JP2604240B2 - Silver halide photographic material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material using a novel polytelluroether compound.

(Prior Art) Conventionally, efforts have been made to obtain silver halide photographic light-sensitive materials having high photographic sensitivity, low fog generation, and little change in photographic performance during storage over time.

For example, in order to improve photographic sensitivity, an organic thioether compound is used in the production of a silver halide photographic emulsion,
It has been known for a long time to use it as a solvent for silver halide or a chemical sensitizer.

For example, U.S. Patent Nos. 3271157, 3531289, and 3574628
No. 4,057,429 and the like, a silver halide photographic emulsion (hereinafter simply referred to as an emulsion) is prepared by the presence of an organic thioether compound during the precipitation step and physical ripening, whereby the silver halide grains are made uniform in size. A technique for producing a so-called monodisperse emulsion is disclosed.

Also, U.S. Pat.Nos. 2521926, 3021215, 3038805
No. 3506443, No. 3057724, No. 3062646, No. 35747
Nos. 09, 3622329, 3625697 and the like disclose techniques for increasing the photographic sensitivity of an emulsion by allowing an organic thioether compound to be present during chemical ripening or immediately before coating during emulsion production.

Also, JP-A-53-57817 includes a tellurium atom,
There is disclosed a technique for increasing the photographic sensitivity of an emulsion by preferably using a tellurium compound substituted with an aromatic ring such as bis- (p-ethoxyphenyl) telluride when forming silver halide grains.

(Problems to be Solved by the Invention) However, when an organic thioether compound is present at the time of emulsion production, fog tends to increase.

In order to prevent the fogging due to the organic thioether compound, a technique of, for example, precipitating at a pH value of 4 or less, or ultra-purifying the organic thioether compound is known. There are drawbacks such as impractical on a target scale.

Further, as described in JP-B-58-27489, it may be used in combination with a specific antifoggant,
Although a thioether compound as described in No. 30571 has been developed, it has been desired to develop a compound which can generate less fog and achieve high sensitivity. However, the thioether compound has not yet been able to achieve its purpose.

Further, the organic telluro ether compound described as preferable in JP-A-53-57817 has an effect of certainly increasing the sensitivity, but as shown in the Examples, the effect is insufficient, and when stored over time, The photographic performance such as photographic sensitivity and gradation deteriorated remarkably.

(Object of the Invention) The object of the present invention is, first, even if the photographic sensitivity is increased,
An object of the present invention is to provide an emulsion which does not increase fog.

A second object of the present invention is to provide a high-sensitivity silver halide photographic light-sensitive material with little deterioration of photographic performance during storage over time. A third object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity and low fog, which is suitable for rapid development processing.

(Means for Solving the Problems) The object of the present invention has been achieved by a silver halide photographic light-sensitive material containing at least one polytelluroether compound represented by the following general formula (I) and a method for producing the same.

Formula (I) L ₁ -Te-L ₂ -Te-L ₃ L ₂ is a divalent compound containing at least one of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom. Represents an organic group.

L ₁ and L ₃ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group Represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group.

 Hereinafter, the general formula (I) will be described in detail.

L ₂ specifically represents R ₁ -X _{1 n} R _2- . R ₁ , R ₂
Are each independently a linear or branched alkylene group (eg,
Methylene group, ethylene group, propylene group, butylene group,
Hexylene group, 1-methylethylene group, etc.), cycloalkylene group (eg, cyclohexylene group, etc.), linear or branched alkenylene group (eg, vinylene group, 1
-Methylvinylene group, etc.), a linear or branched aralkylene group (eg, benzylidene group, etc.), and an arylene group (eg, phenylene, naphthylene, etc.).

X ₁ is -O-, -S-, -Se-, −Te−, And n represents an integer of 0 to 3. However, when n ≧ 2, R ₁ and X ₁ may be any combination of the groups described above.

R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are substituted or unsubstituted alkyl groups (eg, methyl, ethyl, propyl, isopropyl, etc.), substituted or unsubstituted (For example, phenyl group, 2-methylphenyl group, etc.), substituted or unsubstituted alkenyl group (for example, propenyl group, 1-methylvinyl group, etc.), or substituted or unsubstituted aralkyl group (for example, Benzyl group, phenethyl group, etc.).

L ₁ and L ₃ are a substituted or unsubstituted alkyl group (for example,
Methyl group, ethyl group, propyl group, isopropyl group, 2
-Ethoxycarbonylethyl group, etc.), substituted or unsubstituted alkenyl group (eg, propenyl group, 1-methylvinyl group, etc.), substituted or unsubstituted alkynyl group (eg, ethynyl group, propynyl group, etc.), A substituted or unsubstituted aralkyl group (for example, benzyl group, p-
Chlorobenzyl group, phenethyl group, etc.), substituted or unsubstituted cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), substituted or unsubstituted aryl group (eg, phenyl group, 2-methylphenyl group, etc.) ), Substituted or unsubstituted heterocyclic groups (for example,
Pyridyl group, quinolinyl group, morphonyl group, piperidyl group, etc.).

In the general formula (I), L ₁ and L ₃ are preferably an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, a cycloalkyl group, an aryl group or a heterocyclic group substituted with a hydrophilic group. . Examples of such a hydrophilic group include a hydroxy group, an amino group, an ammonium group,
Examples thereof include a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, an ether group, a sulfonamide group, a sulfamoyl group, and a carbamoyl group. Further, the divalent group L _2, preferably R _1, R ₂ represents straight-chain or branched alkylene group, an arylene group, X ₁ is -O -, - S -, - Se
−, And n represents 0 or 1.

Hereinafter, specific examples of the polytelluroether compound represented by the general formula (I) of the present invention are shown, but the compound of the present invention is not limited thereto.

1. HOCH ₂ CH ₂ TeCH ₂ CH ₂ CH ₂ TeCH ₂ CH ₂ OH 3. HOOCCH ₂ CH ₂ TeCH ₂ CH ₂ CH ₂ TeCH ₂ CH ₂ COOH 4. H ₂ NCH ₂ CH ₂ TeCH ₂ CH ₂ CH ₂ TeCH ₂ CH ₂ NH ₂ 2HCl 5. NaO ₃ SCH ₂ CH ₂ CH ₂ TeCH _{2 CH 2 CH 2 TeCH 2 CH 2} CH 2 SO 3 Na 6. HOCH 2 CH 2 TeCH 2 TeCH 2 CH 2 OH 10. HOCH ₂ CH ₂ TeCH ₂ CH ₂ CH ₂ SCH ₂ CH ₂ CH ₂ TeCH ₂ CH ₂ OH _{12. HOCH 2 CH 2 TeCH 2 CH} 2 CH 2 OCH 2 CH 2 CH 2 TeCH 2 CH 2 OH 13. CH 3 CH 2 TeCH 2 TeCH 2 CH 3 14. HOCH 2 CH 2 TeCH 2 CH 2 CH 2 2 CH 2 CH ₂ OH 16. HOCH ₂ CH ₂ TeCH ₂ CH ₂ OCH ₂ CH ₂ TeCH ₂ CH ₂ OH 17. HOCH ₂ CH ₂ TeCH ₂ CH ₂ CH ₂ SCH ₂ CH ₂ CH ₂ TeCH ₂ CH ₂ OH 19. HOCH ₂ CH ₂ TeCH ₂ CH ₂ NHCH ₂ CH ₂ TeCH ₂ CH ₂ OH 20.H ₂ NCH ₂ CH ₂ TeCH ₂ CH ₂ NHCONHCH ₂ CH ₂ TeCH ₂ CH ₂ NH ₂ Regarding the synthesis of the polytelluroether compound (telluride) used in the present invention, one of the general ones is as follows.
There is a method in which diorganyl ditelluride is reduced to generate a tellurate anion, and a substitution reaction is caused with an organic halide to obtain telluride.

An example using this method is "Journal of the Chemical Society, Dalton Transaction" (Ja
rnal of Chemical Society, Dalton transaction) 2143
(1983), "Journal of Chemical Society, Dalton Transaction" (Jarnal of Ch.
emical Society, Dalton transaction) 2003 (1986)
Year).

The polytelluroether compound used in the present invention can be synthesized according to these.

In the present invention, the polytelluroether compound is added in at least one step selected during precipitation of silver halide grains, subsequent physical ripening, chemical ripening, and immediately before coating during emulsion production. Preferably. It is preferably added during precipitation, physical ripening, or chemical ripening.

In the present invention, as a method for forming silver halide grains, a general method well known in the art can be used, but a double jet method is particularly preferable.

The double jet method is a method in which an aqueous solution of silver nitrate and an aqueous solution of one or more halides (for example, an alkali metal halide such as potassium bromide) are simultaneously sprayed by two separate jets into a protective colloid of silver halide (for example, gelatin or gelatin). Derivative) is added to the stirred solution.

In the present invention, in order to add the organic telluro ether compound during precipitation of silver halide and / or during physical ripening, it is preferable to add the organic telluro ether compound to the solution of the protective colloid before the start of precipitation. The protective colloid solution can be added via a jet for adding the halide and / or a jet for adding silver nitrate, or via another jet.

In the present invention, the photographic emulsion is P.Gl.
afkides), Chimie et Physique Photographique, published by Paul Montel (1967), GFDuffin, Photographic Emulsion Chemistry (GFDuffin) Photographic Emulsio
n Chemistry), The Focal P
ress) (1966), by Wier Zürichmann, et al. (V.
L. Zelikman et al) Making and Coating Photographic Emulsion (Making and Coa)
ting Photographic Emulsion), The Focal Press (1964), and the like. That is, any of an acidic method, a neutral method, an ammonia method, and the like may be used, and a method of reacting a soluble silver salt and a soluble halide may be any of a one-sided mixing method, a simultaneous mixing method, a combination thereof, and the like. .

A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used.

The grain size distribution of the silver halide grains in the photographic emulsion is arbitrary, but is preferably monodispersed. Here, monodisperse means that 95% of the particles are within ± 60% of the number average particle size,
A dispersion preferably falls within a size of 40% or less. Here, the number average grain size is the number average diameter of the projected area diameter of the silver halide grains.

Two or more types of silver halide emulsions formed separately may be used as a mixture.

In the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver iodide and silver chloride may be used as the silver halide in the photographic emulsion.

The particle size distribution may be narrow or wide.

Silver halide grains in photographic emulsions are cubic, octahedral,
It may have a regular crystal such as a tetrahedron or a rhombic dodecahedron, or may have an irregular crystal form such as a sphere or a plate, or a crystal form thereof. It may have a composite shape of

It may consist of a mixture of particles of different crystal forms. Further, a crystal having a higher index plane may be used.

The silver halide grains may have different phases between the inside and the surface layer or may consist of a uniform phase. Particles having a double structure or multiple structures may be used.

Also, for example, a junction type silver halide crystal in which an oxide crystal such as PbO is combined with a silver halide crystal such as silver chloride, and a silver halide crystal grown epitaxially (for example, silver chloride on silver bromide, Silver iodobromide, silver iodide and the like are epitaxially grown.), Hexagonal crystals, crystals in which regular hexahedral silver chloride is oriented and overlapped with silver iodide, and the like may be used.

Further, tabular silver halide grains having an aspect ratio of 3 or more, preferably 5 to 20 can also be used. More specifically, US Pat. Nos. 4,434,226, 4,439,520, European Patent 84,637A _2, JP-A-59-99433, "Research Disclosure" Vol. 225, are described in, for example, No.22534 (1 January 1983) I have.

Also, Japanese Patent Application Nos. 63-7581, 63-7852, 63-7553.
The silver halide grains may be formed by the method described in (1).

PH at the time of silver halide grain formation in the present invention, pAg,
Although there are no particular restrictions on conditions such as temperature, the pH value is about 1
~ 10, particularly preferably 2-8, and pAg value of about 5
It is preferred to keep it at about 11, especially 7.8 to 10.5.

Although silver halide grains can be formed at a temperature of about 30 to about 90 ° C, 35 to 80 ° C is particularly preferable.

Of course, pH, pAg and temperature may be changed during the formation of silver halide grains.

In the course of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, or the like may coexist. Particularly preferred are lead salts, iridium salts, rhodium salts and iron salts. Also,
The addition amount thereof may be small or large depending on the intended light-sensitive material.

The amount of the polytelluroether compound of the present invention added during the formation of silver halide grains may be 0.001 to 100 g per mol of silver halide, but is preferably used.
It is 0.003 to 30 g, and particularly preferably 0.005 to 10 g.

Further, simultaneously with the polytelluroether compound of the present invention,
The above-mentioned known thioether compounds, ammonia, thiocyanate (for example, rodankari), and
No. 51252, JP-A-55-77737, U.S. Pat.No.4,221,863
And the compounds described in JP-B-60-11341 and the like may be used in combination.

When the polytelluroether compound of the present invention is used before chemical ripening (for example, during silver halide grain formation), the function as a silver halide solvent can be reduced by the method described in JP-A-60-136736. It can also be deactivated.

In the present invention, as described above, the polytelluroether compound can be added in the chemical ripening step.

In this case, the addition amount of the polytelluroether compound of the present invention is 0.001 to 10 g, preferably 0.1 to 10 g per mol of silver halide.
003 to 1 g is preferred.

Conditions of the chemical ripening step in the present invention, for example, pH, pA
There are no particular restrictions on g, temperature, time, additives, and the like, and the reaction can be performed under conditions generally performed in the art.

For example, the pH value is preferably 3.0 to 8.5, particularly 5.0 to 7.5, the pAg value is preferably 7.0 to 9.5, particularly 8.0 to 9.3, and the temperature is 40 to 85 ° C, particularly preferably 45 to 75 ° C. Is preferably 5 to 200 minutes, particularly preferably 10 to 120 minutes.

In the present invention, as described above, the polytelluroether compound can also be added in the step immediately before coating, and the amount of addition at that time is 0.
001 to 10 g, particularly 0.003 to 5 g, is preferred.

In order to remove soluble salts from the emulsion after the formation of the precipitate or after the physical ripening, a Nudel washing method, which is performed by gelling gelatin, may be used. Inorganic salts, anionic surfactants, anionic polymers (or For example, a sedimentation method (a flocculation method) using a gelatin derivative (for example, an acylated gelatin, a carbamoylated gelatin, or the like) may be used.

Silver halide emulsions are usually chemically sensitized. For chemical sensitization, for example, H. Friese
r) ed. "Die Grundlagender Photographischen Proze"
sse mit Silberhalogeniden ”(Akademische Verlagsgesllschaft, 1968)
Annual publication) pp. 675-734 can be used.

That is, a sulfur sensitization method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a selenium sensitization method, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or another noble metal compound, etc. They can be used alone or in combination. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used.

Examples of the reduction sensitizer include stannous salts, amines, hydrazine derivatives, formamidinesulfinic acid, and silane compounds. In order to sensitize noble metals, gold complex salts such as chloroauric acid and gold dithiocyanate (however,
Gold cyanide is not preferred. In addition to the above, complex salts of metals belonging to the periodic group VIII such as platinum, iridium, and palladium can be used.

In particular, a sensitization method using a noble metal such as a gold compound and a sensitization method using a sulfur compound can be preferably used.

Further, for the purpose of increasing sensitivity, increasing contrast, or promoting development, for example, polyalkylene oxide or derivatives thereof such as ethers, esters, amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives , 3-pyrazolidones and the like. For example, U.S. Patent Nos. 2,400,532, 2,423,549, 2,716,062,
Nos. 3,617,280, 3,772,021, and 3,808,003 can be used.

Further, various compounds can be contained for the purpose of preventing fogging during the production process, storage or photographic processing of the photographic material or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidizoles, mercaptothiazoles, mercaptobenzothiazoles,
Mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines; mercaptotriazines; Thioketo compounds; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetrazaindenes), pentaazaindenes and the like; benzenesulfinic acid, benzene Many compounds known as antifoggants or stabilizers, such as sulphonic acid amides, benzenethiosulphonic acid and the like can be added.

As the binder or protective colloid used for the photosensitive material, gelatin is advantageously used, but a hydrophilic synthetic polymer or the like can also be used. As gelatin, lime-processed gelatin, acid-processed gelatin, derivative gelatin, and the like can also be used.

Further, the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention may have a coating aid, an antistatic,
Various known surfactants may be included for various purposes such as improving slipperiness, emulsifying and dispersing, preventing adhesion, and improving photographic properties (for example, acceleration of development, contrast enhancement, sensitization).

The photographic emulsions of the present invention may be spectrally sensitized with methine dyes and the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hexoxonol dyes. Particularly useful dyes are those belonging to the merocyanine dyes and the complex merocyanine dyes. Any of nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; Nucleus fused with an aromatic hydrocarbon ring, i.e., indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole A nucleus and a quinoline nucleus can be applied. These nuclei may be substituted on carbon atoms.

In a merocyanine dye or a complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-
A 5- to 6-membered heterocyclic nucleus such as a 2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied.

The photographic emulsion of the present invention may contain a color image-forming coupler, that is, a compound (hereinafter abbreviated as coupler) which reacts with an oxidation product of an aromatic amine (usually a primary amine) developing agent to form a dye. The coupler is preferably a non-diffusible coupler having a hydrophobic group called a ballast group in the molecule.
The coupler may be either 4-equivalent or 2-equivalent to silver ion. Further, a colored coupler having a color correcting effect or a coupler which releases a development inhibitor upon development (a so-called DIR coupler) may be included. The coupler may be such that the product of the coupling reaction is colorless.

As the yellow color coupler, a known open-chain ketomethylene coupler can be used. Among these, benzoylacetoaniline and pivaloylacetoaniline compounds are advantageous.

As the magenta coupler, a pyrazolone-based compound, an indazolone-based compound, a cyanoacetyl compound, or the like can be used, and a pyrazolone-based compound is particularly advantageous.

As the cyan coupler, a phenol compound, a naphthol compound or the like can be used.

In addition to the DIR coupler, a compound which releases a development inhibitor upon development may be contained in the photosensitive material. For example, those described in U.S. Pat. Nos. 3,297,445 and 3,379,529 and West German Patent Application (OLS) 2,417,914 are used. it can.

Two or more couplers may be contained in the same layer. The same compound may be contained in two or more different layers.

In order to introduce the coupler into the silver halide emulsion layer, a known method such as the method described in US Pat. No. 2,322,027 is used.

The emulsion of the present invention is usually subjected to physical ripening, chemical ripening and spectral sensitization. The additives used in such processes are described in Research Disclosure No. 17
Volume 6, No. 19643 (December 1978) and Volume 187, No. 187
16 (November 1979), and the relevant locations are summarized in the table below.

Known photographic additives that can be used in combination with the present invention are also described in the above two research disclosures, and their locations are shown in the table below.

The silver halide emulsion of the present invention can be used as a black-and-white silver halide photographic light-sensitive material (for example, an X-ray light-sensitive material, a lithographic light-sensitive material, a negative film for black-and-white photographing) or a color photographic light-sensitive material (for example,
Color negative film, color reversal film, color paper, etc.). Further, it can be used as a light-sensitive material for diffusion transfer (for example, a color diffusion transfer element, a silver salt diffusion transfer element), and a heat-developable light-sensitive material (black and white, color).

The photographic emulsion of the present invention can be applied to a rigid support such as plastic film or paper or a rigid support such as glass, which is commonly used for photographic light-sensitive materials, by dip coating, roller coating, curtain coating, extrusion coating. It is applied by a method or the like. Those useful as flexible supports are cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate,
Examples of the film include a film made of a semi-synthetic or synthetic polymer such as polycarbonate, a baryta layer, and paper coated or laminated with an α-olefin polymer (eg, polyethylene, polypropylene, ethylene / butene copolymer).

The photographic processing of the photosensitive material made by applying the present invention includes:
Any of the known methods can be used. Known treatment liquids can be used. Processing temperature is usually 18 ℃
To 50 ° C, but lower than 18 ° C or 50 ° C
The temperature may exceed ℃. Depending on the purpose, any of a developing process for forming a silver image (black-and-white photographic process) and a color photographic process including a developing process for forming a dye image can be applied.

See Research Disclosure No. 176
No. 17643, pp. 28-29, and Vol. 187, No. 18716, page 651, left column and right column.

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples and Examples.

Synthesis Example (Synthesis Method of Exemplified Compound 1) 1) Synthesis of 2,2'-ditellazidiethanol (C ₄ H ₁₀ O ₂ Te ₂ ) 12.7 g (0.1 mol) of metal tellurium powder was dried under an argon atmosphere under a yellow lamp. Dimethylformamide (DM
F) The mixture was dispersed in 500 ml, 0.11 mol of sodium hydride was added, and the mixture was heated and stirred at 70 ° C for 3 hours. The reaction turned purple. Then cool to room temperature, and then add bromoethanol 7.
8 ml of DMF solution was added. The reaction was allowed to proceed at room temperature for 1 hour, and the reaction solution was poured into about 1 of water, extracted with diethyl ether, washed with water and dried, and the ether was distilled off to obtain about 14 g of an oily product. This is purified by silica gel column chromatography,
9 g of a dark-lit oily target product was obtained. The structure of the target compound was identified by nuclear magnetic resonance spectrum, mass spectrum, and elemental analysis.

2) Method for synthesizing 3,7-ditellura-1,9-nanonediol (Exemplary Compound 1) Dissolve 7.2 g of 2,2'-ditelluradiethanol in 400 ml of dry ethanol, and borohydride under an argon atmosphere under a yellow light. Sodium was added. After the light blue solution becomes transparent, cool to 0 ° C and dibromopropane (20 mmol)
Of ethanol was added. The reaction was slowly warmed to room temperature and stirred for 3 hours. Next, the reaction solution was poured into water, extracted with diethyl ether, dried and concentrated. About 3 g of an oil was obtained. This was purified by silica gel column chromatography.

The nuclear magnetic resonance spectrum and mass spectrum of the target product were consistent with those expected from the structure of the target product (MS, m / z392
(M ⁺ [ ¹³⁰ Te]); NMR (CDCl ₃ ) δ 2.1-2.2 (m.2H), 2.
7-2.9 (m.8H), 3.1-3.4 (br-s.2H), 3.7-4.0 (t.
4H) (Example) Example 1 A silver nitrate aqueous solution and a mixed aqueous solution of potassium bromide and potassium iodide were simultaneously added while vigorously stirring an aqueous solution containing gelatin and potassium bromide at 70 ° C.
A monodispersed octahedral silver iodobromide emulsion containing 2 mol% of silver iodide and having an average grain size of 0.80 μm was prepared.

After removing unnecessary salts by flocculation, the emulsion was divided into 12 parts by adjusting the pH to 6.3 and the pAg to 8.4, and sodium thiosulfate, chloroauric acid and potassium thiocyanate were added to each emulsion. Were added, and the mixture was chemically aged at 60 ° C. so as to exhibit the optimum sensitivity.

In the emulsion thus obtained, the following antifoggant, stabilizer,
A hardener and a coating aid were added, and the mixture was coated on a polyethylene terephthalate film support by a coextrusion method together with a gelatin surface protective layer, followed by drying to obtain Samples 1 to 12.

Antifoggant; 1- (p-carboxyphenyl) -5-mercaptotetrazole Stabilizer; 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene Hardener; 2,4-dichloro-6 -Hydroxy-1,3,5-triazine sodium salt Coating aid: Sodium dodecylbenzenesulfonate The obtained sample was immediately exposed through an optical wedge using a sensitometer (1/100 sec.) Developed at 35 ° C. for 30 seconds with an RD-III developer for use (manufactured by Fuji Photo Film Co., Ltd.), fixed, washed and dried by a conventional method, and measured for photographic sensitivity. The photographic sensitivity is represented by the relative value of the reciprocal of the amount of exposure required to obtain an optical density of fog value +0.2.
100 was set.

The sample was placed in an atmosphere at 35 ° C and 75% relative humidity.
After storage for a day, the same development processing was performed.

As is clear from Table 1, the polytelluroether compound of the present invention not only increases the sensitivity but also increases the sensitivity as compared with the conventional thioether compound (comparison compound (a)) and telluroether compound (comparison compounds (b) and (c)). Thus, there is a great advantage that the decrease in sensitivity when stored at high temperature and high humidity is small.

Example 2 At the time of grain formation in the core portion, 3,6-dithia-1,8-octanediol was used, and then hydrogen peroxide was added. Further, a silver nitrate aqueous solution corresponding to the shell portion and a mixed aqueous solution of potassium bromide and potassium iodide were used. Was added by the double jet method to obtain an internal high iodine type double structure having an average iodine content of 8 mol% and a core-shell ratio of 1: 3, a sphere equivalent diameter of 0.7 μm, and a diameter / thickness ratio of 5.0.
Was prepared, and chloroauric acid, potassium thiocyanate and sodium thiosulfate were added thereto, and the mixture was heated at 60 ° C. for 45 minutes to perform gold-sulfur sensitization.

The obtained emulsion was divided into 5 parts, and the spectral sensitizing dye (S-1)
Was added, and then the compounds shown in Table 2 were added. Further, a coupler dispersion (Cp-1, Oil-1, Oil-2), an antifoggant (1- (m-sulfophenyl) -5-mercaptotetrazole mono-Na salt), a stabilizer (4-hydroxy-6)
-Methyl-1,3,3a, 7-tetrazaindene)
After further 2 minutes, the hardening agent (H-) was added to the one immediately after (A) and the one after continuous dissolution at 40 ° C. for 6 hours (B).
1) and a coating aid (sodium p-dodecylbenzenesulfonate and sodium p-nonylphenoxypoly (ethyleneoxy) propanesulfonate) were added, and coated with a gelatin surface protective layer on a cellulose or triacetate film support. Dried samples 13 (A) to 17 (A),
13 (B) to 17 (B) were obtained. The sample was exposed under a light wedge (1/1 /
100 seconds) After performing the following color development processing, photographic properties were measured, and the results shown in Table 2 were obtained.

The sensitivities in Table 2 were the same as in Example 1 for the samples.
The value of 13 (A) was set to 100, and the others were relatively expressed.

1. Color development 2 minutes 45 seconds (38 ° C) 2. Bleaching 6 minutes 30 seconds 3. Rinse 3 minutes 15 seconds 4. Fixed 6 minutes 30 seconds 5. Rinse 3 minutes 15 seconds 6. Stable 3 minutes 15 seconds The composition of the processing solution used in each step is as follows.

Color developer Sodium nitrilotriacetate 1.0 g Sodium sulfite 4.0 g Sodium carbonate 30.0 g Potassium bromide 1.4 g Hydroxylamine sulfate 2.4 g 4- (N-ethyl-N-β-hydroxyethylamino)
-2-Methyl-aniline sulfate 4.5g Add water 1 Bleaching solution Ammonium bromide 160.0g Ammonia water (28%) 25.0ml Ethylenediaminetetraacetic acid sodium iron salt 130.0g Glacial acetic acid 14.0ml Add water 1 Fixer Sodium tetrapolyphosphate 2.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (70%) 175.0 ml Sodium bisulfite 4.6 g Add water 1 Stabilizer Formalin 8.0 ml Add water 1 Oil-1 Tricresyl phosphate Oil-2 Dibutyl phthalate As is clear from Table 2, the polytelluroether compound of the present invention has less fogging even when the dissolution time until the emulsion is coated is long, as compared with the comparative compound.
In addition, there is an advantage that the decrease in sensitivity is small and the original sensitizing effect is at least about the same.

Example 3 After the compounds shown in Table 3 were added to an aqueous solution containing gelatin and potassium bromide kept at 60 ° C., an aqueous solution of silver nitrate and an aqueous solution of potassium bromide were added simultaneously, and pAg was adjusted to 8.3.
Silver bromide emulsions A to D were prepared by the CDJ method keeping the temperature.

The average particle size was determined using the obtained silver bromide particles and an electron microscope, and the results are shown in Table 3.

As is clear from Table 3, the polytelluroether compound of the present invention can increase the particle size of silver bromide particles as in the case of the comparative compound (b). Moreover, the tellurium compound of the comparative compound (b) needs to be dissolved in acetone and added, which has a disadvantage that the gelatin is easily aggregated by acetone and further the particles themselves are easily aggregated. Because many compounds are soluble in lower alcohols such as methanol and even water, Ag
It has a great advantage that the aggregation of Br particles is small.

(Effect of the Invention) The polytelluroether compound of the present invention is disclosed in JP-A-53-57.
Although the effect of increasing the photographic sensitivity is the same as that of the conventional tellurium compound described in No. 817, the photographic performance of the coated photographic material during storage can be reduced as compared with the compound of JP-A-53-57817. It has the great advantage that degradation is small, and also has the advantage that the change in photographic sensitivity is small even if the dissolution time of the emulsion immediately before coating on the support is long, which is called dissolution aging. Was the result.

Claims (1)

(57) [Claims] 1. A silver halide photographic material comprising at least one compound represented by the following general formula (I). Formula (I) L ₁ -Te-L ₂ -Te-L ₃ L ₂ is a divalent compound containing at least one of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom. Represents an organic group. L ₁ and L ₃ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group Represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group.