the formula I can be obtained by dissolving a compd. shown by the formula IVin a solvent, heating, adding carbon diselenide, and allowing to react.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to silver halide photographic emulsions, particularly H
p! This invention relates to a silver halide photographic emulsion that has been chemically sensitized with a selenium compound, has high sensitivity and low sensitivity to red light, has little fog, and has excellent storage stability.

[Prior art]

Hitherto, in order to increase the sensitivity of silver halide photographic emulsions, sensitization methods have been proposed using sulfur compounds, noble metals, and selenium compounds, either alone or in combination.・Theory ofΦ
The Theory of the Photo
The sensitization method described in "Graphic Process", 4th edition (Macmillan Publishing Co., Ltd., 1977), pages 149-160 is known.

In the so-called selenium sensitization method that uses a selenium compound, generally when the unstable selenium compound described in U.S. Pat. It has been known. Furthermore, methods for improving the drawback of fog formation associated with selenium sensitization methods are disclosed in Japanese Patent Publication No. 13489/1983 and Japanese Patent Application Laid-open No. 1983-13489.
No. 71,320, US Pat. No. 3,420,670, etc., and these methods have been improved to some extent.

However, in recent years, there has been an increasing demand for emulsions that do not cause fog, have low storage deterioration during D storage, are stable, and have high sensitivity. Using
It has become clear that even with the excellent sensitization method described in Publication No. 89, it is not possible to achieve both desired crystal sensitivity and stability. In particular, it has been found that photographic emulsions sensitized by fse selenium compounds have the drawback of being sensitive even in the red light region and causing fogging under red safe light.

[Purpose of the invention]

Therefore, the first object of the present invention is to have stable photographic properties,
Another object of the present invention is to provide a silver halide photographic emulsion that has increased sensitivity without causing fog.

A second object of the present invention is to provide an I silver halide photographic emulsion which has low sensitivity to red light, high sensitivity, and excellent storage stability.

[Structure of the invention]

As a result of intensive research, the inventors of the present invention found that...Silver chloride 1
txto to Ixto mole of water-soluble gold compound per mole...txto-7 to LXI per mole of rogens
O-3 mol of unstable sulfur compound and the following general formula [I]
Chemically sensitized by the compound represented by 'lr%
They discovered that the object of the present invention can be achieved by silver halide photographic emulsion, and completed the present invention.

General formula [11] [In the formula, 2 represents a group of nonmetallic atoms necessary to form a nitrogen-containing bicyclic ring, and R represents a hydrogen atom, a lower alkyl group, a cycloalkyl group, an allyl group, or an aryl group,
R2 is a hydrogen atom, a lower alkyl group, a cycloalkyl group,
It represents an allyl group, an aryl group, or a nitrogen-containing compound group, and may be combined with R1 to form a compound group, and n represents 0 or l. ] The compound represented by the above general formula CI) used in the present invention is called a bicyclic-substituted selenourea compound. This compound is described as a general name in Japanese Patent Publication No. 13489/1982 and Japanese Patent Publication No. 44-15748, etc., but its specific structure has not been disclosed, and it is also described in Japanese Patent Publication No. 13489/1989. As shown in Examples, it has been shown that the Q effect 4 of the present invention cannot be obtained even when an unstable selenourea compound is combined with a water-soluble gold salt and an unstable sulfur compound.

Preferred nericyclic selenourea compounds represented by the general formula [13] include N,N'-substituted selenoureas represented by the following general formula [11].

General formula [■] In the formula, R2, z and n represent the contents defined in the general formula [■]. 1° C.3 represents an alkyl group, a cycloalkyl group, an allyl group, an aryl group, or an aryl group, and may be bonded to R2 to form a heterozygote.

Water-soluble gold compounds useful in the present invention include, for example, U.S. Pat.
．． Gold chloride, potassium oleate, potassium auriolite, potassium auricyanide, potassium aurithiocyanate, gold sulfide, gold selenide, potassium chloroaurate, etc., as described in No. 361 specifications, etc., as well as the following. Examples include gold compounds.

These compounds are preferably added in the form of an aqueous solution during silver halide grain formation, physical ripening, or chemical ripening, and more preferably added at the start of chemical ripening.

The unstable sulfur compounds used in the present invention include:
Alkali metal thiosulfates (e.g. sodium thiosulfate,
Potassium thiosulfate, etc.), ammonicum thiosulfate, thiosemicarbazide, isothiourea (e.g., allylisothioure, etc.), thiocarbamic acid, thioamide (e.g., N-methylmonothiosuccinimide, etc.), and the following thiourea compounds. It will be done.

(a) II H2NCNH2 1 (c) CH3CO-NHC-NHCOCH51 (8) CH2= CH-CH2NHCNH2〇IU These and other useful unstable sulfur compounds include U.S. Pat. 2゜410.
No. 689, No. 2,728,668, No. 2゜999
．． No. 751, No. 3,501,313, British Patent No. 9
No. 97,031, West German Patent No. 1,422,869 Branch Specification, Japanese Patent Publication No. 49-20533, Japanese Patent Publication No. 48-304
No. 19, No. 55-45016, No. 58-80634, etc., or Journal of Photographic Science (J.

Phot, Set, ) Volume 1 (1953) 133
You can punch the compounds listed on the page.

These unstable sulfur compounds may be dissolved in water or a water-miscible organic solvent such as methanol or ethanol alone or in a mixed solvent, and added during formation of silver rhodanide grains, physical ripening, or chemical ripening. It is preferable to add it at the start of chemical ripening.

In the above general formulas ['I] and [■], 2 is a nitrogen-containing 5- or 6-membered heterocycle that may have a fused JJn, such as a triazole ring, thiazole ring, thiazoline ring, selenazole ring, and selenazoline ring. , oxazole ring, oxazoline ring, thiadiazole ring, imidazole ring, imidacilline ring, benzothiazole ring, benzoselenazole ring, benzoxazole ring, benzimidazole ring, pyridine ring, pyrimidiX ring, quinoline ring, etc. means a group of metal atoms.

The heterocycle includes a halogen atom (for example, a chlorine atom, a bromine atom, etc.), an alkyl group, preferably a lower alkyl group (for example, a methyl group, an ethyl group, etc.), an aryl group (for example, a phenyl group, etc.), an amino group, preferably a substituted Amino groups (e.g. diethylamino group, dimethylamino group, etc.), alkoxy groups,
Preferably FIN: class alkoxy groups (e.g. methoxy group, ethoxy group, etc.), alkoxycarbonyl groups (e.g. methoxycarbonyl group e), sulfamoyl group, utt,
< may be substituted with a substituted sulfamoyl group (eg, dimethylaminosulfonyl group, etc.), carbamoyl group, preferably tL<U substituted carbamoyl group (eg, dimethylaminocarbonyl group, etc.), carboxy group, nitrile group, etc.

Examples of the cycloalkyl group represented by R1, R2 and R5 include a 7-clopentyl group and a cyclohexyl group, and the alkyl group is preferably a lower alkyl group, and the lower alkyl group is preferably a straight alkyl group having 1 to 6 carbon atoms. Examples include chain or branched alkyl groups (for example, methyl, ethyl, propyl, pentyl, isopropyl, 2-methylbutyl, etc.), and the lower alkyl group is -.
halogen atoms (e.g., fluorine atoms, chlorine atoms, etc.), human mixi groups, lower alkoxy groups (e.g., methoxy groups, etc.), hydroxyalkoxy groups (e.g., 2-hydroxyethoxy groups, etc.), alkoxyaluroxy groups (e.g., 2-methoxyethoxy groups, etc.) ), a substituted amine group (for example, dimethylamino group, etc.), an alkoxycarbonyl group (for example, λ is methoxycarbonyl, ethoxycarbonyl, etc.), a carbamoyl group, a sulfamoyl group, a nitrile group, an aryl group, etc. Particularly preferred are alkyl groups substituted with aryl groups (eg, benzyl group, phenethyl group, etc.).

Further, examples of the aryl group include phenyl group, tolyl group,
Anisole group, chlorophenyl group, diethylaminophenyl group, cyanophenyl group, carbamoylphenyl group,
It can be divided into methylsulfonylphenyl group, sulfamoylphenyl group, etc.

The nitrogen-containing heterocyclic group represented by R2 and R) is a fused &T
A 5- or 6-membered nitrogen-containing heterocyclic group that may have h, such as an oxadiazole ring, a thiadiazole ring, a pyridine ring, a quinoline ring, an indole ring, an oxazole ring,
Benzoxazole ring, thiazole ring, benzothiazole ring, imidazole ring, benzoimidazole ring, selenazole ring, benzoselenazole ring, pyrimidine ring, etc., and these heterocycles include methyl group, methoxy group, and phenyl group. , a halogen atom (example i-1r! 7 atoms, chlorine atom, etc.), a nitrile group, a methoxycarbonyl group, a carbamoyl group, a sulfamoyl group, etc. may be substituted.

Further, examples of the ring formed by bonding with R1 include a piperidine ring, a morpholine ring, and the like.

The compounds represented by the general formulas [11 and ["l[] can be synthesized, for example, as follows.

That is, (1), the symmetric heterocyclic acid selenourea is
Excess amount of amine compound represented by the following general formula [1]?
It is dissolved in an inert solvent such as carbon tetrachloride or benzene, heated to reflux under a nitrogen atmosphere, and carbon diselenide is added dropwise to react. The reaction is stopped when the generation of hydrogen selenide gas is stopped, and the desired product can be obtained by concentrating, cooling, purifying, and recrystallizing if necessary.

General formula [11 Note that 2 in the formula has the same meaning as 2 in general formula [1).

In addition, 12), asymmetrically treated alkyl group-substituted selenoureas,
A primary amine compound among the amine compounds represented by the general formula [1] or [1v] is dissolved in an inert solvent such as total carbon tetrachloride or benzene, and carbon diselenide is introduced under a nitrogen gas atmosphere to carry out the reaction. Then, an excess amount of one of the amine compounds is added and heated under reflux until the generation of hydrogen selenide gas is completed, and if necessary, the excess amount of amine is removed by washing with water. After that, the desired product can be obtained by drying and condensing to precipitate crystals and recrystallizing several times.

In the formula, R1 and 1tL2 are RIR in the general formula [■]
It is synonymous with 2.

Next, compounds represented by general formulas (I) and (Ir) (
υ is referred to as the selenourea compound of the present invention.

), but the invention is not limited to these.

[Exemplary compounds]

e ■-h (51, Se (hereinafter referred to as Atoday)) The selenourea compound of the present invention is dissolved in water or a water-temperature eleventh organic solvent such as methanol or ethanol, alone or in a mixture, and dissolved at any time during emulsion production. It is preferably added at the start of chemical ripening.

The usage of the cereurea complex of the present invention varies depending on the type of silver halide photographic emulsion, the type of compound used, etc., but it is usually silver halide 5 1 mol IJ) 3XlO mol to 1Xl0 mol It is preferable that

The value of pAg (logarithm of the reciprocal of silver ion concentration) during chemical ripening is preferably 8.0 to 11.0.

Other chemical sensitizers can also be used in combination during chemical ripening. Chemical sensitizers that can be used in combination include, for example, selenium compounds described in U.S. Pat. No. 3,420,670, U.S. Pat. No. 2゜487.850, No. 2,518,698, No. 2,521.925, No. 2
, No. 521,926, No. 2,419゜973, No. 2,
No. 694,637, reducing substances such as amines and stannous salts described in U.S. Pat. No. 2,983,610, U.S. Pat.
Examples include salts of noble metals such as platinum, palladium, iridium, and rhodium, which are described in Japanese Patent No. 245 and No. 2.566.263.

Sulfur sensitization with the compounds of the present invention can be carried out using halogenated #solvents such as thiocyanate (ammonium thiocyanate etc.).
) or 4-substituted thiourea (tetramethylurea ate).

The silver halide photographic emulsion of the present invention may be of any halogen composition such as silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, or silver chloride;
Glafkidea)
Photographic (Cbjrr; is etPhysi
que Photographique ) (Pau
(Published by Monte 1, 1967) Niji F. Dufuyn (G.

F. Duffin), Photographic Emulsion 1-e Chemistry (Photographic Emulsion)
Emuls-fan Cbemistry ) ('
f'ha Focal Press Published 196 Year 966
2010 L Zelikman (V, L, Zel-ikn
Co-authored by lan) et al., Making and Coating 9
Photographic Emulsion (Ma-1cing
and Coating Photographic
Emulsion) (Tbe Focal Pre
It can be prepared using the method described in S.S., 196, 964. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof.

In addition, a method of forming particles under an excess of ions (
A so-called back mixing method) can also be used.

As one type of simultaneous mixing method, a method of keeping pAg' in the liquid phase in which silver halide is produced, ie, a so-called Chondrald double jet method, can also be used.

The silver halide grain size distribution of the silver halide photographic emulsion of the present invention may be narrow or wide, but so-called monodisperse grains having a narrow distribution width and uniform grain size are preferred. Here, monodisperse means I.When the irregularity of silver halide grain size is expressed by the following formula C■ (size distribution), 2
It means 0% or less, preferably 151 or less.

cv=-xto.

γ However, S is the standard deviation value, and Y is the diameter γ1 of each particle when the particle projection image is converted into a circular image with the same area, and its number ni, Σn1γi A = □ Σni defined by the formula represents the average particle diameter .

The silver halide grains contained in the silver halide emulsion of the present invention have regular (R
The particles may have a regular particle shape, an irregular shape such as a twin crystal, or a mixture of the two, but regular particles are preferable.

The effects of the present invention are particularly remarkable in the above-mentioned monodisperse core/shell type silver halide grains.

The halogen composition content between the interior (core part) and the surface layer (shell part) of the core/7L type silver halide grains preferably used in the present invention may be approximately continuous, even if the grains have a square boundary. It may also change depending on the situation.

The method for producing the core/shell type silver halide grains is described, for example, in West German Patent No. 1.169.290, British Patent No. 1,027,146, and Japanese Patent Application Laid-Open No. 1987-1.
The methods described in Japanese Patent Publication No. 54232, Japanese Patent Publication No. 51-1417, etc. can be employed.

In the present invention, two or more silver halide emulsions formed separately may be optionally mixed and used.

In the process of silver halide grain formation or physical ripening,
Cadmium salts, bent lead salts, lead salts, thallium salts, iridium salts or complex salts thereof, lonrum salts or complex salts thereof, iron salts or iron salts, etc. may be coexisting.

The silver halide emulsions of this invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar-cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes.

Particularly useful dyes are cyanine dyes, merocyanine dyes and dyes belonging to the complex merocyanine color family. For these pigments, any nuclei commonly used for cyanine pigments can be applied as basic heteronuclear nuclei. Namely, pyrroline nucleus, oxazinone nucleus, thiazoline nucleus, virol nucleus,
Oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ape is fused to these nuclei; That is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, etc. can be applied.

Sensitizing dyes that can be used are, for example, German Patent No. 929.080, US Pat. No. 2,231,658, and US Pat.
748-kun, same No. 2.503.776, same No. 2,51
No. 9.001, No. 2,912,329, No. 3, 6
No. 55.394, No. 3,656,959, No. 3,
No. 672.897, British Patent No. 3,694,217, British Patent No. 1,242,588, Japanese Patent Publication No. 14030/1984, and the like.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. A typical example is U.S. Patent No.
．． 68fu No. 545, same No. 2,977, 229, same No. 3
, No. 397,060, No. 3,522.052, No. 3,527,641-¥4, No. 3,617.293, No. 3,628,964, No. 3,666. 480
No. 3,679,428, No. 3,703.37
No. 7, No. 3,769,301, No. 3.814.6
No. 09, No. 3,837,862, British Special Plan No. 1 and 3
44,281, Japanese Patent Publication No. 43-4936, etc.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. For example, aminostilbene compounds substituted with nitrogen-containing heterocyclic groups (e.g., U.S. Pat. No. 2,933,390, U.S. Pat. No. 3,
635,721), aromatic organic acid formaldehyde condensates (such as those described in U.S. Pat. No. 3,743,5),
10), cadmium salts, azaindene compounds, etc. U.S. Patent No. 3,615,6
No. 13, No. 3,615,641, No. 3,617.
Particularly useful are the combinations described in US Pat. No. 3,635,721 and US Pat.

The silver halide photographic emulsion of the present invention may contain, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, and quaternary ammonium salts for the purpose of increasing sensitivity, increasing contrast, or accelerating development. Compounds, urethane derivatives, raw material derivatives, imitasol fat conductors, 3-pyrazolidones, etc. may also be included. For example, U.S. Patent Nos. 2,400,532, 2,423,549, and 2,716,062.
No. 3,617,280, No. 3,772,02
1, No. 3,808,003, etc. can be used.

The silver halide emulsion of the present invention contains an antifoggant (Antif).
oggant) and stabilizer (s±abilizer)
It may contain k. As a compound, “An
tifogants and atabilizers
Those described in the section sJ can be used.

The silver halide emulsion may contain a developing agent. As a developing agent, "Developer Pirga" in Product Licensing Index, Volume 92, P107-108.
gents” can be used.

Silver halide can be dispersed in colloids that can be hardened by various organic or inorganic hardeners. As a hardening agent, Product Licensing Index, No. 9
Those described in Volume 2 Pt07 r) iartten-ers Section 40 can be used.

Silver halide emulsions may contain coating aids. As coating aids, those described in Product Licensing Index, Vol. 92, Pt08, section ``Coating aids'' can be used.

The silver halide emulsion of the present invention can contain so-called color couplers. As a color coupler, product license index, volume 92 Pt
The materials described in the section 07, ``Color Materials'' may be used.

On the photosensitive material side prepared using the silver halide photographic emulsion of the present invention, the photographic emulsion layer and other hydrophilic colloid layers include
Dyes may be included as filter dyes or for various purposes such as preventing irradiation. As such dyes, Product Licensing-Intex, Volume 92 Pt09 r Absorbing an
d filter dyos J c2) is used.

The silver halide photographic emulsion of the present invention also contains an antistatic agent, a plasticizer, a matting agent, a moistening agent, an ultraviolet absorber, a whitening agent,
It may contain an air antifoggant and the like.

The silver halide emulsion used in the present invention is used as a vehicle in Product Licensing Intex, Vol. 92, P.
t08 r Vehicles J section (1971
Use the vehicle described in February).

The silver halide emulsion of the present invention is coated onto a supporting body together with other photographic layers as required. , the application method is Flow Duct・
Licensing Index, Volume 92 Pt09 r
The methods described in Coating procedures J may be used. Further, as the support, those described in Product Licensing Index, Vol. 92, P108, R5upports J may be used.

The silver halide photographic emulsion of the present invention is used for various purposes. The analogy is used for the following purposes:

Emulsions for color positives, emulsions for color paper, emulsions for color negatives, emulsions for color reversal (sometimes containing couplers, some without), emulsions for photographic materials for plate making (for example, lithium film salt, etc.), Emulsions used in photosensitive materials for cathode ray tube displays, emulsions used in photosensitive materials for X-ray recording (especially materials for direct and indirect photography using screens), colloid transfer process (Coll)
oidtransf6r process ) (as described, for example, in U.S. Pat. No. 2.716.059)
Emulsion used for silver salt diffusion transfer Bromo X (5ilv
er 5alt diffusi-on transf
er process) (for example, US%i No. 2.3
No. 52,014, No. 2,543,181, No. 3.
Emulsions used in color diffusion transfer processes (as described in U.S. Pat. No. 3,087,817, U.S. Pat. No. 3,086,885, etc.);
No. 567, No. 2.983,606, No. 3゜253
．． No. 915, No. 3,227,550, No. 3゜22
No. 7.551, No. 3,227,552, No. 3゜4
No. 15.644, No. 3,415,645, No. 3゜415, No. 6-16, Research Disclosure No. 1
Emulsion used in Volume 51, Entry 15162, P75-87 (described in November 1976, etc.), tie transfer process (1mbibitiontransf)
er process ) (U.S. Patent No. 2.882.
156), silver dye bleaching method [Friedman's 1llstory of
Co-1or Photography” Ame
rican PhotographicPudlish
ers Co 1944 (especially Chapter 24) and Br1
tissue Journal of Photography
hy”Vollll, P-308-309APr, 7.
Emulsions used in direct positive photosensitive materials (for example, U.S. Pat. No. 2,497,875)
No. 2,588,982, No. 3,367,77
No. 8, No. 3,501,306, No. 3,501,3
No. 05, No. 3,672,900, No. 3.477.
No. 852, No. 2.717,833, No. 3.023
, No. 102, No. 3.050.395, No. 3.50
Emulsions used in photothermographic materials (for example, U.S. Pat. No. 3,152,90)
No. 4, No. 3,312,550, No. 3,148,1
22, British Patent No. 1,110,046, etc.), and photosensitive materials for physical development (for example, British Patent No. 920.277, British Patent No. 1.131.23).
8)).

The silver rognide emulsion of the present invention is particularly suitable for inner color in a multilayer structure, particularly for reversal force 2, negative color emulsion, black and white negative emulsion (black and white island negative, micro negative, etc.), It is usefully used as an emulsion for color diffusion transfer processes, an emulsion for direct positive light-sensitive materials, and an SFA image type emulsion in a core/shell type.

Exposure to obtain a photographic image may be carried out using a conventional method. Namely, natural light (sunlight), tungsten lamp,
Any of a wide variety of known light sources can be used, such as fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, and cathode ray tube flying spots. The brain light time is not limited to exposure times of 1/l 000 seconds to 1 second, which can be obtained with a normal camera, as well as exposures shorter than 1/1000 seconds, such as exposures using xenon flash lamps or cathode ray tubes.
It is also possible to use light for a period longer than 10" to 1/10 seconds. The spectral composition of the light used for the light source can be adjusted with a steep filter depending on necessity. Laser light is used for exposure. Alternatively, exposure may be performed using light emitted from a phosphor excited by electron beams, Xk', γ rays, α rays, or the like.

Photo νL of a photosensitive material made using the photographic emulsion of the present invention
For processing, either one of the known methods or two can be used:
Wear. For example, the photo processing described in Product Licensing Index, Volume 92 Pito, Section 5LJ of ProcessingJ may be used.

〔Example〕

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

Example 1 In order to clarify the difference between the sensitizing effect and stability of conventionally known unstable selenides, particles with a particle diameter of 0.8 were obtained by the Chondral double jet method with pAg k maintained at 8.0.
μm silver iodobromide (silver iodide content 2.0 mol) octahedral emulsion? Prepared. This emulsion was divided into 8 equal parts and each emulsion was heated at 50°C.
Optimum ripening was carried out by heating to 1 mole of chloride, adding J)l+v of potassium chloroaurate, 3μ of thiosulfuric acid, and the selenium sensitizer shown in Table 1 below. Ta.

After chemical ripening, appropriate amounts of saponin as a coating aid and hydroxyne chloride S-) riazine as a hardening agent were added, and each emulsion was coated on a cellulose acetate film support with 45 q/100 t of silver and 30 ml of gelatin.
Samples 1 to 8 were prepared by coating at a ratio of /1OOcI/I.

This specimen 1 to 8 were all wedged through the Teigesten light.
After exposure for 150 seconds, a developer of the following composition was used for 20 seconds.
After developing for 5 minutes at ℃, it was fixed and washed with water.

[Developer composition]

Automatic densitometer (manufactured by Konishiroku Photo Industry Co., Ltd.) for each developed sample? 1 to find the photographic characteristic curve, [Fog +
Sensitivity was expressed as the reciprocal of the exposure required to give an optical density of 0.13.

The results are shown in Table-1. The sensitivity is the total sensitivity of sample 1, 100.
It is expressed as a relative value.

As is clear from Table 1, the combination sensitization of the selenide adducts according to the present invention increases sensitivity and suppresses fog compared to the conventional combination sensitization using selenium compounds.

Example 1-2 Next, high temperature storage treatment was performed to demonstrate that the combination technology of the present invention has superior storage stability compared to the conventional technology.

A hexahedral silver iodobromide emulsion (emulsion A with a silver iodide content of 4 mol) and an average grain size of 0.8/Xn was prepared by a method similar to that described in Japanese Patent Publication No. 57-154232. ) and a core/shell type silver iodobromide (4 molar silver iodide content) hexahedral emulsion with an average grain size of 0.6 μm covered by an AgBr shell with a thickness of 0.02/jm. (
Emulsion B) and? , respectively, were prepared. Emulsion A and emulsion Bf were each divided into 6 parts, and for each emulsion - chloroauric acid in silol per mole of silver halide, 2qcDN-ethylruger(2-thiazolyl)thiourea, and a selenium sensitizer shown in Table 2 below. All the components were added and subjected to optimal chemical ripening at 50°C.

Next, appropriate amounts of 4-didroquine-6-mether-1.3.3a, 7-chitrazaindene, l-phenyl-5-mercaptotetrazole as a stabilizer and saponin as a coating aid were added to each emulsion, and a cellulose acetate-based support was added. The cloth was dried on top and a fee of 9-20 was stolen.

Each sample'f: 55℃±2℃, relative humidity 55℃
After aging for 72 hours, the aging-treated and untreated samples were exposed, exposed, fixed, washed, and measured in the same manner as in Example 1, and the quality curves were determined. ? I asked for it.

The results obtained are shown in Table-2.

The method of displaying the ribs is similar to Example-1 and +=, Sample 1.
The sensitivity of No. 4 without aging treatment is expressed as a relative value with 1oo as the sensitivity.

As is clear from Table 2 above, as shown in Samples N[114 and 20], emulsions A and B tend to be sensitized with slight fog when stored at high temperatures.

For these emulsions, samples subjected to combination J and ρ sensitization using the selenium compound according to the present invention did not exhibit significant fogging, which is characteristic of selenium sensitization, even when stored under high-temperature conditions. It is stabilized with a feeling.

Furthermore, the effects of the present invention are more obvious in the case of core/shell type emulsions than in ordinary grain emulsions of uniform composition.

10,000, Samples sensitized using known selenium compounds and nitrogen-containing nitrogen-free ring-substituted selenourea compounds other than those of the present invention are as follows:
Both homogeneous composition grain emulsions and core/shell type emulsions provide higher sensitivity than conventional gold-sulfur sensitization, but they cannot be said to sufficiently suppress fog, and fog progresses after storage at high temperatures, resulting in poor sieve sensitivity. Although it is maintained, the photographic characteristics have deteriorated.

Example 3 A polydisperse tabular AgBrJ (silver iodide content of 6 mol %) emulsion (designated emulsion C) with an average grain size of 0.6 μm was prepared by double jet method, and JP-A-57-154232 The average particle size is 0 using the same method as described in the publication.
．． A 6 μm 14-hedral AgBrJ (6 mol % silver iodide content) monodisperse emulsion (emulsion) and a thickness of 0.04
Tedecahedral core/shell type AgBrJ with an average grain size of 0.6 μm (
6 molar silver iodide content) monodisperse emulsion (milk 1!il
J and E) were prepared, respectively.

Each of the 14 emulsions prepared above was divided into four parts, and for each emulsion, 0.8 μ of chloroauric acid and 2.5 μ of N,N-diphenylthiourea thioneanic acid were added per mole of silver halide. Addition of ammonium 150~ and the selenium compound shown in coating-3 below 1. Optimal chemical ripening was performed at 52°C.

Each emulsion was then added with 4-hydroxy-6-methyl-1,3,3&,7-titrazaindene as a stabilizer, l-phenyl-5-mercapto-tetrazole as a coating aid, saponin as a coating aid, and 1.2% as a hardener. - appropriate amounts of bis(vinylsulfonyl)ethane, per mole of silver halide,
! >50 my 5-chloro-2-[2-((5-phenyl-3-(3-sulfobutyl)-2(3H)-benzoxazinolidenecomethyl)-1-butenyl]-3-(
3-sulfo-10vir) benzoxacillium hydroxide inner salt was added and further protected dispersed polymer.
As a zenta coupler, l -(2,4,6-)lichlorophenyl)-3-[3-(2,4-di-t-amylphenoxyacetamido)benzγmido]-5-pyrazoΩ
1-(2,4,6-drichlorophenyl)-3-(
3-dodecylsuccinimitohendzamide)-5-pyrazolone, 1-(2,
A dispersion of 4,6-)lichlorophenyl)-4-(1-naphthylazo)-3-(2-chloro-5-octadecenylsuccinimideanili/)-5-pyrazolone and dotesyl gallate was added.

The emulsion thus prepared was coated on a cellulose triacetate base support and dried to prepare a sample.

Next, each sample was exposed to l/100 seconds through a green light filter (manufactured by Tokyo Shibaura Electric Co., Ltd.) and a red light filter (
Wedge exposure 4 for 300 seconds via Tokyo Shibaura Electric Co., Ltd.)
After that, a color negative development process was performed as described below.

[Development conditions]

Processing process (38℃) Processing time Color development...2 minutes 45 seconds Whitening...6 minutes 30 seconds Washing...3 minutes 15 seconds Wearing... Washing with water for 6 minutes and 30 seconds Stabilization for 3 minutes and 15 seconds... 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

Color developing solution composition: Whitening solution composition: Fixing solution composition: Stabilizing composition: The temperature of each obtained dye image was measured through a green filter to check the green light sensitivity and fog.

The results obtained are shown in Table 3.

Note that the sensitivity display method was the same as in Example-1), and the sample was 21.25.29 nol/lo for each emulsion.

All sensitivities of second exposure processing are expressed as relative values, with each sensitivity being 100.

As is clear from Table 3 above, the sample sensitized with 4 combinations of selenium compounds according to the present invention (23°24.27, 2
It can be seen that 8.31 and 32) l;j all have higher green light sensitivity than the other samples.

On the other hand, the red light sensitivity and maximum density showed small values for the sample according to the present invention, suggesting that the red light safe light fog characteristics were improved.

In addition, although the common effects of the invention are shown for all the emulsions used, even better results are obtained for monodisperse emulsions, and even better for core/7-type monodisperse emulsions. It turns out that it can be done.

Patent Applicant: Roku Konishi Photo Industry Co., Ltd. ``r-Nani NeichijE'' (spontaneous) May 14, 1980 Special, ) 1 Director-General, Mr. Kazuo Wakasugi■ ・Display of 11 cases Patent Application No. 4850 of 1988 No. 2 Name of the invention Silver halide photographic emulsion 3 Supplementary information: Person doing 1-/Relationship with 11 cases Applicant name Title (127) Roku Konishi Photo Industry Co., Ltd. 4 Agent
105 5 Date of Jli Notice of Show Cause (Voluntary) 6 Supplement 1 ``Number of inventions increased due to 7 Sleeve 1 [Specifications subject to:, l) (Detailed description of invention column) Contents of amendment (4Ili Application Sho 5fll -4850) The specification is amended as follows.

1. On page 3, lines 2 and 3, the phrase ``If used, the sulfur sensitization method'' should be corrected to ``If used, the sulfur sensitization method''.

2 In structural formula (2) on page 7 and correct it.

3, page 14, line 4 [in the formula, Z has the same meaning as Z in the general formula CI]" is amended to read "in the formula, Z and n have the same meaning as Z in the general formula CI)".

4 On page 20, line 9, “3XIQ-4 moles per mole ~
I
X IQ-"Mole-lXl0"4 5 In page 25, line 10, page 26, line 9, and page 27, line 14, the term ``heterocyclic J'' is corrected to ``heterocyclic ring J.''

6 On page 28, line 18, the word "Protact" is corrected to "Product."

7 Structural formula 〇 on the bottom line of page 37 8 In page 42, line 15, [urea ammonium thiocyanate + 50 mg J] is corrected to ``urea, 15011 g of ammonium thiocyanate.''

9 In Table 3 on page 47, in the column of "Relative sensitivity of 300 seconds of red light exposure", the numerical values of Document No. 21 to 32 are corrected as follows.

Note No. 21 r 2.2Xro-3J r 2.2X
Corrected to fO-5J.

No, '22 r 2.8X+o-3J r 2.8
Corrected to XlO-5J.

No, 23 r 6. lXl0” J r G, IX
Corrected to +o-6J.

No, 24 r 5.3X1o-' J r 5.3
Corrected to XlO-6J.

No, 25 r 1.5XlO-3J r 1.5X
Corrected to IO-5J.

No, 28 r 1.6XlO-3J r 1-6X
Corrected to +o-5J.・No, 27(7) r 1.8
Corrected XlO” J to r 1.8XlO-6J.

No, 28 r 2.2XIO” J r 2.2X
Corrected to +o-6J.

No, 29 r 1.4XlO-3J r 1.4X
Corrected to lO-5J.

No, 30 r t, 5x+o-3J r 1.5x
Corrected to lO-5J.

No, 31 r 1.3Xro rumors' r 1.3X1
Corrected to 0-6J.

No, 32 r 1.2X+o-J r 1.2Xl
Corrected to O-6J.

I”d

Claims (1)

[Claims] ...I
o" mol of a water-soluble gold compound, chemically sensitized with an unstable sulfur compound of 1X10 -IXIO mol per 1 mol of silver halide, and a compound represented by the following general formula [I]. Silver halide photographic emulsion. General formula [I] [In the formula, 2 represents a group of nonmetallic atoms necessary to form a nitrogen-containing multicyclic ring, and R1 is a hydrogen atom, an alkyl group, a cycloalkyl group, Represents an allyl group or an aryl group, R2
is a hydrogen atom, an alkyl group. It represents a cycloalkyl group, an allyl group, an aryl group, or a nitrogen-containing heterocyclic group, and may be combined with R1 to form a heterocycle, and n represents O or l't-. ]