JP2000231171A - Silver halide photographic emulsion and method for sensitization thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic emulsion having high sensitivity by measuring an absorption spectrum caused by the chalcogen sensitization center of the emulsion which is sensitized with a chalcogen and controlling the absorption to be in a narrow range. SOLUTION: The silver halide photographic emulsion is sensitized with chalcogen and shows the absorption spectrum of the chalcogen sensitization center with a halfwidth between 1,200 cm-1 and 3,900 cm-1. Preferably, the halfwidth of the absorption is <=3,600 cm-1, more preferably <=3,200 cm-1, and especially preferably <=2,800 cm-1, and is >=1,200 cm-1. The smaller the halfiwdth, the sharper spectrum is obtd. Further, it is preferable to combine chalcogen sensitization with noble metal sensitization such as gold sensitization together. The use amt. of the chalcogen and the noble metal sensitizer depends on the silver halide particles used or chemical sensitization conditions, and 10-8 to 10-2 mol of sensitizers, preferably about 10-7 to 10-3 mol can be used to 1 mol of silver halides.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic emulsion and a method for sensitizing the same, and more particularly to a silver halide photographic emulsion having improved storage stability and fog.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for silver halide photographic light-sensitive materials having high sensitivity, excellent graininess, gradation and high sharpness, good preservability, and rapid processing with further development progress. It is getting stronger.

[0003] Silver halide emulsions are usually subjected to chemical sensitization using various chemical substances in order to obtain desired sensitivity, gradation and the like. Specific methods include sulfur sensitization, chalcogen sensitization such as selenium sensitization and tellurium sensitization, noble metal sensitization using a noble metal such as gold, and reduction sensitization using a reducing agent. Used alone or in combination.

[0004] Of these, chalcogen sensitization is the most basic chemical sensitization method for silver halide photographic emulsions, and various studies have hitherto been made for high sensitivity. However, as high sensitivity is obtained, defects such as a change in sensitivity during storage, an increase in fog, and a change in gradation always increase, and improvement thereof has been strongly desired. Usually, improvements have been made by adding compounds such as antifoggants and stabilizers, but these have been accompanied by various adverse effects such as impairing the original high sensitivity and delaying the progress of development. In order to solve these drawbacks, it has been strongly desired to improve the chalcogen sensitization center itself to one that is strong in preservability, but there is no specific means to achieve it and no means for its detection, so trial and error is required. It has only been done.

[0005]

SUMMARY OF THE INVENTION The first object of the present invention is as follows.
Is to provide a silver halide photographic emulsion having high sensitivity. A second object of the present invention is to provide a silver halide photographic emulsion having high storability and high sensitivity. A third object of the present invention is to provide a chemical sensitization method for preparing a silver halide photographic emulsion having good storability and high sensitivity.

[0006]

The above objects of the present invention are:
This was achieved by the following (1) and (2). (1) Chalcogen-sensitized silver halide photographic emulsion
And chalcogen sensitization produced by the chalcogen sensitization
Half-width of absorption spectrum at center is 3900cm^-1Below, 1
200cm^-1Silver halide photography characterized by the above
True emulsion. (2) Method of sensitizing a silver halide photographic emulsion to chalcogen
, The chalcogen formed by the chalcogen sensitization
Half width of absorption spectrum at sensitization center is 3900 cm ^-1Less than
Below, 1200cm^-1What to do by controlling so that
Characteristic method of chalcogen sensitization of silver halide photographic emulsion
Law.

[0007]

The present invention will be described more specifically. An object of the present invention is to provide a chalcogen sensitized product, wherein the half width of the absorption spectrum of the chalcogen sensitized center produced thereby is 3%.
Is achieved by a silver halide photographic emulsion, wherein 900cm less than ^-1 1200 cm ^-1 or more, preferably a half-width of absorption 3600 cm ^-1 or less, more preferably 3
200 cm ^-1 or less, preferably especially 2800 cm ^-1 or less, 1
200 cm ^-1 or more is sufficient. The smaller the half width value, the sharper the absorption.

The chalcogen sensitizing center is made of silver sulfide, silver selenide or silver telluride. For example, a silver halide emulsion sensitized with sulfur has an absorption of silver sulfide which is a sulfur sensitizing center in the visible region. Was previously known. For example, Journal of Photographic Science, 1
4, 181 (1966), 16: 102 (1
968), and the Photographic Society of Japan, Vol. 59, p. 435 (199)
6 years). However the absorption spectrum of a sulfur sensitization center known in these are very broad, half-value width was very large be around 5000 cm ^-1 exceeding 4000 cm ^-1. Moreover, no attempt has been made to control chalcogen sensitization to a high degree and precision by using this. The present invention measures the absorption spectrum provided by the chalcogen sensitized centers of a chalcogen sensitized emulsion and by controlling it to a particular shape, specifically to a narrower absorption than previously known, The object of the present invention has been achieved.

The chalcogen sensitization in the present invention is sulfur sensitization, selenium sensitization, and tellurium sensitization, and they can be used alone or in combination.

[0010] In sulfur sensitization, an unstable sulfur compound is used and is described by Chimie et Physique Photograph by P. Grafkides.
ique (Paul Momtel, 1987, 5th edition), Resea
Unstable sulfur compounds described in rchDisclosure, Vol. 307, No. 307105, etc. can be used. Specifically, thiosulfates (eg, hypo), thioureas (eg, diphenylthiourea, triethylthiourea, N-
Ethyl-N ′-(4-methyl-2-thiazolyl) thiourea, carboxymethyltrimethylthiourea), thioamides (eg, thioacetamide), rhodanines (eg, diethyl rhodanine, 5-benzylidene-N-ethyl rhoda) Nin), phosphine sulfides (eg, trimethylphosphine sulfide), thiohydantoins, 4-oxo-oxazolidine-2-thiones, disulfides or polysulfides (eg,
Known sulfur compounds such as dimorpholine disulfide, cystine, hexathiocan-thione), mercapto compounds (eg, cysteine), polythionates, elemental sulfur, and active gelatin can also be used. Particularly preferred are thiosulfates, thioureas and rhodanines.

In the selenium sensitization, an unstable selenium compound is used and disclosed in JP-B-43-13489 and JP-B-44-157.
No. 48, JP-A-4-25832, JP-A-4-109340
No. 4-271341, No. 5-40324, No. 5
-11385, Japanese Patent Application No. 4-202415, 4-3
No. 30495, No. 4-333030, No. 5-4203
Nos. 5-4204, 5-106977, 5-
No. 236538, No. 5-241642, No. 5-286
No. 916, etc. can be used. Specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, trifluoromethylcarbonyl-trimethylselenourea, acetyl-trimethylselenourea), selenoamides (eg, selenoamide, N, N -Diethylphenyl selenamide), phosphine selenides (eg, triphenylphosphine selenide, pentafluorophenyl-triphenylphosphine selenide), selenophosphates (eg, tri-p-tolylselenophosphate, Tri-n-butylselenophosphate), selenoketones (eg, selenobenzophenone), isoselenocyanates, selenocarboxylic acids, selenoesters, diacylselenides, and the like may be used. Further, non-labile selenium compounds described in JP-B-46-4553 and JP-B-52-3449, such as selenous acid, selenocyanate, selenazoles and selenides, can also be used. In particular, phosphine selenides, selenoureas and selenocyanates are preferred.

In tellurium sensitization, an unstable tellurium compound is used and disclosed in JP-A-4-224595 and JP-A-4-27713.
No. 41, 4-333430 and 5-303157
Nos. 6-27573, 6-175258, 6
-180478, 6-208186, 6-20
Nos. 8184, 6-317867 and 7-14057
No. 9, 7-301879, 7-301880, and the like can be used. Specifically, phosphine tellurides (for example,
Butyl-diisopropylphosphine telluride, tributylphosphine telluride, tributoxyphosphine telluride, ethoxy-diphenylphosphine telluride), diacyl (di) tellurides (for example, bis (diphenylcarbamoyl) ditelluride, bis (N- Phenyl-N-methylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) telluride, bis (N
-Phenyl-N-benzylcarbamoyl) telluride, bis (ethoxycarbonyl) telluride), telluroureas (e.g., N, N'-dimethylethylenetellurourea,
(N, N'-diphenylethylene tellurourea) telluramides, telluroesters and the like may be used. Particularly, diacyl (di) tellurides and phosphine tellurides are preferable.

It is preferable to use a combination of a chalcogen sensitizer of the present invention with a noble metal sensitizer such as a gold sensitizer.
For noble metal sensitization, see P. Grafkides, Chimie et Ph.
ysique Photographique (Paul Momtel, 1987
Year, 5th Edition), Research Disclosure Magazine, 307, 30
Noble metal salts such as gold, platinum, palladium, and iridium described in No. 7105 and the like can be used, and gold sensitization is particularly preferable. Specifically, chloroauric acid,
In addition to potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, U.S. Pat.
Nos. 642,361, 5,049,484, 5,0
49,485, 5,169,751, 5,25
No. 2,455, Belgian Patent No. 691,857 and the like can also be used. Specifically, a combination of gold sulfur sensitization, gold sulfur selenium sensitization, gold sulfur tellurium sensitization, and gold sulfur selenium tellurium sensitization is preferable.

Since the absorption spectrum of a silver halide emulsion when gold sensitization is used in combination with chalcogen sensitization changes with the gold sensitizer, the absorption spectrum of the chalcogen sensitized center formed by chalcogen sensitization is measured. For this purpose, it is necessary to remove the influence of gold sensitization for measurement. In order to eliminate the effect of the gold sensitizer, the absorption spectrum obtained when potassium cyanide was added in an amount of several to several tens of moles of the gold sensitizer was observed. half-width of it may be controlled to be 3900Cm ^-1 below 1200 cm ^-1 or more.

The amount of the chalcogen or the noble metal sensitizer used in the present invention varies depending on the silver halide grains used and the conditions of chemical sensitization.
^0-8 to ^10-2 mol, preferably about ^10-7 to ^10-3 mol can be used.

The conditions for chemical sensitization in the present invention include:
Although there is no particular limitation, the pAg is 6 to 11, preferably 7 to 10, and the pH is 4 to 10, preferably 5 to 5.
8. The temperature is 40 ° C to 95 ° C, preferably 45 ° C to
85 ° C.

The measurement of the absorption spectrum of the chalcogen sensitized center of the chalcogen-sensitized silver halide emulsion in the present invention is described in Journal of Photographic Science, Vol. 14, 181 (1966), and Vol. 102 pages (1968), and Photographic Society of Japan 5
9, p. 435 (1996). Specifically, the liquid emulsion is placed in a measuring cell having a thickness of 1 cm or several hundred μm on a glass dry plate.
The diffuse reflectance is measured with a spectrophotometer having an integrating sphere with reference to an unchemically sensitized silver halide emulsion as a thick film having a thickness of at least m. Kubelka-Munk
The value converted by equation (1-R) ² / 2R is plotted on the ordinate and the absorption spectrum is plotted on the abscissa, and the absorption value at half the peak height at the absorption maximum is expressed in cm ^-1 unit. The half width of the absorption is obtained by converting to The measurement of the absorption spectrum of the chalcogen sensitized center can be easily performed on-line at the time of chemical ripening, which is very effective in controlling the same.

If the addition amount of the chalcogen sensitizer is too small to obtain an absorption spectrum, it may be measured at an addition amount several times to several tens times the amount and applied. Also,
For example, when there is a compound having an absorption that interferes with the measurement of the absorption spectrum of the chalcogen sensitized center, such as absorption by a dye, the dye is added to the reference side to cancel the absorption, or the compound is not desorbed by an appropriate means. What is necessary is just to measure it after decoloring.

There are several methods for narrowing the half width of the absorption spectrum of the chalcogen sensitized center of the emulsion to be chalcogen sensitized. Specifically, as shown in Examples, various methine-based sensitizing dyes such as cyanine dyes and merocyanine dyes, and so-called antifoggants and chalcogen enhancers such as stabilizers having a hetero ring and adsorbing to silver halide grains. It is preferable to add a compound which influences the generation and growth of feeling to the extent of the present invention while measuring the absorption spectrum. Of course, if the absorption can be sharpened, the absorption can be performed by various other means, and the present invention is not limited to the above. The addition of a sensitizing dye or an antifogging agent during chemical sensitization has hitherto been performed, but these were merely added, whereas the present invention provides a chalcogen-sensitized silver halide. These are used to optimally measure and control the absorption spectrum of the chalcogen sensitized center formed by the chalcogen sensitization of the emulsion, and to control the chemical sensitization which has not been known until now. Is the way.

In the present invention, reduction sensitization may be further used. In particular, reduction sensitization is preferably performed during the formation of silver halide grains. In reduction sensitization, P. Grafkides
Written by Chimie et Physique Photographique (Paul Momtel
Published by 1987, 5th edition), Research Disclosure
307, 307105, etc. can be used. Specifically, aminoiminomethanesulfinic acid (also called thiourea dioxide), borane compound (for example, dimethylaminoborane), hydrazine compound (for example, hydrazine, p-tolylhydrazine), polyamine compound (for example, diethylenetriamine, triethylene Tetramine), stannous chloride, silane compounds, reductones (eg, ascorbic acid), sulfites, aldehyde compounds, hydrogen gas, and the like may be used. Further, reduction sensitization may be performed in an atmosphere having a high pH or an excess of silver ions (so-called silver ripening). In the present invention, thiosulfonates (eg, sodium benzenethiosulfonate), disulfide compounds (eg, bis (4-acetanilidephenyl) disulfide, lipoic acid), iodine, mercury salts and the like are particularly preferable. It is preferable to use a silver oxidizing agent such as an acid salt or a disulfide compound in combination.

In the present invention, the chemical sensitization of silver halide is preferably carried out in the presence of a silver halide solvent. Specifically, thiocyanates (for example, potassium thiocyanate), thioether compounds (for example, U.S. Pat. Nos. 3,021,215 and 3,271,157, JP-B-58-30571, JP-A-60-30) -136736, especially 3,6-dithia-1,8-octanediol and the like; tetrasubstituted thiourea compounds (for example, JP-B-59-11892, U.S. Pat. No. 4,221,86)
No. 3 compounds, especially tetramethylthiourea),
Further, a thione compound described in JP-B-60-1134,
Mercapto compounds described in JP-B-63-29727,
Examples include a mesoionic compound described in JP-A-60-163442, a selenoether compound described in U.S. Pat. No. 4,782,013, a teretherether compound described in JP-A-2-118566, and a sulfite. Among these, thiocyanates, thioether compounds, tetrasubstituted thiourea compounds and thione compounds can be preferably used, and thiocyanates are particularly preferable. As the usage,
It is about 10 ^-5 to 10 ^-2 mol per mol of silver halide.

Next, a description will be given of a silver halide emulsion sensitized by chalcogen in the present invention and a silver halide photographic light-sensitive material using the same (sometimes referred to simply as a light-sensitive material). The silver halide photographic material has a silver halide emulsion layer on a support.

The silver halide grain used in the present invention may be a final grain having two to multiple grains having different iodine compositions between the inside of the grain and the surface layer (such as a high iodine content or a high iodine content on the surface). Also, grains whose latent image is mainly formed on the surface (eg, a negative emulsion) may be formed, and grains whose main image is mainly formed inside the grains (eg, an internal latent image type emulsion, a directly fogged emulsion which has been previously fogged) The particles are preferably such that a latent image is mainly formed on the surface. The silver halide emulsion used in the present invention has tabular silver halide grains whose final grain shape has an aspect ratio of 2 or more,
It preferably contains tabular silver halide grains having an average aspect ratio of 6 or more, particularly preferably 8 or more, and preferably 60% or more of the total projected area is occupied by such tabular silver halide grains. The diameter of the tabular grains is 0.
It is preferably from 15 to 5.0 μm (equivalent circle diameter). The thickness of the tabular grains is 0.02 to 1.0 μm,
It is preferably 0.03 to 0.5 μm, particularly preferably 0.1 to 0.5 μm.
It is preferably from 0.3 to 0.3 μm. The average aspect ratio is determined as an arithmetic average of the aspect ratio of each grain for at least 100 silver halide grains.

When the final particles are normal crystals, spherical or three-dimensional particles, the diameter is 0.05 μm to 3 μm, preferably 0.08 μm to 2 μm, and the coefficient of variation is 30%.
A monodispersed emulsion having a content of 20% or less, more preferably 15% or less, is more preferred. The main plane of the tabular grains of the final grains may be the (111) plane or the (100) plane.

When monodisperse tabular grains are used, more preferable results can be obtained. The structure and production method of the monodisperse tabular grains are described in, for example, JP-A-63-151618, but the shape is briefly described as follows: 70% or more of the total projected area of the silver halide grains is a minimum. The ratio of the length of the side having the maximum length to the length of the side having the length is a hexagonal shape having a value of 2 or less, and a tabular silver halide having two parallel surfaces as outer surfaces. Further, the coefficient of variation of the grain size distribution of the hexagonal tabular silver halide grains (the value obtained by dividing the variation (standard deviation) of the grain size represented by the circle-converted diameter of the projected area thereof) by the average grain size. ) Is 30% or less, preferably 20%
In the following, it is particularly preferable to have a monodispersity of 15% or less.

Further, the final grain emulsion of the present invention preferably has dislocation lines. Dislocations of tabular grains, for example, J.
F. Hamilton, Phot.Sci. Eng., 11, 57, (1967) and T.
Shiozawa, J. Soc. Phot. Sci. Japan, 35, 213, (19
It can be observed by a direct method using a transmission electron microscope at low temperature described in 72). The dislocation lines may be edge dislocations or spiral dislocations. 5 or more per particle,
It is preferable to have 10 or more dislocation lines.
Further, it is preferable to have dislocation lines around the tabular grains (fringe portions).

When forming the silver halide grains,
As a silver halide solvent for controlling the growth of grains, for example, ammonia, rodancali, rodanammon, thioether compounds (for example, US Pat. No. 3,27
No. 1,157, No. 3,574,628, No. 3,7
Nos. 04,130, 4,297,439 and 4,
276, 374), thione compounds (for example,
Nos. 144443, 53-82408, 55-7
7737), amine compounds (for example, JP-A-54-10).
0717) can be used.

In the course of silver halide grain formation or physical ripening, a ruthenium salt (eg, hexacyanoruthenium), a zinc salt, a chromium salt, an iridium salt or a complex salt thereof (eg, iridium hexachloride), a rhodium salt or a complex salt thereof (eg, Rhodium chloride), an iron salt or an iron complex salt (for example, yellow blood salt) may be allowed to coexist. Particularly, iridium salts, iron salts, and rhodium salts are preferred. Particularly, a hexacoordinate compound is preferable. As a binder or protective colloid which can be used in the emulsion layer or intermediate layer of the photographic material, gelatin is advantageously used, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol It is possible to use various synthetic hydrophilic polymer substances such as a single or copolymer of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole. it can.

The tabular grains of the present invention are described in "Cleve, Photography Theory and Practice" by Cleve.
(1930)), p. 131; Photographic Science and Engineering (Gutoff, Photog)
raphic Science and Engineering), Vol. 14, 248
257 (1970); U.S. Patent No. 4,434,2.
No. 26, No. 4,414,310, No. 4,433,04
8 and 4,439,520 and British Patent 2,1
12,157 and the like. Examples of gelatin include general-purpose lime-processed gelatin, acid gelatin, and the journal of the Japan Science Photographic Society (Bull. Soc. P.
hot. Japan), No. 16, page 30 (1966) may be used, or a hydrolyzate of gelatin may be used.

The photographic light-sensitive material may contain an inorganic or organic hardener in any hydrophilic colloid layer constituting the photographic light-sensitive layer or the back layer. For example, chromium salt,
Aldehyde salts (for example, formaldehyde, glyoxal, glutaraldehyde) and N-methylol-based compounds (for example, dimethylol urea) are specifically mentioned. Active halogen compounds (for example, 2,4-dichloro-6
-Hydroxy-1,3,5-triazine and its sodium salt) and active vinyl compounds (e.g., 1,3-bisvinylsulfonyl-2-propanol, 1,2-bis (vinylsulfonylacetamido) ethane, bis (vinylsulfonylmethyl) ) A vinyl polymer having an ether or vinylsulfonyl group in the side chain) is preferred because it rapidly cures a hydrophilic colloid such as gelatin and gives stable photographic properties. N-carbamoylpyridinium salts (eg, (1-morpholinocarbonyl-3-pyridinio) methanesulfonate) and haloamidinium salts (eg, 1- (1-chloro-1-pyridinomethylene) pyrrolidinium-2-naphthalenesulfonate) also cure. Excellent early.

The silver halide photographic emulsion used in the present invention is preferably spectrally sensitized with a methine dye or the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes,
Styryl dyes and hemioxonol dyes are included. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes.
That is, the pyrroline nucleus includes 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 aromatic hydrocarbon ring is fused to these nuclei, i.e., indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, A benzimidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may have a substituent on a carbon atom.

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

These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. For example, an aminostilbenzene compound substituted with a nitrogen-containing heterocyclic nucleus group (for example, those described in U.S. Pat. Nos. 2,933,390 and 3,635,721), formaldehyde condensation of an aromatic organic acid (Eg, US Pat. No. 3,743,743)
510), cadmium salts, azaindene compounds and the like. US Patent 3,615,6
No.13, No.3,615,641, No.3,617,29
The combinations described in JP-A Nos. 5 and 3,635,721 are particularly useful.

The silver halide photographic emulsion used in the present invention contains various compounds for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. Can be done. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, and aminotriazole , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrithion; azaindenes; Triazaindenes, tetraazaindenes (especially 4-hydroxy-6
-Methyl (1,3,3a, 7) tetraazaindene),
Many compounds known as antifoggants or stabilizers, such as pentaazaindenes; benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonamide, can be added.

The photographic light-sensitive material contains one or more surfactants for various purposes such as coating aids, antistatic properties, improvement of slipperiness, emulsification / dispersion, prevention of adhesion, and improvement of photographic properties (eg, development acceleration, high contrast, sensitization). May be included.

The photographic light-sensitive material is used as a filter dye,
Alternatively, a water-soluble dye may be contained in the hydrophilic colloid layer for the purpose of preventing irradiation or halation and other various purposes. As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, and azo dyes are preferably used.In addition, cyanine dyes, azomethine dyes, triarylmethane dyes, and phthalocyanine dyes are also useful. . The oil-soluble dye may be emulsified by an oil-in-water dispersion method and added to the hydrophilic colloid layer.

The photographic light-sensitive material is provided on a support with at least 2
It can be constructed as a multilayer multicolor photographic material having two different spectral sensitivities. The multilayer natural color photographic material usually has at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The arrangement order of these layers can be arbitrarily selected as needed. The preferred layer arrangement is from the support side in the order of red sensitivity, green sensitivity and blue sensitivity, blue sensitivity, green sensitivity and red sensitivity or blue sensitivity, red sensitivity and green sensitivity. In addition, any emulsion layer having the same color sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the reaching sensitivity, or a three-layer constitution may be used to further improve the graininess.
Further, a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. An emulsion layer having a different color sensitivity may be inserted between emulsion layers having the same color sensitivity. A reflective layer of fine grain silver halide or the like may be provided below the high-sensitivity layer, particularly the high-sensitivity blue-sensitive layer, to improve the sensitivity. Additives used in the silver halide emulsion used in the present invention are Research Disclosure Nos. 17643 and 17643.
18716 and No. 307105, and the relevant portions are summarized in the table below.

Types of Additives RD17643 RD18716 RD307105 [December 1978] [November 1979] [November 1989] 1. Chemical sensitizer page 23 page 648 right column page 866 2. Sensitivity increasing agent, page 648, right column 3. Spectral sensitizers, pages 23 to 24, page 648, right column 866 to 868, super sensitizers, page 649, right column Brightener 24 page 647 page right column 868 page 5. 5. Fogging prevention, pages 24 to 25, page 649, right column, pages 868 to 870 Agents and stabilizers 6. Light absorber, page 25-26, page 649, right column, page 873, filter-page 650, left column, dye, infrared ray absorber. 7. Stain prevention, page 25, right column, page 650, left to right column, page 872 8. Dye image stability page 25 650 page left column page 872 Hardener page 26, page 651, left column, pages 874-875 10. Binder page 26, page 651, left column, pages 873-874 11. Plasticizer, lubrication page 27, page 650, right column page 876 agent 12. Coating aids, 26-27 Page 650 Right column 875-876 Surfactant 13. Static 27 Page 650 Right column 876-877 Inhibitor 14. Matting agent 878-879

Other techniques and inorganic and organic materials that can be used in the photographic light-sensitive material of the present invention are described in the following portions of European Patent 436,938A2 and in the patents cited below. 1. 1. Layer structure: page 146, line 34 to page 147, line 25 2. Yellow coupler; page 137, line 35 to page 146, line 33, page 149, lines 21 to 23; 3. Magenta coupler; page 149, lines 24 to 28; EP 421,453 A1, page 3, line 5 to page 25, line 55 4. Cyan coupler; page 149, lines 29 to 33; EP 432,804 A2, page 3, line 28 to page 40, line 2. 5. Polymer coupler; page 149, lines 34 to 38; EP 113,334A2, page 113, line 39 to page 123, line 37. 6. Colored coupler: page 53, line 42 to page 137, line 34, page 149, line 39 to line 45 From page 7, line 1 to page 53, line 41, page 149, line 46 Puller to page 150, line 3; page 3, line 1 of EP 435,334A2 Page 29, line 50 8. 8. Antiseptic / antifungal agent; page 150, lines 25-28 Page 149, lines 15-17, anger 10. Other additives; page 153, lines 38-47; EP 421, 453A1, page 75, lines 21-84. Page 56, line 27, page 40 to page 37, line 40 11. Dispersion method; page 150, lines 4 to 24 12. Support; page 150, lines 32 to 34 13. Page 150, lines 35 to 49; 14. Color development step; page 150, line 50 to page 151, line 47 15. Desilvering step; page 151, lines 48 to 152 Page 53, line 16. Automatic developing machine; page 152, line 54 to page 153, line 2 17. Rinse / stabilization process; page 153, lines 3 to 37

The present invention can be applied to various color and black-and-white photographic materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers, color diffusion transfer type photosensitive materials and heat development type color photosensitive materials. . Research Disclosure No. 171
23 (July 1978), or by utilizing a three-color coupler mixture or as described in U.S. Pat.
The present invention can be applied to black-and-white photographic materials for X-rays and the like by utilizing the black color couplers described in U.S. Pat. No. 461 and British Patent 2,102,136. Stencil film such as squirrel film or scanner film,
The present invention is also applied to X-ray film for direct medical treatment, indirect medical treatment, or industrial use, negative black-and-white film for photography, black-and-white photographic paper, COM or ordinary microfilm, silver salt diffusion transfer type photosensitive material and printout type photosensitive material. it can.

Preferred embodiments of the present invention are shown below. (1) is chalcogen sensitization, the silver halide photographic emulsion half-width of the absorption spectrum of chalcogen sensitization centers generated by the chalcogen sensitization wherein there 3900Cm ^-1 below 1200 cm ^-1 or more. (2) Chalcogen sensitized, the half width of the absorption spectrum of the chalcogen sensitized center generated by the chalcogen sensitization is 3600 cm ^-1 or less, preferably 3200 cm ^-1 , more preferably 2800 cm ^-1 or less, and 1200 cm ^A silver halide photographic emulsion, characterized in that the number is at least ^-1 . (3) The silver halide emulsion according to (1), wherein gold sensitization is used in combination. (4) The silver halide emulsion according to (1), which is used in combination with reduction sensitization, particularly when silver halide grains are formed. (5) A silver halide emulsion, wherein the chalcogen sensitization according to (1) is particularly sulfur sensitization and selenium sensitization. (6) The silver halide emulsion according to (1), wherein a sensitizing dye, preferably a merocyanine dye or a cyanine dye, particularly a cyanine dye is added during chalcogen sensitization. (7) The silver halide emulsion according to (1), wherein a nitrogen-containing heterocyclic compound, particularly a heterocyclic compound containing two or more nitrogen atoms, is added during chalcogen sensitization. (8) The chalcogen sensitized silver halide grains of the present invention have an aspect ratio of 2 or more, preferably 6 or more, particularly 8
The above tabular grains. (9) The main plane of the tabular grains according to (8) is {111}.
The surface must be silver halide grains. (10) The main plane of the tabular grains according to (8) is {100}
The surface must be silver halide grains. (11) The silver halide grains of the present invention contain dislocation lines, and especially 5 or more grains per grain. (12) The silver halide grains of the present invention have a portion where epitaxy is formed. (13) The coefficient of variation of the grain size of the silver halide grains of the present invention is 30% or less, preferably 20% or less, particularly 15% or less. (14) A method of chalcogen sensitization of a silver halide emulsion, wherein the chalcogen sensitization is controlled by measuring an absorption spectrum of the chalcogen sensitization center according to (1). (15) A silver halide photographic material containing at least one silver halide emulsion according to (1).

[0042]

The present invention will be described in more detail with reference to the following Examples, but it should be understood that the present invention is not limited to these Examples. Example 1 0.05 g of potassium bromide and gelatin 30 kept at 75 ° C.
While stirring to 1 liter of an aqueous solution containing 1 g of the above solution, 75 ml of an aqueous solution of silver nitrate (1M) and an aqueous solution of potassium bromide (1M) were simultaneously added over 4 minutes while maintaining the silver potential at 0 mV with respect to a saturated calomel electrode. Thereafter, a silver nitrate aqueous solution (1
M) 675 ml and an aqueous potassium bromide solution (1 M) were added over a period of 36 minutes while maintaining the silver potential at -30 mV. The pH was kept at 9.5 during the first half of the silver nitrate addition and at 5.0 during the second half of the addition. After particle formation, desalting and washing with ordinary flocculation method using a polymer flocculant, gelatin and water are added, and p
H was adjusted to 6.5 and pAg to 8.6. The resulting silver bromide emulsion is a monodispersed octahedral emulsion having a grain diameter of 0.31 μm and a variation coefficient of the grain diameter of 11%.

This emulsion was subdivided and subjected to the following chemical ripening. (Em-A) (Comparative emulsion) This partially divided emulsion was heated to 60 ° C., and sodium thiosulfate (3.2 × 10 ⁻⁵ mol / mol Ag) was added thereto.
After aging for 0 minutes, Em-A was obtained. (Em-B) (Comparative emulsion) Em-B was obtained in the same manner as Em-A except that sodium thiosulfate was added at 4.8 × 10 ⁻⁶ mol / mol Ag.

(Em-C) (Invention) This emulsion, which was partially subdivided, was treated at 40 ° C. with Dye-1;
{5,5'-diphenyl-N, N'-sulfobutyl-mo
Nomethine oxacyanine Na salt （(1.0 × 10 ^-3Mo
Immediately after the addition of Ag / mol Ag) to 60 ° C.
Sodium thiosulfate (4.2 × 10^-FiveMol / mol A
g) was added, and Compound 20;
Phenyl-5-mercaptotetrazole Na salt｝ (8
× 10^-FourMol / mol Ag), and aged for 60 minutes.
mC was obtained. (Em-D) (Invention) Dye-1 was converted to (1.6 × 10^-3Mol / mol Ag), thiosulfur
Sodium acid (4.8 × 10^-FiveMol / mol Ag) compound
Object-1 is 6 × 10^-FourEm- except that mol / mol Ag was used.
Em-D was obtained in the same manner as in C.

(Em-E) (Invention) This emulsion, which was partially subdivided, was prepared at 40 ° C. with dye-1 (1.2 × 10 ⁻³ mol / mol Ag) and compound-1 (6
× 10 ⁻⁴ mol / mol Ag) and 10 minutes later, sodium thiosulfate (4.2 × 10 ⁻⁵ mol / mol Ag) was added.
Immediately after the temperature was raised to 65 ° C., Dye-1 (0.4 ×
10 ⁻³ mol / mol Ag) and Compound-1 (2 × 10 ⁻⁴ mol / mol Ag) were further added, and the mixture was aged for 35 minutes and Em-E
I got

Em-A to Em were prepared such that after chemical ripening, Dye-1 was 1.8 × 10 ^-3 mol / mol Ag and Compound-1 was 1.2 × 10 ^-3 mol / mol Ag. Each required amount was additionally added. Referring to the unripened emulsion to which Dye-1 and Compound-1 were added, Em-A to E were placed in a 1 cm cell, and Dye-1 and Compound-1 hardly hindered the absorption of lead sulfide. The absorption (reflectance) was measured with a spectrometer having an integrating sphere as it was, and the half width results shown in Table 1 were obtained.

[0047]

[Table 1]

As shown in Table 1, simply using the sodium sensitizer sodium thiosulfate results in absorption having a large half width, but it is necessary to use an appropriate amount of dye-1 or compound-1 at an appropriate time. As a result, a sharp absorption having a small half width was obtained.

Example 2 Em-A to E obtained in Example 1 were added to gelatin, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, sodium poly-styrenesulfonate, dodecylbenzene Sodium sulfonate is added and co-extruded onto a triacetyl cellulose film support having an undercoat layer together with a protective layer containing gelatin, polymethyl methacrylate particles, phenoxyethanol, and 1,2-bis (vinylsulfonylacetylamino) ethane. Applied. These samples were exposed to sensitometric exposure (10
Second) through an optical wedge, and then MAA-
After developing with one developer at 20 ° C. for 10 minutes, the solution was stopped, fixed, washed with water and dried by a conventional method, and the density was measured. The relative humidity is 80% RH, the temperature is 60 ° C, and the relative humidity is 30% RH.
H, and stored at a temperature of 65 ° C. for 4 days, and then subjected to the same development processing. The relative sensitivity is represented by the reciprocal of the exposure required to obtain an optical density of fog + 0.2, and the value of Sample 1 immediately after coating was set to 100.

[0050]

[Table 2]

As is apparent from Table 2, the emulsions C to C having a small half width were compared with the emulsions A and B having absorption having a large half width.
E was highly preferable because it gave a high sensitivity and had little fogging when stored in an atmosphere of high temperature and high humidity or high temperature and low humidity. The smaller the half width is, the more preferable it is. By monitoring the absorption of the chalcogen sensitized center, it becomes possible to take chemical sensitization with high sensitivity and good storage stability, and this is a completely new method.

Example 3 As in Em-A, D and E of Example 1, except that chloroauric acid (2.4 × 10 ⁻⁵ mol / mol Ag) and potassium thiocyanate (2 × 10 ⁻³ mol / mol Ag) were used. Mol Ag) was added immediately after the addition of sodium thiosulfate to adjust Em-F, G, and H. Then, the same processing as in Example 2 (however, the storage property is 55
30% RH for 4 days) to obtain the results shown in Table 3. However, the absorption spectrum was obtained by sampling a part of the emulsion after completion of ripening and adding it to KCN (2.4 × 10 ⁻⁴ mol / mol A).
g) was added. The relative sensitivity was set at 100 immediately after the sample 10 was applied.

[0053]

[Table 3]

As is clear from Table 3, the smaller the half width of absorption, the higher the sensitivity and the smaller the fogging under forced aging.

Example 4 Tabular silver bromide grains having a thickness of 0.08 μm and an equivalent circle diameter of 0.6 μm were prepared as seed crystals. Seed crystals containing 6 g of Ag
It was dissolved in 0 liter of distilled water, adjusted to a pAg of 8.2 and a pH of 5, kept at 70 ° C, and stirred vigorously. Subsequently, particles were formed in the following procedure. AgNO ₃ (166 g)
A mixed aqueous solution of an aqueous solution, KBr and KI (KI was 5 mol%) was added while maintaining the pAg at 8.4. At this time, a reduction sensitizer thiourea dioxide (1.8 mg) was also added. 55 ° C
The aqueous solution of the AgI fine grain emulsion (AgNO ₃ 8g)
Was added immediately. An aqueous solution of AgNO ₃ (38 g) and an aqueous KBr solution were added while maintaining the pAg at 8.9,
Finally, sodium benzenethiosulfonate (51 mg) was added.

The mixture was cooled to 35 ° C., washed with water by a conventional flocculation method, and 50 g of gelatin was added.
Ag 8.5. The resulting emulsion contained tabular grains having an average sphere equivalent diameter of 0.65 μm and an aspect ratio of 6 or more, 72% of the total projected area, and contained many dislocation lines when observed by an electron microscope. After a portion of the emulsion was heated to 56 ° C., chloroauric acid (8 × 10 ⁻⁶ mol / mol Ag), potassium thiocyanate (2 × 10 ⁻³ mol / mol Ag), sulfur sensitizer Sodium sulfate (1.4 × 10 ⁻⁵ mol / mol Ag) and selenium sensitizer pentafluorophenyl-diphenyl-phosphine selenide (7 × 10 ⁻⁶ mol / mol A)
g) and aged for 80 minutes to give compound-1 (8
× 10 ^-4 mol / mole Ag) and added to Emulsion-1 (Comparative Example)
I got

Further, while keeping a part of the subdivision of this emulsion at 40 ° C., the compound-1 of Example 1 (6 × 10 ⁻⁴ mol / mol Ag) was added thereto, and then used in Emulsion-I. Equal amounts of chloroauric acid, potassium thiocyanate, sodium thiosulfate,
After pentafluorophenyl-diphenyl-phosphine selenide was added, the temperature was immediately raised to 58 ° C., and 30 minutes later, compound-1 (2 × 10 ⁻⁴ mol / mol Ag) was added.
After ripening for one minute, Emulsion-J (the present invention) was obtained.

Thereafter, a sensitizing dye: {anhydro-5-chloro-5'-phenyl-9-ethyl-3,3'-di (3-sulfopropyl) benzoxacarbocyanine hydroxide sodium salt}; magenta coupler 3- {3- [2- (2,4-di-te
rt-amylphenoxy) butylamino] benzoylamino} -1- (2,4,6-trichlorophenyl) pyrazolone-5-one oil; tricresyl phosphate stabilizer; 4-hydroxy-6-methyl-1,3 , 3a,
7-tetrazaindene antifoggant; 1- (m-sulfophenyl) -5-mercaptotetrazole monosodium salt and 1- (p-carboxyphenyl) -5-mercaptotetrazole Coating aid; sodium dodecylbenzenesulfonate 1,2-bis (vinylsulfonylacetylamino) ethane, a preservative; phenoxyethanol, and coextrusion onto a triacetylcellulose film support having an undercoat layer together with a gelatin protective layer containing methyl polymethacrylate particles. Applied.

These samples were exposed (1 second) under a light wedge and subjected to the following development processing. (Processing method) Step Processing time Processing temperature Color development 2 minutes 15 seconds 38 ° C. Bleaching 6 minutes 30 seconds 38 ° C. Water washing 2 minutes 10 seconds 24 ° C. Fixing 4 minutes 20 seconds 38 ° C. Water washing (1) 1 minute 05 seconds 24 ℃ Water washing (2) 1 minute 00 seconds 24 ° C. Stabilization 1 minute 05 seconds 38 ° C. Drying 4 minutes 20 seconds 55 ° C.

Next, the composition of the processing solution is shown. (Color developing solution) (Unit g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 5 mg hydroxylamine sulfate 2.4 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 Water and 1.0 liter pH 10.05

(Bleaching solution) (Unit g) Sodium ferric ethylenediaminetetraacetate trihydrate 100.0 Disodium ethylenediaminetetraacetate 10.0 Ammonium bromide 140.0 Ammonium nitrate 30.0 Aqueous ammonia (27%) 6 Add 0.5 ml water, add 1.0 liter, pH 6.0

(Fixing solution) (unit g) Disodium ethylenediaminetetraacetate 0.5 Sodium sulfite 7.0 Sodium bisulfite 5.0 Ammonium thiosulfate aqueous solution (70%) 170.0 ml Water was added to add 1.0 liter pH 6.7

(Stabilizing solution) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether 0.3 (average degree of polymerization: 10) Disodium ethylenediaminetetraacetate 0.05 Water was added. 1.0 liters pH 5.0-8.0

The density of the treated sample was measured with a green filter. Table 4 shows the obtained photographic performance results. The relative sensitivity is represented by a relative value of a reciprocal of an exposure amount required to obtain an optical density of a fog value + 0.2.
00. In addition, the results when stored in an atmosphere at 50 ° C. and a relative humidity of 30% for 4 days are also shown. The half width of the absorption at the center of chalcogen sensitization was 10% by mole of gold, sulfur, and selenium sensitizers used in Emulsions I and -J, respectively, and ripened in the same manner. 10 of gold
The measurement was performed by adding a molar amount of KCN.

[0065]

[Table 4]

As is evident from Table 4, the emulsion of the present invention having a small half width of absorption was excellent with little fogging and change in sensitivity during storage.

Example 5 2.3 g of sodium chloride and gelatin 2 kept at 50 ° C.
An aqueous silver nitrate solution (480 ml by adding water to 120 g of AgNO ₃ ) and an aqueous sodium chloride solution (480 ml by adding water to 42 g of NaCl) were simultaneously added to 800 ml of an aqueous solution of pH 4.5 in which 5 g was dissolved. The resulting emulsion was a cubic, monodisperse silver chloride emulsion having a grain size of 0.25 μm in side length. Then, after washing with water and desalting by a usual flocculation method using a polymer flocculant, 76 g of gelatin and water were further added to adjust the pH to 6.2 and the pAg to 7.0 at 40 ° C.

This emulsion was subdivided, and 2.5 × 10 ⁻⁴ mol / mol Ag of sodium thiosulfate was added at 55 ° C.
After aging for 0 minutes, compound-2; {1- [3- (3-methylureido) phenyl] -5-mercaptotetrazole} (4 × 10 ⁻⁴ mol / mol Af) and compound-3; 2
-Methylthio- {4-hydroxy-6-methyl-1,
3,3a, 7-tetrazaindene {(8 × 10 ^-4 mol /
Mol Ag) to obtain Emulsion-K (Comparative Example).

At 40 ° C., compound 2 (4 × 10 ⁻⁴ mol / mol Ag) and compound 3
(8 × 10 ^-4 mol / mol Ag), the temperature was raised to 58 ° C., and sodium thiosulfate was added at 2.5 × 10 ^-4 mol / mol A.
g and ripening for 90 minutes to obtain Emulsion-L. Table 5 shows the half width of absorption of these emulsions.

[0070]

[Table 5]

Emulsion-L had a much smaller half-width of absorption than Emulsion-K. Emulsion-K 'and Emulsion-L' were prepared in the same manner as in Example 2 except that the sodium thiosulfate used in Emulsions-K and -L was changed to 6.4 × 10 ^-5 mol / mol Ag. (However, all forced aging was performed at 50 ° C.), the emulsion-L 'of the present invention showed good fog and change in sensitivity during storage compared to the emulsion-K' with little change. .

Example 6 Emulsion-J obtained in Example 4 was optimally chemically sensitized and spectrally sensitized, and then subjected to Example 2 of JP-A-9-146237.
The sample 201 was used as an emulsion for the third layer of the light-sensitive material and subjected to the same processing as in the example of the same JP-A-Hei-Hei.

Claims (2)

[Claims] 1. A chalcogen-sensitized silver halide photographic emulsion, wherein the half width of the absorption spectrum of the chalcogen sensitized center formed by the chalcogen sensitization is 3900 cm ^-1.
A silver halide photographic emulsion having a size of 1200 cm ^-1 or more. 2. A method for chalcogen sensitizing a silver halide photographic emulsion, wherein the half width of the absorption spectrum of the chalcogen sensitized center formed by the chalcogen sensitization is 3900.
cm ^-1 or less, chalcogen sensitization method of the silver halide photographic emulsion, which comprises carrying out controlled to be in the 1200 cm ^-1 or more.