JPH117097A - Silver halide emulsion and silver halide photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide emulsion superior in a fog to sensitivity ratio and a sensitivity to graininess ratio and improved in storage stability by chemically sensitizing it by using a specified compound. SOLUTION: This silver halide emulsion is chemically sensitized by using the compound having a group adsorbable to silver halide and an instable tellurium atom site in the molecule and this compound is represented by the formula in which A is a group adsorbable to silver halide, such as an atomic group having a mercapto group or thionyl group or forming an imino silver; L is a divalent bonding group, comprising C, H, O, N, and/or S, for example, a 1-20C alkylene group; Z is an atomic group including an instable tellurium atom site, such as an atomic group having a telluroamide or polytelluride or phosphotelluride group; (m) is 0 or 1; and (n) is 1, 2, or 3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide emulsion and a silver halide light-sensitive material using the same. More specifically, the present invention relates to a silver halide emulsion having excellent fog / sensitivity and sensitivity / granularity and improved storage stability. The present invention relates to an emulsion and a silver halide light-sensitive material using the same.

[0002]

2. Description of the Related Art While silver halide color photographic light-sensitive materials are said to be mature products with extremely high degree of perfection, the required performance is wide-ranging, such as high sensitivity, high image quality, and little fluctuation in performance due to storage conditions. Further, in the future, it is necessary to take into account rapid processing aptitude which has advanced development progress and the like, and the required level has been increasing in recent years.

[0003] In particular, in terms of high sensitivity, due to the recent technological advancement of digital cameras, in order to maintain the superiority of silver halide photographic materials, further high sensitivity which keeps fog low and is compatible with storability. Is necessary.

Techniques for increasing the sensitivity of silver halide emulsions, that is, sensitization techniques, relate to a method for producing a silver halide emulsion, chemical sensitization of a silver halide emulsion, spectral sensitization of a silver halide emulsion, Various methods are known, such as those based on a method for designing a silver halide photosensitive material and those relating to a development process of the silver halide photosensitive material.
Among them, the most preferable and essential method is to reduce the inefficiency of the silver halide crystal during the photosensitive process and improve the quantum efficiency. One of the means is chemical sensitization, such as sulfur sensitization, selenium sensitization, chalcogen sensitization such as tellurium sensitization, noble metal sensitization using a noble metal such as gold, and reduction sensitization using a reducing agent. These are used alone or in combination.

[0005] Above all, when gold sensitization is used in combination with sulfur sensitization, selenium or tellurium sensitization, a remarkable increase in sensitivity can be obtained, but fog also increases. In particular, gold-selenium sensitization and tellurium sensitization have a particularly large fog increase as compared with gold-sulfur sensitization, and there has been a demand for a technique for suppressing the generation of fog, as well as a sensitization technique with less fog during storage and less fluctuation in sensitivity.

In response to such demands, a technique of performing chemical sensitization with a compound having an adsorbing group to a silver halide and a chalcogen moiety to suppress the generation of fog is disclosed in Japanese Patent Application Laid-Open Nos. -8668, selenium in Japanese Patent Publication No. 5-18091, JP-A-9-15
777, 6-208186 and 6-208184
Nos. 6-31767, 6-175258, 6-43576, 4-25832, 4-109
No. 240, No. 4-147250, Japanese Patent Application No. 8-9107
0, etc. However, it is expected that the fogging / sensitivity is still insufficient, and that the inhibitory effect on silver halide is expected to be strong. However, the ultimate sensitivity is slightly inferior and further improvement has been desired.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide emulsion excellent in fog / sensitivity and sensitivity / granularity and having improved storage stability, and a silver halide photosensitive material using the same. To provide.

[0008]

The above object of the present invention has been attained by the following constitutions.

(1) A silver halide emulsion chemically sensitized using a compound having an adsorptive group to silver halide and an unstable tellurium atom site in the molecule.

(2) The compound according to (1), wherein the compound having an adsorptive group to silver halide and an unstable tellurium atom site in the molecule is a compound represented by the following general formula (I). The silver halide emulsion as described above.

[0011]

Embedded image

[In the formula, A represents an atom group containing a group that can be adsorbed to silver halide, L represents a divalent linking group, and Z represents an atom group containing an unstable tellurium atom site. m is 0 or 1
And n represents an integer of 1 to 3. (3) having at least one photosensitive silver halide emulsion layer on a support, wherein the silver halide emulsion according to (1) or (2) is contained in at least one silver halide emulsion layer; A silver halide color light-sensitive material characterized by containing.

(4) A silver halide light-sensitive material comprising the compound described in the above (1) or (2).

(5) The silver halide color light-sensitive material as described in (3), containing the compound as described in (1) or (2) above.

Hereinafter, the present invention will be described in detail.

The compound represented by formula (I) will be described in detail.

In the general formula (I), the atom group having a group adsorbable to silver halide represented by A is an atom group having a mercapto group (for example, mercaptooxadiazole, mercaptotetrazole, mercaptotriazole , Mercaptodiazole, mercaptothiazole, mercaptothiadiazole, mercaptooxazole, mercaptoimidazole, mercaptobenzothiazole, mercaptobenzoxazole, mercaptobenzimidazole, mercaptotetrazaindene, mercaptopyridyl, mercaptoquinolyl, 2-mercaptopyridyl, mercaptophenyl, mercapto An atomic group having a thione group (for example, thiazoline-2-thione, oxazoline-2-thione, imidazoline-2-thione, Atomic groups forming imino silver (for example, triazole, tetrazole, benzotriazole, hydroxyazaindene, benzimidazole, indazole and the like), groups such as benzothiazoline-2-thione, benzimidazoline-2-thione, thiazolidine-2-thione, etc. Groups), an atom group having an acetylene group (for example,
2- [N- (2-propynyl) amino] benzothiazole, each group such as N- (2-propynyl) carbazole, and the like.

As a specific example of an atom group containing an unstable tellurium atom site represented by Z, an atom group having a tellurourea group (eg, N, N'-diethyltellurourea, N-ethyl-N '-(2 -Thiazolyl) tellurourea, N-phenyltellurourea, N, N'-diethyl-N, N'-dimethylenetellurourea, N, N'-dimethylene-N, N'-dimethyltellurourea, etc.), telluroamide group (For example, each group such as tellurobenzamide, N, N-diethyl-telluroacetamide, N, N-dimethyl-tellurobenzamide, N, N-tetramethylene- (p-tolyl) tellurobenzamide), polytelluride, A group of atoms having a phosphine telluride group (for example, butyl-di-
An isopropylphosphine telluride, triscyclohexylphosphine telluride, diethylphosphine telluride, each group of dimethylphenylphosphine telluride, etc.) an atom group having a tellurophosphate group (for example,
Groups such as tris (p-tolyl) tellurophosphate and trisbutyltellurophosphate), an atom group having a tellurophosphoric amide group (for example, each group such as hexamethyltellurophosphoric amide), and a telluroester group. Atom group (e.g., p-methoxytellurobenzoic acid = O-isopropyl ester, tellurobenzoic acid = Te- (3'-oxobutyl) ester, p-methoxytellurobenzoic acid = O-
(Each group such as (3'-oxocyclohexyl) ester),
Atomic group having a telluride group (for example, bis (2,6-dimethoxybenzoyl) telluride, bis (n-butoxycarbonyl) telluride, bis (N-methyl-N-benzylcarbamoyl) telluride, bis (N, N-dimethylcarbamoyl) ) Each group such as telluride), an atom group having a telluroketone group (for example, each group such as 4-methoxytelluroacetophenone, 4,4-methoxytellurobenzophenone)
And the like. Other examples of the atomic group having an unstable tellurium site include JP-A-4-20460 and JP-A-4-20460.
-33043, 5-303157, 5-306
No. 268, No. 5-306269, No. 6-17528
Nos. 6-17529, 6-27573, 6-
No. 180478, No. 6-208184, No. 6-208
No. 186, No. 6-317867, No. 7-104415
, No. 7-140579, and No. 7-301880. These groups of atoms can be formed from any part of the substituent via a linking group L,
Alternatively, a covalent bond is directly formed with the atomic group A containing a group that can be adsorbed on the silver halide.

In the general formula (I), the divalent linking group represented by L is a group composed of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom and a sulfur atom. An alkylene group having 1 to 20 carbon atoms (e.g., methylene, ethylene, propylene, hexylene, etc.), an arylene group (e.g., phenylene, naphthylene, etc.), -CONR _1- , -SO ₂ NR _2- , -O-, -S
_{-, - NR 3 -, -} NR 4 CO -, - NR 5 SO 2 -, - N
R ₆ CONR ₇ —, —CO—O—, —O—CO—, —CO
-, -CH = N-, -N = CH- and the like.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ each represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.
As the aliphatic group represented by R _{1 to} R ₇ , a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, isopropyl, 2-ethyl-hexyl, cyclopentyl, cyclohexyl, etc.) Group), alkenyl group (for example, propenyl, 3-pentenyl, 2-butenyl, cyclohexenyl, etc.), alkynyl group (for example, propargyl, 3-pentynyl, etc.), aralkyl (for example, benzyl, phenethyl, etc.) Each group). The aromatic group is a monocyclic or condensed ring group having 6 to 10 carbon atoms, specifically, a phenyl group or a naphthyl group, and the heterocyclic group is an oxygen atom, a sulfur atom, a nitrogen atom. And a 5- to 7-membered monocyclic or condensed-ring group containing, specifically, furyl, thienyl, benzofuryl,
Examples include groups such as pyrrolyl, indolyl, thiazolyl, imidazolyl, morpholyl, piperazyl, and pyrazyl. Each of the groups represented by R _{1 to} R ₇ can be substituted with an arbitrary group at an arbitrary position. Examples of the substituent include a hydroxy group and a halogen group (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom). , Cyano group, amino group (for example, methylamino,
Groups such as anilino, diethylamino, 2-hydroxyethylamino, etc., acyl groups (eg, acetyl, benzoyl, propanoyl, etc.), carbamoyl groups (eg, carbamoyl, N-methylcarbamoyl, N, N-
Groups such as tetramethylenecarbamoyl, N-methanesulfonylcarbamoyl, N-acetylcarbamoyl), alkoxy groups (eg, methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethoxy, etc.), and alkoxycarbonyl (eg, methoxy) Carbonyl, ethoxycarbonyl, 2-methoxyethoxycarbonyl, etc.), sulfonyl group (for example, methanesulfonyl, trifluoromethanesulfonyl, benzenesulfonyl, p
Each group such as -toluenesulfonyl), a sulfamoyl group (for example, each group such as sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl, N-ethylsulfamoyl), an acylamino group (for example, acetamido, trifluoro) Groups such as acetamide, benzamide, thienocarbonylamino, benzenesulfonamide, etc., and alkoxycarbonylamino groups (eg, respective groups such as methoxycarbonylamino, N-methyl-ethoxycarbonylamino).

Specific examples of the compound of the present invention are shown below.
The compound of the present invention is not limited to this.

[0022]

Embedded image

[0023]

Embedded image

[0024]

Embedded image

[0025]

Embedded image

The compound of the present invention can be synthesized by utilizing a known substitution reaction. For example, a method represented by the following equation is used.

(W)-[A] -COOH + Z-NH ₂ → condensing agent → (W)-[A] -CONH-Z (formula 1) (W)-[A] -NH ₂ + Z-COOH → Condensing agent → (W)-[A] -NHCO-Z (Formula 2) (W)-[A] -COCl + Z-NH ₂ → Base → (W)-[A] -CONH-Z (Formula 3) ) (W)-[A] -NH ₂ + Z-COCl → base → (W)-[A] -NHCO-Z (Formula 4) (W)-[A] -X + Z-NRH → base → ( W)-[A] -N (R) -Z + HX (Formula 5) (W)-[A] -NRH + ZX → Base → (W)-[A] -N (R) -Z + HX (Formula 6) (W)-[A] -X + Z-OH → Base → (W)-[A] -OZ + HX (Formula 7) (W)-[A] -OH + Z− X → base → (W)-[A] -OZ + HX (Formula 8) In the formulas 5, 6, 7, and 8, X is a group that leaves after the reaction, and is, for example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom) or a sulfonic acid ester group (for example, , P-toluenesulfonate, trifluoromethanesulfonate, m-chlorobenzenesulfonate, etc.).

(W)-[A] -CHO + Z-H ₂ → Base → (W)-[A] -CH = Z (Formula 9) (W)-[A] -H ₂ + Z-CHO → Base → (W)-[A] = CH-Z (Formula 10) The amount of the compound represented by the general formula (I) (tellurium compound) used in the present invention depends on the chalcogen compound used,
It depends on silver halide grains, chemical sensitization environment, etc.
The amount is preferably 10 ^-8 to 10 ^-2 mol, more preferably about 10 ^-7 to 10 ^-3 mol, per mol of silver halide. The chemical sensitization environment in the present invention is not particularly limited, but the pAg is preferably 6 to 11, more preferably 7 to 10, the pH is preferably 4 to 10, more preferably 5 to 8, and the temperature is The temperature is preferably from 40C to 90C, more preferably from 45C to 80C.

It is preferable to use the silver halide emulsion of the present invention in combination with sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization other than the present invention.

In the sulfur sensitization, an unstable sulfur compound can be used, and specific examples thereof include 1,3-diphenylthiourea, triethylthiourea, and 1-ethyl-3- (2-thiazolyl) thiourea. Preferred are thiourea derivatives, rhodanine derivatives, dithicarbamic acids, polysulfide organic compounds, thiosulfates, elemental sulfur and the like. In addition, as the elemental sulfur, α-sulfur belonging to the orthorhombic system is preferable. Other U.S. Pat. Nos. 1,574,944 and 2,410,6
Nos. 89, 2,278,947 and 2,728,66
No. 8, 3,501, 313, 3,656,955
And sulfur sensitizers described in West German Application (OLS) 1,422,869, JP-A-56-24937, and JP-A-55-45016.

In selenium sensitization, an unstable selenium compound can be used. For example, US Pat. No. 1,574,94
No. 4, No. 1, 602, 592, No. 1, 623, 499
JP-A-60-150046, JP-A-4-2583
2, No. 4-109240, and No. 4-147250. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, N, N-dimethylselenourea, N, N, N′-triethylseleno). Urea, N, N, N'-trimethyl-N'-
Heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, etc., selenoketones (for example, , Selenoacetone, selenoacetophenone, etc.), selenoamide (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid,
Methyl-3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.), selenides (dimethyl selenide, triphenylphosphine selenide, pentafluorophenyl-).
Diphenylphosphine selenide).
Particularly preferred selenium sensitizers are selenoureas, selenamides, and selenides.

Specific examples of techniques for using these selenium sensitizers are disclosed in the following patent specifications. US Patent 1,57
4,944, 1,602,592, 1,62
No. 3,499, No. 3,297,466, No. 3,29
7,447, 3,320,069, 3,40
8,196, 3,408,197, 3,44
2,653, 3,420,670 and 3,59
No. 1,385, French Patent Nos. 2,693,038, 2,093,209, JP-B Nos. 52-34491, 52-34492, 53-295, and 57-22.
No. 090, JP-A-59-180536 and JP-A-59-18.
Nos. 5330, 59-181337, 59-187
No. 338, No. 59-192241, No. 60-1500
No. 46, No. 60-151637, No. 61-24673
8, JP-A-3-4221, JP-A-3-24537, JP-A-3-11838, JP-A-3-116132, JP-A-3-3-1
No. 48648, No. 3-237450, No. 4-1683
No. 8, No. 4-25832, No. 4-32831, No. 4
-96059, 4-109240, 4-140
No. 738, No. 4-140739, No. 4-147250
No. 4,184,331, No. 4-190225, No. 4-191729, No. 4-19535, British Patent 255,846, No. 861,984. E. FIG.
Spencer et al. Journal of Photo
graphic science magazine, vol. 31, 158-
169 (1983).

In tellurium sensitization, an unstable tellurium compound can be used. For tellurium sensitizers and sensitization methods, see US Pat. Nos. 1,623,499 and 3,320,
Nos. 069, 3,772,031, 3,531,
Nos. 89 and 3,655,394; British Patent 235,2
No. 11, No. 1, 121, 469, No. 1, 295, 46
No. 2, No. 1,396,696, Canadian Patent 800,9
No. 58, JP-A-4-20464 and the like.
Specifically, phosphine tellurides (for example, butyl-
Diisopropylphosphine telluride, tributylphosphine telluride, etc.), telluroureas (eg, N, N
-Dimethylethylene tellurourea, N, N-diphenylethylene tellurourea), telluramides and the like.

In noble metal sensitization, Research
Noble metal salts such as gold, platinum, palladium and iridium described in Disclosure Magazine, Vol. 307, No. 307105 can be used, and gold sensitization is particularly preferable. Useful gold sensitizers include chloroauric acid, gold thiosulfate, gold thiocyanate, and the like.
7,856, 5,049,485, 5,62
0,841, Japanese Patent Publication No. 44-15748,
And organic gold compounds disclosed in Nos. 147537 and 4-70650.

In reduction sensitization, Research
Reducing compounds described in Disclosure Magazine, Vol. 307, No. 307105, JP-A-7-78685, and the like can be used. Specifically, aminoiminomethanesulfinic acid (also known as thiourea dioxide), borane compounds (eg, dimethylamine borane, etc.), hydrazine compounds (eg, hydrazine, p-tolylhydrazine, etc.), polyamine compounds (eg, diethylenetriamine, triethylene Ethylene tetramine), stannous chloride, silane compounds, reductones (eg, ascorbic acid), sodium sulfite, aldehyde compounds, hydrogen gas and the like. Further, reduction sensitization may be carried out in an atmosphere having a high pH or an excess of silver ions as disclosed in Japanese Patent Application Nos. 8-277938, 8-251486, and 8-182,035.

Of these chemical sensitizations, it is preferable to combine them with gold sensitization.

Depending on the properties of the compound to be used, the above-mentioned various sensitizers can be added either by adding water or an organic solvent such as methanol alone or in a mixed solvent, or by adding a gelatin solution in advance. The method of mixing and adding may be the method disclosed in JP-A-4-140739, that is, the method of adding in the form of an emulsified dispersion of a mixed solution with an organic solvent-soluble polymer.

Next, the silver halide emulsion of the present invention will be described. The shape and the halogen composition of the silver halide grains used in the present invention are not particularly limited. However, the preferred form of the silver halide grains differs depending on the use. For example, the following tabular grains (hereinafter referred to as tabular grains) are preferred as silver halide grains used in a color negative film.

In the present invention, the tabular grains refer to 2
Having two parallel principal planes, the ratio of the circle-equivalent diameter of the principal plane (diameter of a circle having the same projected area as the principal plane) to the distance between the principal planes (ie, the thickness of the particles), ie, the aspect ratio of 2 or more. Say particles. In the invention, 50% or more of the total projected area of all the grains of the tabular grains is preferably tabular grains having an aspect ratio of 3 or more, and more preferably 5 or more. The diameter of the tabular grains in the present invention is preferably 0.3 to 10 μm, more preferably 0.5 to 10 μm.
To 5.0 μm, more preferably 0.5 to 2.0 μm. The thickness of the particles is preferably between 0.05 and 0.8 μm. The measurement of the particle diameter and the particle thickness in the present invention can be obtained by the method described in U.S. Pat. No. 4,434,226.

The size distribution of the tabular grains of the present invention is obtained by dividing the coefficient of variation of the circle-equivalent diameter of the principal plane (the diameter of a circle having the same projected area as the principal plane) by dividing the standard deviation of the diameter distribution by the average diameter. ) Is preferably 30% or less, and 20%
It is more preferred that:

The halogen composition of the silver halide grains is preferably silver bromide or silver iodobromide, and the silver iodide content is preferably from 0.1 mol% to less than 5 mol%. More preferably, it is at least 0.5 mol% and less than 3 mol%.

In the present invention, the phrase "substantially free of silver chloride" means that the silver halide grains have a silver chloride content of 0.1.
It means that it is 5 mol% or less.

The intergranular distribution of the silver iodide content of the silver halide grains of the present invention is determined by calculating the coefficient of variation of the silver iodide content (the standard deviation of the silver iodide content intergranular distribution is the average silver iodide content). Is preferably 30% or less, and more preferably 20% or less.

The tabular grains of the present invention may have at least two or more phases having different halogen compositions inside the grains. The silver iodide content of the maximum silver iodide-containing layer in the silver halide grains excluding the outermost layer is preferably less than 5 mol%, more preferably less than 2 mol%. The volume fraction of the phase in the particles is preferably 30% or more and 90% or less.

The structure relating to the halogen composition in the grains is represented by X
It can be examined by a line diffraction method, a composition analysis method using EPMA, or the like.

The silver iodide content of the outermost layer of the silver halide grains in the present invention means a value determined by the following method. The silver iodide content of the outermost layer of the grain is determined by an XPS method (X-ray Photoelectron Spec).
Troscopy (X-ray photoelectron spectroscopy) as follows. The sample was cooled to −115 ° C. or less in an ultra-high vacuum of 1 × 10 ⁻⁸ torr or less.
Irradiation at mA, Ag3d5 / 2, Br3d, I3d3 /
Measure for two electrons. The integrated intensity of the measured peak is determined by a sensitivity factor.
The silver iodide content of the outermost layer is determined from these intensity ratios.

The silver iodide content of the outermost layer of the silver halide grains of the present invention is preferably 8 mol% or more.
More preferably, it is at least mol%.

Further, the maximum silver iodide-containing phase in the grain in the present invention does not include a high iodine localization region generated by an operation described later for forming dislocation lines.

As a method for producing tabular grains, methods known in the art can be appropriately combined. For example, Japanese Patent Application Laid-Open Nos. 61-6643, 61-146305, and 6
2-157024, 62-18556, 63-
No. 92942, No. 63-163451, No. 63-22
Known methods described in JP-A Nos. 0238 and 63-31244 can be referred to. For example, a double jet method, a double jet method, a so-called controlled double jet method which maintains a constant pAg in a liquid phase in which silver halide is formed, which is a type of the double jet method, and a soluble silver halide having a different composition, respectively. A triple jet method, which is added independently, can also be used. A forward mixing method can be used, and a method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. If necessary, a silver halide solvent can be used. Silver halide solvents often used include ammonia, thioethers and thioureas. For thioethers, reference can be made to U.S. Pat. Nos. 3,271,157, 3,790,387, 3,574,628 and the like. The mixing method is not particularly limited, and a neutral method using no ammonia, an ammonia method, an acidic method, and the like can be used.However, from the viewpoint of reducing fogging of silver halide grains, it is preferably pH.
(The logarithm of the reciprocal of the hydrogen ion concentration) is 5.5 or less, more preferably 4.5 or less.

The silver halide grains of the present invention contain iodide ions. In this case, there is no particular limitation on the method of adding iodide ions during grain growth, and they may be added as an ion solution such as potassium iodide. Further, for example, it may be added as silver iodide fine particles.

In the silver halide emulsion of the present invention, the formation of at least a part of the silver halide emulsion using silver halide fine grains makes the halogen composition distribution between grains more uniform and reduces the unevenness of photosensitive quantum efficiency. It is more preferable that the grains are grown using silver halide fine grains throughout the grain growth. However, in the present invention, "growing using silver halide fine grains over the whole grains" does not include the seed grains when the seed grains are used.

The grain formation using the silver halide fine grains is as follows.
Grains may be grown using only silver halide fine grains as in the grains disclosed in JP-A-1-183417, JP-A-1-183644, JP-A-1-183645 and the like.
What is necessary is just to supply at least one of the halogen elements by silver halide fine particles. In this case, the iodide ions are preferably supplied by silver halide fine particles. As claimed in Japanese Patent Application No. 3-218608, the number of silver halide fine grains used for grain growth is two or more, and even if at least one of them is composed of only one kind of halogen element, Good.

It is desirable to use silver halide grains having a lower solubility than the growing silver halide grains, as in the claims of JP-A-2-16737.
It is particularly desirable to use silver iodide as a silver halide grain having a small solubility product.

The dislocation of tabular grains is described, for example, in J. Am. F. Ha
Milton, Photo. Sci. Eng. , 11
(1967), 57; Shiozawa, J .; Sc
i. Photo. Sci. Japan, 35 (197
2) Observation can be performed by the method described in 213, that is, a direct method using a transmission electron microscope at a low temperature. That is, silver halide grains taken out so as not to apply enough pressure from the emulsion to generate dislocations on the grains are placed on a mesh for an electron microscope to prevent damage (printout, etc.) by an electron beam. Observation is performed by a transmission method while the sample is cooled. At this time, the thicker the particle, the more difficult it is for the electron beam to pass therethrough.
The use of an electron microscope (200 kV) for a thickness of 5 μm allows more clear observation. From the grain photograph obtained by such a method, the position and number of dislocations for each grain when viewed from a direction perpendicular to the main plane can be determined.

The dislocation position of the grains of the present invention does not necessarily have to be at a specific location, but preferably exists at the fringe portion of the tabular grains.

The fringe portion of the tabular grains referred to in the present invention refers to the outer periphery of the tabular grains. More specifically, the fringe portion of the tabular grains projected from the center of gravity of the tabular grain projection surface as viewed from the principal plane side to each side of the grains is: Outside (side side) of 50% of the length of the perpendicular,
It preferably refers to a region outside 70%, more preferably outside 80%.

The dislocation lines inside the grains referred to in the present invention are dislocation lines existing in regions other than the above-mentioned fringe portion.

The number of dislocations in the tabular grains of the present invention is preferably such that grains containing 10 or more dislocations account for at least 50% of the total projected area of the silver halide grains in the emulsion.
More preferably, it is 0% or more.

The method of introducing dislocation lines according to the present invention is not particularly limited, but a method of adding an aqueous solution of an iodide ion such as potassium iodide and a solution of a water-soluble silver salt by double jet at the position where the dislocation is to be introduced, or A method of adding silver halide fine particles, a method of adding only an iodine ion solution,
The method can be carried out by a method using an iodide ion releasing agent as described in No. 11781. A method of adding an aqueous iodide ion solution and a water-soluble silver salt solution by a double jet,
A method of adding silver iodide fine particles and a method of using an iodide ion releasing agent are preferable, and a method of using silver iodide fine particles is more preferable. The aqueous solution of iodide ions is preferably an aqueous solution of an alkali iodide, and the aqueous solution of a water-soluble silver salt is preferably an aqueous solution of silver nitrate.

The dislocation line is preferably introduced at a position where the dislocation line has grown to 50 to 95% of the silver amount of the whole grain, and more preferably at a position which is less than 60 to 80%.

The silver halide emulsion used in the present invention is preferably spectrally sensitized with a methine dye or the like. The sensitizing dyes may be used alone or in combination of two or more. A dye which does not have a spectral sensitizing effect together with the sensitizing dye itself, or a compound which does not substantially absorb visible light and which enhances the sensitizing effect of the sensitizing dye, is contained in the emulsion. You may. Examples of sensitizing dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxonol dyes, oxonol, polymethine dyes including merostyril and streptocyanin, and the like. I can do it.

The silver halide emulsion used in the present invention is
Various antifoggants and stabilizers can be contained for the purpose of preventing fogging during the manufacturing process, storage or processing of the photosensitive material and stabilizing photographic performance. Specifically, tetrazaindenes, azoles, benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, promobenzimidazoles, mercaptothiazoles, mercaptobenzimidazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles, mercaptopyrimidines, mercaptotriazines, thioketo compounds, and also benzenethiosulfinic acid, benzenesulfinic acid, benzenesulfonamide, hydroquinone derivatives, aminophenol derivatives, gallic acid Derivatives, ascorbic acid derivatives and the like.

In the present invention, chemical sensitization may be carried out in the presence of a silver halide solvent. US Pat. No. 3,271,157 discloses a silver halide solvent used in the present invention.
No. 3,574,628, JP-A-54-1019.
Thioethers described in JP-A-53-158917, JP-A-53-82408, and JP-A-55-778.
Thiourea derivatives described in JP-A Nos. 37-55-2982, etc .; silver halide solvents having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319; Examples thereof include imidazoles, sulfites, and thiocyanates described in JP-A-54-100717.

Known photographic additives that can be used in the color light-sensitive material of the present invention include RD17643, page 25, VIII-A to page 27, XIII, RD18716, 650 to 651,
RD308119, page 1003, paragraphs VIII-A to 1012
In Section XXI-E, and specific examples of various couplers, RD17
Pp. 643, 25, VII-C to G, RD308119, 1
Page 001, paragraphs VII-CG.

In the present invention, the aforementioned RD17643
Page 28, section XVII, RD 18716, pages 647-8, and RD
The support described in section 308119, page 1009, XVII can be used.

The light-sensitive material includes RD308119, 1
An auxiliary layer such as a filter layer or an intermediate layer described in section VII-K on page 002 can be provided.

The light-sensitive material is RD308119, VII
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in the section -K can be adopted.

[0068]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 [Preparation of seed emulsion-1] Seed emulsion-1 having two parallel twin planes was prepared by the following method.

(E-5 solution) Deionized alkali-treated gelatin (average molecular weight: 15,000) 244.0 g Potassium bromide 156.6 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _{19.8 (CH 2 CH 2 O) n} H (m + n = 9.77) 10% methanol solution 0.48mL water at 34.0L (F-5 solution) 3716ML silver nitrate 1200g water (G-5 solution) deionized alkali treatment Gelatin (average molecular weight 15,000) 31.6 g Potassium bromide 906.0 g With water 4.0 L (H-5 solution) Ammonia water (28%) 299 mL (I-5 solution) Water 8.0 L (J-5 solution) Ossein gelatin 400.0 g Water 4832 mL (K-5 solution) Potassium bromide 69.2 g Water 386 mL (L-5 solution) 56% by weight acetic acid aqueous solution 1000 mL 1000 mL Using a stirring device described in JP-A-62-160128, 3
Solution K-5 was added to solution E-5 which was vigorously stirred at 0 ° C., and then solution F-5 and solution G-5 were mixed by double jet method.
Per minute to produce silver halide nuclei.

Thereafter, the J-5 solution was added, the temperature was raised to 68 ° C. over 41 minutes, the H-5 solution was further added, and aging was performed for 7 minutes. Thereafter, the solution I-5 was further added, and 1 minute later, L
The pH was adjusted to 4.7 using solution -5, and desalting was immediately performed by a conventional method.

When this seed emulsion-1 was observed with an electron microscope, it was found that the single grain having an average grain size (grain size in terms of projected area circle) having two twin planes parallel to each other and having a grain size distribution of 16% was obtained. It was a dispersion spherical emulsion.

[Preparation of Emulsion Em-1] Emulsion Em-1 was prepared using Seed Emulsion-1 and the following solution.

(H-6 solution) Ossein gelatin 223.6 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) ) Of 10% methanol solution 3.6 mL seed emulsion-1 equivalent to 0.774 mol of water 5904 mL (solution I-6) 3.5 N silver nitrate aqueous solution 6490 mL (solution J-6) 3.5 N aqueous potassium bromide solution 7500 mL (K-solution) (Six liquids) Required amount of silver iodide fine grain emulsion SMC-1 consisting of 3.0% by weight of gelatin and silver iodide fine grains (average grain size: 0.05 μm). (L-6 solution) 1.75N aqueous solution of potassium bromide required amount (M-6 solution) 56% by weight aqueous acetic acid solution required amount (N-6 solution) 3.5N aqueous potassium bromide solution 500mL << silver iodide fine particles Tone of emulsion SMC-1 5 liters of a 6.0% by weight aqueous solution of gelatin containing 0.06 moles of potassium iodide was vigorously stirred. A 7.06 moles aqueous solution of silver nitrate and a 7.06 moles aqueous solution of potassium iodide were each 2 liters. Was added over 10 minutes. During this time, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the preparation of the particles, the pH was adjusted to 5.0 using an aqueous sodium carbonate solution. The average particle size of the obtained silver iodide fine particles is 0.05 μm.
Met. This emulsion is designated as SMC-1.

Solution H-6 was added to the reaction vessel, and while vigorously stirring, solution I-6, solution J-6 and solution K-6 were added according to the combination shown in Table 1 by the simultaneous mixing method. Seed crystals were grown to prepare a core / shell type silver halide emulsion.

Here, the addition speed of the I-6 solution, the J-6 solution, and the K-6 solution was changed in a function-like manner with respect to the addition time in consideration of the critical growth rate. The generation of small particles and the deterioration of the particle size distribution due to Ostwald ripening between growing particles were prevented.

In the crystal growth, first, the first addition was performed while controlling the solution temperature in the reaction vessel to 75 ° C. and the pAg to 8.8, and then the solution temperature in the reaction vessel was reduced to 60 ° C. in 15 minutes. Solution -6 was added for 4 minutes, and K-6 solution was added in an amount corresponding to 2% of the total silver used, followed by a second addition. Second
The addition was performed by setting the solution temperature in the reaction vessel to 60 ° C. and the pAg to 9.
8. The pH was controlled at 5.8. For control of pAg and pH, L-6 solution as needed,
M-6 solution was added.

After the particles are formed, desalting is carried out according to the method described in JP-A-5-72658, and then gelatin is added and dispersed, and pAg 8.06 at 40 ° C., pH 5.0.
8 were obtained.

When the silver halide grains in this emulsion Em-1 were observed with an electron microscope, the average grain size was 1.30 μm.
m, and hexagonal tabular monodispersed silver halide grains having a particle size distribution of 17% and an average aspect ratio of 8.0. The tabular silver halide grains had dislocation lines at the fringe portions.

[0080]

[Table 1]

This emulsion Em-1 was subdivided and emulsions A to J were prepared by the following method.

After heating to 58 ° C., SD-1 was added to 4 × 1
0 ^-4 mol / mol Ag, SD-2 8 × 10 ^-5 mol / mol Ag, SD-3 5 × 10 ^-5 mol / mol Ag, and 2
After 0 minutes, as shown in Table 2, the sulfur sensitizer, chloroauric acid 3.2
× 10 ^-6 mol / mol Ag, potassium thiocyanate 3.5
× 10 ⁻⁴ mol / mol Ag, 2.5 × 10 ⁻⁶ mol / mol Ag triphenylphosphine selenide 1/100
Aged to optimize the second sensitivity. At the end of ripening, the stabilizer ST-1 and the antifoggant AF-1 were added, the temperature was lowered, and the mixture was cooled and solidified, and the respective emulsions (emulsions A to J) were obtained.
Was prepared.

To each of the obtained emulsions, ethyl acetate and magenta coupler M-1 dissolved in tricresyl phosphate (OIL-1) were added and emulsified and dispersed in an aqueous solution containing a dispersing aid (SU-1) and gelatin. Dispersion, spreading agent (SU-
2) and a hardener (H-1, H-2) were added to prepare a coating solution, each of which was coated on a cellulose triacetate support subbed by a conventional method, dried and coated to form a single emulsion layer. Samples 101 to 110 were prepared.

The single emulsion layer coating samples (Samples 101 to 101)
110) is shown.

<Coating Formula> Sequentially from the support side First layer: Red-sensitive silver halide emulsion layer Emulsion Silver coating amount 1.5 g / m ² Magenta coupler (M-1) 0.33 g / m ² Tricresyl phosphate (OIL-1) 0.50 g / m ² gelatin 3.5 g / m ² Second layer: surface protective layer PM-1 0.15 g / m ² PM-2 0.04 g / m ² Gelatin 0.65 g / m ²

[0086]

Embedded image

[0087]

Embedded image

The sample obtained as described above was
Using a K light source, wedge exposure was performed through a Toshiba glass filter Y-48, and development was performed according to the following processing steps.

<< Sensitivity >> The sensitivity of each sample is represented by the reciprocal of the exposure amount at which the green density gives an optical density of fog + 0.15.
Sample No. The relative values are shown with the value of 101 as 100.

<< Fog >> Fog was indicated by the minimum density value of the characteristic curve obtained by measuring the green density of the developed sample.

<< Granularity >> Further, the granularity of the magenta color image was evaluated by RMS granularity. For RMS granularity, the area of green density fog + 0.3 is the opening scanning area of 1800 μm
² Scan with a microdensitometer with a slit width of 10 μm and a slit length of 180 μm, and measure the standard deviation of the variation of
The double value was determined, and is shown in Table 2 as a relative value when Sample 101 was taken as 100. The smaller the value, the better the graininess.

<< Preservability (ΔFog) >> Further, in order to evaluate fog generated during storage, the sample was conditioned for 24 hours at a temperature of 23 ° C. and a relative humidity of 65%, and then sealed in a resin can. Aged at a temperature of 55 ° C. for 5 days. After each of the samples was subjected to a development process together with the samples stored in a refrigerator, the difference between the minimum density values of the obtained characteristic curves was evaluated as a fog increase width during storage (Δfog). Table 2 shows the results.

<< Development processing >> Processing step Processing time Processing temperature Replenishment amount * Color development 3 minutes and 15 seconds 38 ± 0.3 ° C. 780 cc Bleaching 45 seconds 38 ± 2.0 ° C. 150 cc Fixing 1 minute and 30 seconds 38 ± 2. 0 ° C. 830 cc Stability 60 seconds 38 ± 5.0 ° C. 830 cc Drying 1 minute 55 ± 5.0 ° C. * The replenishing amount is a value per 1 m ² of the photosensitive material.

The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions and replenishers were used.

Color developer water 800 cc Potassium carbonate 30 g Sodium bicarbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-amino- 3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Add water to make 1 liter, and add potassium hydroxide or 20%
Adjust to pH 10.06 with sulfuric acid.

Color developing replenisher water 800 cc Potassium carbonate 35 g Sodium bicarbonate 3 g Potassium sulfite 5 g Sodium bromide 0.4 g Hydroxylamine sulfate 3.1 g 4-Amino-methyl-N-ethyl-N- (β-hydroxylethyl) Aniline sulfate 6.3 g Potassium hydroxide 2 g Diethylenetriaminepentaacetic acid 3.0 g Add water to make 1 liter, and add potassium hydroxide or 20%
The pH is adjusted to 10.18 using.

Bleaching solution water 700 cc Ammonium iron (III) 1,3-diaminopropanetetraacetate 125 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 40 g Ammonium bromide 150 g Glacial acetic acid 40 g Add water to make 1 liter. And adjust to pH 4.4.

Bleach replenisher 700 cc 1,3-diaminopropanetetraacetate iron (III) ammonium 175 g ethylenediaminetetraacetic acid 2 g sodium nitrate 50 g ammonium bromide 200 g glacial acetic acid 56 g After adjusting the pH to 4.4 using ammonia water or glacial acetic acid. Add water to make 1 liter.

Fixer water 800 cc Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.2 using aqueous ammonia or glacial acetic acid, add water to make 1 liter.

Fixing replenisher water 800 cc Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.5 using aqueous ammonia or glacial acetic acid, add water to make 1 liter.

Stabilizing solution and stabilizing replenishing solution water 900 cc para-octylphenyl polyoxyethylene ether (n = 10) 2.0 g dimethylol urea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzoisothiazolin-3-one 0.1 g Siloxane (UCC L-77) 0.1 g Ammonia water 0.5 cc Add water to make 1 liter, then add ammonia water or 50
Adjust to pH 8.5 with% sulfuric acid.

Table 2 shows the above results.

[0103]

[Table 2]

[0104]

Embedded image

As is clear from Table 2, the compound represented by the general formula (I) of the present invention has a higher fog ratio than the comparative compound.
The sensitivity, sensitivity / granularity relationship was excellent, and the fog during storage was smaller and improved as compared with Comparative Compound-4 having no adsorptive group. That is, a comparative compound having an adsorptive group in the molecule
2 and -3 have low fog, but at the same time have low sensitivity. On the other hand, the compound represented by the general formula (I) of the present invention suppresses the occurrence of fog, has no granularity deterioration, and has high sensitivity. Achieved.

Example 2 Emulsions B and D obtained in Example 1 were used as Sample Nos. In Example 1 of Japanese Patent Application No. 9-9423. When the same processing and evaluation as in Example 1 were performed using the 10th layer in the light-sensitive material configuration of Example 107,
Emulsion D of the present invention showed good results.

[0107]

According to the present invention, fog / sensitivity and sensitivity /
It was possible to provide a silver halide emulsion having an excellent grain relationship and improved storage stability, and a silver halide photosensitive material using the same.

Continued on the front page (72) Inventor Hiroshi Otani 1 Konica Stock Company, Sakuracho, Hino-shi, Tokyo In-house

Claims (5)

[Claims] 1. A silver halide emulsion chemically sensitized using a compound having an adsorptive group to silver halide and an unstable tellurium atom site in the molecule. 2. The compound according to claim 1, wherein the compound having an adsorptive group to silver halide and an unstable tellurium atom site in the molecule is a compound represented by the following general formula (I). Silver halide emulsion. Embedded image [In the formula, A represents an atom group containing a group that can be adsorbed to silver halide, L represents a divalent linking group, and Z represents an atom group containing an unstable tellurium atom site. m represents 0 or 1, and n represents an integer of 1 to 3. ] 3. A support comprising at least one photosensitive silver halide emulsion layer on a support, wherein at least one silver halide emulsion layer contains the silver halide emulsion according to claim 1 or 2. A silver halide color light-sensitive material. 4. A silver halide light-sensitive material comprising the compound according to claim 1 or 2. 5. A silver halide color light-sensitive material according to claim 3, comprising the compound according to claim 1. Description: