JPH0792601A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a photographic sensitive material high in sensitivity and small in residual dye stains after development processing, in change of performance in the case of applying pressure to the photosensitive material and in change of performance due to its exposure before and after its storage. CONSTITUTION:This photosensitive material have on its support at least one silver halide emulsion layer and this layer contains a silver halide emulsion chemically sensitized by using at least one kind of selenium sensitizer and spectrally sensitized by using a benzimidazolocarbocyanine having a polarographic half-wave oxidation potential of nobler than 0.7VvsSCE and baser than 1.1VvsSCE.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has a high sensitivity and a small amount of residual color after development processing, changes when pressure is applied to the photosensitive material (pressure property), and changes in performance due to storage of the photosensitive material before exposure (raw storage). Property) and a change in storage of the light-sensitive material after exposure (latent image storability) are small.

[0002]

2. Description of the Related Art In silver halide photographic light-sensitive materials,
High sensitivity and excellent graininess are required. The technology for increasing the sensitivity is to increase the sensitivity of the light-sensitive material to reduce the amount of light required for the light exposure, and to reduce the size of silver halide grains required to give the same sensitivity. It is very important because it can improve the image quality. It is known that it is useful to use a selenium sensitizer at the time of chemical sensitization as a means for that. For example, JP-B-4-37979 discloses that a silver halide emulsion having high sensitivity and excellent storage stability of fog can be obtained by combining selenium sensitization, a specific cyanine dye and a monodisperse emulsion. . However, according to this method, there are problems that the sensitivity changes greatly during storage and that many residual colors remain after development processing. These are important problems to provide a higher quality silver halide photographic light-sensitive material, and their solution has been desired. In particular, since the silver halide color reversal photographic light-sensitive material is directly used for appreciation after development, the performance change and the residual color after development are serious problems, and their solution is strongly desired. Was there. Further, in JP-A-61-32840, a combination of a spectral sensitizing dye partially overlapping with the general formula (S-1) of the present invention and a tabular silver halide emulsion having an average aspect ratio of 5 or more is used to improve the Although it is disclosed that a light-sensitive material having high sensitivity and good storage stability can be obtained, it is still insufficient for higher requirements such as pressure resistance. No specific measures for these problems are described, and there is no description about introducing dislocation lines into tabular silver halide grains or using a selenium sensitizer during chemical sensitization.
Regarding the selenium sensitization method, in addition to the above, HE Spencer et al., Journal of Photographic Science, Vol. 31, 1
It is well known in the art as described in pages 58 to 169 (1963), etc.
As described in No. 838, No. 3-116132, No. 4-25832, No. 3-237450, etc.,
Improvements have been made in selenium sensitizers and their usage.

[0003]

SUMMARY OF THE INVENTION Accordingly, the object of the present invention is to provide a high sensitivity, little residual color after development, and little change in performance when pressure is applied to the light-sensitive material and little change in performance due to storage before and after exposure. An object is to provide a silver halide photographic light-sensitive material. Furthermore, it is to provide a silver halide color reversal photographic light-sensitive material having such characteristics.

[0004]

The above-mentioned problems of the present invention are as follows.
It was achieved by the following means. (1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide emulsion contained in the silver halide emulsion layer contains at least one selenium sensitizer. It is characterized by being chemically sensitized, spectrally sensitized with a benzimidazolocarbocyanine compound having a polarographic half-wave oxidation potential nobler than 0.7 V _VS SCE and less noble than 1.1 V _VS SCE. (2) In the silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide emulsion contained in at least one emulsion layer has an aspect ratio of Two or more tabular silver halide grains account for 50% or more and 100% or less of the projected area of all silver halide grains in the emulsion. Child is emulsions having at least 10 or more dislocation lines per one grain, and a polarographic half-wave oxidation potential 0.7 V _VS SCE than noble, 1.1V
_A silver halide photographic light-sensitive material characterized by being spectrally sensitized with a benzimidazolocarbocyanine compound, which is baser than _VS SCE, and (3) a silver halide emulsion using at least one selenium sensitizer. A silver halide photographic light-sensitive material according to item (2), which is chemically sensitized, and (4) a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support. ,
The silver halide emulsion contained in at least one emulsion layer is a silver halide emulsion having a relative standard deviation of the grain size distribution of 20% or less and a layered structure of three or more phases having different iodide contents. Moreover, the polarographic half-wave oxidation potential is more noble than 0.7V _VS SCE and 1.1V _VS SCE.
A silver halide photographic light-sensitive material characterized by being spectrally sensitized with a more base benzimidazolocarbocyanine compound, (5) a silver halide emulsion is chemically sensitized using at least one selenium sensitizer. A silver halide photographic light-sensitive material as described in (4) above,
(6) Yellow colloidal silver is contained in a layer adjacent to the silver halide emulsion layer containing the above silver halide emulsion, (1), (2), (3), (4) or (5) (7) a silver halide photographic light-sensitive material, and (7) a silver halide emulsion layer containing a silver halide emulsion or a layer adjacent thereto containing a silver iodobromide emulsion whose surface and / or inside is covered. (1), (2), (3), (4),
A silver halide photographic light-sensitive material according to item (5) or (6),
(8) The silver halide photographic light-sensitive material is a silver halide color reversal photographic light-sensitive material for daylight light sources or tungsten light sources (1), (2),
In the silver halide photographic light-sensitive material described in (3), (4), (5), (6) or (7) and (9) the silver halide photographic light-sensitive material, a benzimidazolocarbocyanine compound is represented by the following general formula: (1), (2), (3), (4), (5), (6), characterized by being represented by (S-1)
The silver halide photographic light-sensitive material according to item (7) or (8).

[0005]

[Chemical 2]

In the general formula (S-1), V ₁ , V ₂ ,
V ₃ and V ₄ represent a hydrogen atom or an electron-withdrawing group,
_At least two or more of the substituents represented by ₁ , V ₂ , V ₃ and V ₄ are electron withdrawing groups. R ₁₁ is _{- (CH 2) s (CF} 2) m H or - (CH _{2) s}
Represents a group represented by (CF ₂ ) _m F, and s is 0 to 3
Represents an integer, and m represents an integer from 1 to 8. R ₁₂ ,
R ₁₃ and R ₁₄ may be the same or different, and are — (CH
_{2) p (CF 2) q} H group or a - (CH _{2) p} (CF
₂ ) represents a _q F group, an optionally substituted alkyl group or alkenyl group having a total carbon number of 10 or less, and R ₁₂ ,
At least one of R _{13 and} R ₁₄ is a group having a sulfo group or a carboxy group. p represents an integer of 0 to 3, and q represents an integer of 1 to 8. X ₁₁ represents a counter ion necessary for neutralizing the charge. n ₁₁ represents 0 or 1, and is 0 in the case of an inner salt.

The spectral sensitizing dye composed of a benzimidazolocarbocyanine compound used in the present invention (hereinafter referred to as benzimidazolocarbocyanine spectral sensitizing dye) has a polarographic half-wave oxidation potential (Eox ^1/2 ) of 0.7 V vsSC.
It is a benzimidazolocarbocyanine spectral sensitizing dye that is more noble than E and less noble than 1.1 V _VS SCE.
The preferable range of the polarographic half-wave oxidation potential is 0.7 to
1.0 V _VS SCE, more preferably 0.75
It is 1.0V _VS SCE. The polarographic half-wave oxidation potential is more noble than 0.7 V _vs SCE, and the raw preservation property is greatly improved, but when it becomes noble than 1.1 V _vs SCE, the potential of the photoexcited state absorbing visible light is increased. Becomes too lower than the conduction band of silver halide, and the spectral sensitization efficiency decreases. The polarographic half-wave oxidation potentials of sensitizing dyes are T. Tani, K. Ohzeki, K. Seki, Journal of
the Electrochemical Society, Volume 138, 1411-1415 and J. Lenhard, Journal of Imaging Science, Volume 30,
It can be measured by the phase discrimination second harmonic AC voltammetry method described on pages 27 to 35.

The compound represented by formula (S-1) of the present invention will be described in more detail below. V ₁ , V ₂ , V
More preferable electron-withdrawing groups represented by ₃ and V ₄ are a halogen atom and a lower perfluoroalkyl group (more preferably a total carbon number of 5 or less, for example, trifluoromethyl group, 2,2,2-trifluoroethyl group). , 2, 2,
3,3-tetrafluoropropyl group and the like),
Acyl group (total carbon number is preferably 8 or less, for example, acetyl group, propionyl group, benzoyl group, mesityl group, benzenesulfonyl group and the like), alkylsulfamoyl group (total carbon number is 5 or less, more preferably, , A methylsulfamoyl group, an ethylsulfamoyl group, etc.), a carboxy group, an alkoxycarbonyl group (more preferably a total carbon number of 5 or less, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, etc. ) And a cyano group and the like. R ₁₁ is _{- (CH 2) s (CF} 2) m H or - (C
H ₂ ) _s (CF ₂ ) _m F represents a group, s represents an integer of 0 to 3, and m represents an integer of 1 to 8. The larger s is, the smaller the electronic effect of the fluorine atom is. Therefore, smaller s is preferable, and 0 or 1 is particularly preferable.

R ₁₂ , R ₁₃ and R _{14, which} may be the same or different, are-(CH ₂ ) _p (CF ₂ ) _q H groups _or-
(CH ₂ ) _p (CF ₂ ) _q F group represents an optionally substituted alkyl group or alkenyl group having 10 or less carbon atoms, and at least one of R ₁₂ , R _{13 and} R ₁₄ is A group having a sulfo group or a carboxy group.
p represents an integer of 0 to 3, and q represents an integer of 1 to 8. The larger p is, the smaller the electron effect of the fluorine atom is. Therefore, smaller p is preferable, and 0 or 1 is particularly preferable. More preferable substituents other than the sulfo group and the carboxy group of the alkyl group and the alkenyl group represented by R ₁₂ , R ₁₃ and R ₁₄ include a halogen atom (eg, a fluorine atom,
Chlorine atom, bromine atom), hydroxy group, alkoxy group having 6 or less carbon atoms (eg, methoxy group, ethoxy group, propoxy group, butoxy group), optionally substituted aryl group having 8 or less carbon atoms (eg, Phenyl group, tolyl group, sulfophenyl group, carboxyphenyl group, etc.), heterocyclic group (eg, furyl group, thienyl group, etc.), carbon number 8
The following optionally substituted aryloxy groups (for example, chlorophenoxy group, phenoxy group, sulfophenoxy group, hydroxyphenoxy group, etc.) Acyl groups having 8 or less carbon atoms (for example, benzenesulfonyl group, methanesulfonyl group, acetyl group) , Propynyl groups, etc.), alkoxycarbonyl groups having 6 or less carbon atoms (eg, ethoxycarbonyl group, butoxycarbonyl group, etc.), cyano groups, alkylthio groups having 6 or less carbon atoms (eg, methylthio group, ethylthio group, etc.), 8 carbon atoms. The following optionally substituted arylthio group (for example, phenylthio group, tolylthio group, etc.), optionally substituted carbamoyl group (for example, carbamoyl group, N-ethylcarbamoyl group, etc.), C8 The following acylamino groups (eg, acetylamino group, methane Honylamino group, etc.), ureido group having 6 or less carbon atoms (for example, ureido group, 3-methylureido group, 3-ethylureido group, etc.), acylaminocarbonyl group having 8 or less carbon atoms (eg, acetylaminocarbonyl group, propionyl). Aminocarbonyl group, etc.),
An alkyl- or aryl-substituted sulfonylaminocarbonyl group having 8 or less carbon atoms (for example, a benzenesulfonylaminocarbonyl group, a methanesulfonylaminocarbonyl group, an ethanesulfonylaminocarbonyl group, etc.) and the like are more preferable. Two or more of these substituents may be included. Particularly preferred specific examples include, for example, methyl group, ethyl group, propyl group, allyl group, pentyl group, hexyl group, methoxyethyl group, ethoxyethyl group, phenethyl group, tolylethyl group, sulfophenethyl group, 2,2-difluoroethyl. Group, 2,2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, carbamoylethyl group, hydroxyethyl group, 2- (2-hydroxyethoxy) ethyl group, carboxymethyl group, carboxy Ethyl group, ethoxycarbonylmethyl group, sulfoethyl group, 2-chloro-3-sulfopropyl group, 3-
Sulfopropyl group, 2-hydroxy-3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2-
(2,3-dihydroxypropyloxy) ethyl group, 2
Examples thereof include a-[2- (3-sulfopropyloxy) ethoxy] ethyl group, an acetylaminocarbonylethyl group, an acetylaminocarbonylmethyl group, a methylsulfonylaminocarbonylethyl group and an ethylsulfonylaminocarbonylethyl group. In addition, R ₁₁ represents-(CH
_{2) s (CF 2) m} H _{group, - (CH 2) s (} CF 2) m
The F group is also an alkyl group represented by R ₁₂ , R ₁₃ and R ₁₄ ,
More preferably used.

Specific examples of the group represented by R ₁₁ include difluoromethyl group, trifluoromethyl group, 1,
1,2,2-tetrafluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group,
2,2,3,3-tetrafluoropropyl group, 2,2
3,3,3-pentafluoropropyl group, 2,2,3
3,4,4-hexafluorobutyl group, 2,2,3
3,4,4,5,5-octafluoropentyl group, 2,
2,3,3,4,4,5,5,6,6-decafluorohexyl group, 2,2,3,3,4,4,5,5,6,6
7,7-dodecafluoroheptyl group, 2,2,3,3,
4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononyl group etc. are mentioned. In the sensitizing dye represented by the general formula (S-1), V ₁ , V
_It is particularly preferable that the sum of Hammett's substituent constants (σ _p ) of the groups represented by ₂ , V ₃ and V ₄ is 0.5 or more. X ₁₁ is preferably K ⁺ , Na ⁺ , HN ⁺ (E
t) ₃ , pyridinium cation, I ⁻ , Br ⁻ , ClO
₄ ^-, etc. p- toluenesulfonate and the like as a preferable example.

The benzimidazolocarbocyanine compound used in the present invention and the spectral sensitizing dye represented by formula (S-1) can be incorporated in the silver halide emulsion of the present invention by dispersing them directly in the emulsion. Or water, methanol, ethanol, propanol, acetone, methyl cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy- It may be added to the emulsion by dissolving it in a solvent such as 1-butanol, 1-methoxy-2-propanol, phenoxyethanol, acetonitrile, tetrahydrofuran, N, N-dimethylformamide or a mixed solvent. Further, as described in US Pat. No. 3,469,987, etc., a dye is dissolved in a volatile organic solvent, the solution is dispersed in water or a hydrophilic colloid, and this dispersion is added to an emulsion. As described in JP-B-46-24185, a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it, and adding the dispersion to an emulsion, JP-B-44-23389, As described in JP-B-44-27555, JP-B-57-22091, etc., a dye is dissolved in an acid and the solution is added to the emulsion, or an acid or a base is allowed to coexist with the dye to prepare an aqueous solution and the emulsion is added to the emulsion. How to add,
US Pat. No. 3,822,135, US Pat.
No. 025, etc., a method of adding an aqueous solution or colloidal dispersion in the presence of a surfactant into an emulsion, described in JP-A-53-102733 and JP-A-58-105141. As described in JP-A No. 51-74624, a dye is directly dispersed in a hydrophilic colloid, and the dispersion is added to an emulsion. A method of adding the solution into the emulsion can also be used. Also, ultrasonic waves can be used for dissolution.

The sensitizing dye used in the present invention may be added to the silver halide emulsion of the present invention at any step in the preparation of emulsions which has been found to be useful so far. For example, US Pat. No. 2,735,766, US Pat. No. 3,628,960, US Pat. No. 4,183,756.
No. 4,225,666, JP-A-58-18.
No. 4,142, JP-A-60-196749 and the like, as disclosed in the specification such as silver halide grain formation step or / and before desalting, during the desalting step and / or after desalting, Before the start of aging, JP-A-58-1139
As disclosed in the specification of No. 20, etc., it may be added at any time or step immediately before the chemical ripening or during the step or before the emulsion is coated after the chemical ripening and before the coating. Also, US Pat. No. 4,225,666,
As disclosed in the specification of JP-A-58-7629, the same compound alone or in combination with a compound having a different structure can be used, for example, in the same step, or during the grain forming step and the chemical aging step. Alternatively, it may be added by dividing it into different processes such as after completion of chemical ripening, or before chemical ripening or during and after completion of the chemical ripening. It may be added by changing. In addition, a predetermined amount may be added in a short time, or may be continuously added in any step for a long time, for example, from the nucleation in the particle forming step to the completion of the particle formation or most of the chemical ripening step. May be. In such a case, the addition speed may be a constant flow rate, or the flow rate may be accelerated or decelerated.

The addition amount of the benzimidazolocarbocyanine spectral sensitizing dye of the present invention varies depending on the shape and size of silver halide grains, but is 4 × 10 ⁻⁶ to 8 × 10 ⁻ per mol of silver halide. It can be used in ³ moles. For example, when the silver halide grain size is 0.2 to 1.3
In the case of μm, the surface area of the silver halide grain is 2 × 10 ⁻⁸ per 1 m ² (coverage when the occupied area is 100 A ° ² is 1.2% {coverage when the occupied area is 60 A ° ² is 0. .7
%, The coverage rate when the occupied area is 200 A ° ² , 2.4%})
~ 3.5 × 10 ^-6 mol (coverage 210.8% when occupied area 100A ° ² {coverage 126.4% when occupied area 60A ° ² , occupied area 200A ° ² The coating amount is 421.7%}), and the addition amount is preferably 2.5 × 10 ^−7.
(Occupied area 100A ° ^2, and coverage 15.1% when the {occupation area 60A ° ² and covered 9.1% of the time were}) to 2. 0
× 10 ^-6 (coverage 12 when the occupied area is 100 A ° ²
0.5% (coverage when occupation area is 60 A ²⁾ 72.2
%) Mol is more preferable. The sensitizing dye of the present invention can be used in combination with other sensitizing dyes. The combined use of such sensitizing dyes is often used to obtain a desired spectral sensitivity distribution or for supersensitization. Other sensitizing dyes to be combined with the sensitizing dye of the present invention are not particularly limited, but for example, JP-A-59-20022.
The sensitizing dyes represented by formula (III) or (IV) described on page 9 to page 15 of JP-A No. 61-32840, cited above, are preferably used. Of these, those having less residual color after development are more preferable for use in combination with the spectral sensitizing dye of the present invention. The color sensitivity of the silver halide emulsion layer relating to the combined use of the sensitizing dye and the emulsion of the present invention is not particularly limited, but it is usually preferably used in the green-sensitive emulsion layer. The combined use with the other sensitizing dyes specifically mentioned above is preferably used mainly in the green-sensitive emulsion layer. In addition, the case where the sensitizing dye of the present invention is supplementarily used in the red-sensitive emulsion layer is also considered. Specific examples of the compound represented by formula (S-1) are shown below, but the invention is not limited thereto.

[0014]

[Table 1]

[0015]

[Table 2]

[0016]

[Table 3]

Next, the silver halide grains chemically sensitized with a selenium compound will be described. As the selenium sensitizer used in the present invention, selenium compounds disclosed in conventionally known patents can be used. That is, it is usually used by adding an unstable selenium compound and / or a non-unstable selenium compound and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. As the unstable selenium compound, compounds described in JP-B-44-15748, JP-B-43-13489, JP-A-4-25832 and JP-A-4-109240 are preferably used. Specific examples of unstable selenium compounds include isoselenocyanates (eg, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (eg, 2-selenopropione). Acid, 2-selenobutyric acid), selenoesters, diacyl selenides (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium and the like. .. The preferred types of labile selenium compounds have been described above, but are not limiting. Speaking to a person skilled in the art of an unstable selenium compound as a sensitizer for a photographic emulsion, the structure of the compound is not so important as long as selenium is unstable, and the organic portion of the selenium sensitizer molecule is It is generally understood that it has no role other than to support selenium and to make it present in the emulsion in an unstable form. In the present invention, the labile selenium compound having such a broad concept is advantageously used.

As the non-labile selenium compound used in the present invention, JP-B-46-4553 and JP-B-52-34 are used.
The compounds described in JP-B No. 492 and JP-B-52-34491 are used. Examples of non-labile selenium compounds include selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, Examples include 2-selenaoxazolidinethione and derivatives thereof. Among these selenium compounds, compounds represented by the following general formulas (Se-I) and (Se-II) are preferable.

[0019]

[Chemical 3]

In the general formula (Se-I), Z ₁ and Z ₂ may be the same or different and each represents an alkyl group (eg, methyl, ethyl, t-butyl, adamantyl, t-).
Octyl), alkenyl groups (eg vinyl, propenyl), aralkyl groups (eg benzyl, phenethyl), aryl groups (eg phenyl, pentafluorophenyl, 4-chlorophenyl, 3-nitrophenyl,
4-octylsulfamoylphenyl, α-naphthyl), a heterocyclic group (for example, pyridyl, thienyl, furyl, imidazolyl), —NR ₁ (R ₂ ), —OR ₃ or —SR ₄ is represented. R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. Examples of the alkyl group, aralkyl group, aryl group or heterocyclic group include the same examples as Z ₁ . However, R ₁ and R ₂ may be a hydrogen atom or an acyl group (for example, acetyl, propanoyl, benzoyl, heptafluorobutanoyl, difluoroacetyl, 4-nitrobenzoyl, α-naphthoyl, 4-trifluoromethylbenzoyl). Good. In formula (Se-I), Z ₁ preferably represents an alkyl group, an aryl group or —NR ₁ (R ₂ ), and Z ₂
Represents -NR ₅ (R ₆ ). R ₁ , R ₂ , R ₅ and R
₆ may be the same or different, a hydrogen atom,
Represents an alkyl group, an aryl group, or an acyl group. In the general formula (Se-I), more preferably N, N-dialkylselenourea, N, N-N'-trialkyl-N'-acylselenourea, tetraalkylselenourea, N, N-
Dialkyl-arylselenoamide, N-alkyl-N
-Aryl-aryl-selenoamide.

[0021]

[Chemical 4]

In the general formula (Se-II), Z ₃ , Z ₄ and Z
₅ may be the same or different, and an aliphatic group,
An aromatic group, a heterocyclic _{group, -OR 7, -NR 8 (R} 9), -
Represents SR ₁₀ , SeR ₁₁ , X or a hydrogen atom. R ₇ ,
R ₁₀ and R ₁₁ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, R ₈ and R ₉ represent an aliphatic group,
It represents an aromatic group, a heterocyclic group or a hydrogen atom, and X represents a halogen atom. In the general formula (Se-II), Z
_The aliphatic group represented by ₃ , Z ₄ , Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group or aralkyl group (for example, , Methyl, ethyl, n-propyl, isopropyl, t
-Butyl, n-butyl, n-octyl, n-decyl, n
-Hexadecyl, cyclopentyl, cyclohexyl, allyl, 2-butenyl, 3-pentenyl, propargyl,
3-pentynyl, benzyl, phenethyl). In the general formula (Se-II), Z ₃ , Z ₄ , Z ₅ , R ₇ ,
The aromatic group represented by R ₈ , R ₉ , R ₁₀ and R ₁₁ is a monocyclic or condensed ring aryl group (eg, phenyl, pentafluorophenyl, 4-chlorophenyl, 3-sulfophenyl, α-naphthyl, 4 -Methylphenyl).

In the general formula (Se-II), Z ₃ , Z
_The heterocyclic group represented by ₄ , Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a saturated 3- or 10-membered ring containing at least one of a nitrogen atom, an oxygen atom or a sulfur atom. Unsaturated heterocyclic groups (eg pyridyl, thienyl, furyl, thiazolyl, imidazolyl, benzimidazolyl)
Represents In formula (Se-II), the cations represented by R ₇ , R ₁₀ and R ₁₁ represent an alkali metal atom or ammonium, and the halogen atom represented by X is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Represents In general formula (Se-II), preferably Z
₃ , Z ₄ or Z ₅ is an aliphatic group, an aromatic group or -OR
₇ , R ₇ represents an aliphatic group or an aromatic group.
In formula (Se-II), more preferably trialkylphosphine selenide, triarylphosphine selenide,
Represents trialkylselenophosphate or triarylselenophosphate. Below, the general formula (Se-I)
Specific examples of the compounds represented by and (Se-II) are shown below, but the present invention is not limited thereto.

[0024]

[Chemical 5]

[0025]

[Chemical 6]

[0026]

[Chemical 7]

[0027]

[Chemical 8]

These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol, alone or in a mixed solvent, or disclosed in JP-A-4-140738 and JP-A-4-14.
No. 0742, No. 5-11381, No. 5-11381
Nos. 5-11385 to 5-11388 can be added at the time of chemical sensitization. It is preferably added before the start of chemical sensitization. The selenium sensitizer used is not limited to one type, and two or more types of the above selenium sensitizers can be used in combination. The unstable selenium compound and the non-unstable selenium compound may be used in combination. Further, a tellurium sensitizer may be used in combination with the selenium sensitizer. The addition amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the type and size of silver halide, the temperature and time of ripening, and the like. It is 1 × 10 ⁻⁸ mol or more per mol. It is more preferably 1 × 10 ⁻⁷ mol or more and 3 × 10 ⁻⁵ mol or less. The temperature of chemical ripening when a selenium sensitizer is used is preferably 45 ° C. or higher. More preferably, it is 50 ° C. or higher and 80 ° C. or lower. pAg and pH are arbitrary.
For example, the effect of the present invention can be obtained in a wide range of pH from 4 to 9. It is more effective to perform selenium sensitization in the presence of a silver halide solvent.

As the silver halide solvent which can be used in the present invention, US Pat. Nos. 3,271,157, 3,531,289, 3,574,628 and JP-A-54- (A) Organic thioethers described in 1019, 54-158917 and the like, JP-A-53-82.
(B) thiourea derivatives described in JP-A No. 408, 55-77737, 55-2982 and the like, JP-A-53-1.
No. 44319 (c) silver halide solvent having a thiocarbonyl group sandwiched between oxygen or sulfur atom and nitrogen atom, (d) imidazoles described in JP-A No. 54-100717, (e) ) Sulfite, (f) thiocyanate and the like. Particularly preferred solvents are thiocyanate and tetramethylthiourea.
Although the amount of the solvent used varies depending on the type, for example, in the case of thiocyanate, the preferable amount is 1 × 10 ⁻⁴ mol or more and 1 × 10 ⁻² mol or less per mol of silver halide.

The silver halide emulsion of the present invention can achieve higher sensitivity and lower fog by combined use of sulfur sensitization and / or gold sensitization in chemical sensitization. Sulfur sensitization is usually performed by adding a sulfur sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain period of time. The gold sensitization is usually carried out by adding a gold sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. For the above-mentioned ion sensitization, known sulfur sensitizers can be used. For example, thiosulfate, thioureas, allyl isothiocyanate,
Examples include cystine, p-toluenethiosulfonate, rhodanine and the like. Other US Pat. No. 1,574,94
No. 4, No. 2,410,689, No. 2,278,9
No. 47, No. 2,728,668, No. 3,501,
No. 313, No. 3,656,955, German Patent No. 1,422,869, Japanese Patent Publication No. 56-24937.
And sulfur sensitizers described in JP-A-55-45016 can also be used. The addition amount of the ion sensitizer may be an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as pH, temperature, and size of silver halide grains, but 1 × 10 ^-7 mol or more per mol of silver halide,
It is preferably 5 × 10 ⁻⁴ mol or less.

As the gold sensitizer for the above-mentioned gold sensitization, the oxidation number of gold may be +1 valence or +3 valence, and a gold compound usually used as a gold sensitizer can be used. Representative examples include chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyl trichlorogold and the like. The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ mol per mol of silver halide. At the time of chemical ripening, it is not necessary to place a particular limitation on the timing and order of addition of the sulfur sensitizer and / or the gold sensitizer which can be used in combination with the silver halide solvent and the selenium sensitizer or the tellurium sensitizer. Alternatively, for example, the above compounds can be added at the same time as the initial (preferably) chemical ripening or during the progress of chemical ripening, or at different addition points. In addition, upon addition, an organic solvent capable of mixing the above compound with water or water, for example, methanol,
It may be added after being dissolved in a single liquid or a mixed liquid such as ethanol and acetone.

In the present invention, the total calcium content in the light-sensitive material is preferably 3 mg / m ² or more.
It is more preferably from mg / m ^{2 to} 50 mg / m ² and even more preferably from 7 mg / m ^{2 to} 30 mg / m ² . If the calcium content is higher than these values, fog at storage, especially at high temperature and high humidity, will increase, which is not preferable, and if it is lower than this, the sensitivity will be low, which is not preferable.

The silver halide emulsion of the present invention is preferably reduction-sensitized during the grain formation process. Applying reduction sensitization during the grain formation process of a silver halide emulsion basically means that it is performed during nucleation, ripening and growth.
The reduction sensitization may be carried out at any stage of nucleation, physical ripening and growth which are the initial stages of grain formation. Most preferred is a method of reduction sensitization during the growth of silver halide grains. Here, during the growth, a method of performing reduction sensitization in the state where the silver halide grains are physically ripened or are being grown by the addition of a water-soluble silver salt and a water-soluble alkali halide,
It is meant to include a method of performing reduction sensitization in a state where the growth is temporarily stopped during the growth and then further growing.

The above-mentioned reduction sensitization is a method of adding a known reducing agent to a silver halide emulsion, pAg1 called silver ripening.
Method of growing or aging in a low pAg atmosphere of 7,
Any method of growing or aging in a high pH atmosphere of pH 8 to 11 called high pH aging can be selected. Also, two or more methods can be used in combination. The method of adding a reduction sensitizer is a preferable method because the level of the reduction sensitizer can be finely adjusted. Known examples of reduction sensitizers include stannous salts, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, and borane compounds. In the present invention, these known compounds can be used by selecting from known compounds, and two or more kinds of compounds can be used in combination. As the reduction sensitizer, stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and ascorbic acid derivatives are preferable compounds. The addition amount of the reduction sensitizer depends on the emulsion production conditions, so it is necessary to select the additive, but the range of 10 ^-8 to 10 ^-3 mol per mol of silver halide is suitable. The reduction image sensitizer can be dissolved in water or a solvent such as alcohols, glycols, ketones, esters and amides and added during grain formation.
It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time for particle formation. Further, particles may be formed using an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide. In addition, it is also a preferable method to add the solution of the reduction sensitizer in several batches or to add the solution continuously as the grains are formed. In the silver halide emulsion of the present invention, more preferably 5 × 10 ⁻⁵ mol or more of a palladium compound is added per mol of silver halide after the completion of the grain formation process and preferably before the desalting step.

Here, the palladium compound is palladium 2
It means a valent salt or a tetravalent salt. Preferably the palladium compound is represented by M ₂ PdX ₆ or M ₂ PdX ₄ . Here, M represents a hydrogen atom, an alkali metal atom or an ammonium group. X is a halogen atom (eg chlorine,
Bromine, iodine atom). Specifically, K ₂ PdC
l ₄ , (NH ₄ ) ₂ PdCl ₆ , Na ₂ PdCl ₄ , (N
_{H 4) 2 PdCl 4, Li} 2 PdCl 4, Na 2 PdCl
₆ , K ₂ PdBr ₄ or K ₂ PdBr ₆ are preferred. Most preferably, these palladium compounds are used in combination with thiocyanate ions in an amount 5 times or more that of the palladium compound.

The tabular silver halide grains in the present invention will be described. The tabular silver halide grain (hereinafter, referred to as "tabular grain") in the present invention has two parallel main planes facing each other, and the circle-equivalent diameter of the main plane (the same projected area as the main plane It means a particle whose diameter is greater than twice the distance between principal planes (that is, the thickness of the particle). Such tabular silver halide grains having an aspect ratio of 2 or more have a projected area of 50 of all silver halide grains in the emulsion.
% Or more and 100% or less, preferably 65% or more and 100% or less, more preferably 80% or more and 99% or less.

The average grain diameter / grain thickness ratio of the emulsion having tabular grains in the present invention is preferably from 2 to 40, and particularly preferably from 3 to 20. Here, the aspect ratio (tabular grain diameter / grain thickness ratio) is obtained by averaging the grain diameters / grain thickness ratios of all the tabular grains. As a simple method, the average diameter of all the tabular grains and
It can also be determined as a ratio to the average thickness of all tabular grains. The diameter (corresponding to a circle) of tabular grains in the present invention is 0.3.
˜5.0 μm, preferably 0.3 to 4.0 μm, and more preferably 0.3 to 3.0 μm. The grain thickness is 0.
It is less than 5 μm, preferably 0.05 μm or more and less than 0.5 μm, and more preferably 0.08 to 0.3 μm. The particle diameter and particle thickness in the present invention can be determined from electron micrographs of the particles as in the method described in US Pat. No. 4,434,226. The halogen composition of the tabular grains is preferably silver iodobromide or silver chloroiodobromide, and particularly, the silver iodide content is 0.1 to 20 mol%, preferably 1 to 10 mol%, more preferably 1 ~ 5 mol%
Of silver iodobromide is preferred.

The tabular grains have (111) planes and (100) planes.
It is possible to select one formed from a plane or a mixed plane of (111) plane and (100) plane. Further, other Miller index planes may be mixed. The flatness (= particle diameter (μm) / (particle thickness μm) ² ) is 2
It is preferably 0 or more and 4000 or less, more preferably 25 or more and 2000 or less, but not limited to this.

Next, dislocation lines of tabular grains will be described.
A dislocation line is a linear lattice defect on the slip plane of a crystal at the boundary between a region that has already slipped and a region that has not slipped yet. Regarding dislocation lines of silver halide crystals, 1) C.
R. Berry, J. Appl, Phys., 27, 636 (1956), 2) C.
R. Berry, DC Skilman, J. Appl. Phys., 35, 2165
(1964), 3) JF Hamilton, Phot. Scl. Eng., 11, 5
7 (1967), 4) T. Shiozawa, J. Soc. Phot. Sci. Ja
p., 34, 16 (1971), 5) T. Shiozawa, J. Soc. Phot.
There are documents such as Sci. Jap., 35, 213 (1972), and the analysis can be performed by an X-ray diffraction method or a direct observation method using a low-temperature transmission electron microscope. When directly observing dislocation lines using a transmission electron microscope, be careful not to apply pressure enough to generate dislocation lines on the grains, place the silver halide grains taken out from the emulsion on a mesh for electron microscope observation, The sample is observed by a transmission method in a cooled state so as to prevent damage (for example, printout) due to an electron beam.

In this case, the thicker the particles, the more difficult it is for an electron beam to pass therethrough. Therefore, it is better to use a high-voltage electron microscope (200 kV or more for a thickness of 0.25 μm) for clearer observation. You can On the other hand, the effects of dislocation lines on the photographic performance are GC Farnell, RB Fli.
nt, JB Chanter, J. Phot. Sci., 13, 25 (1965), where large-size tabular silver halide grains with high aspect ratio form latent image nuclei and defects in the grains. It has been shown that and are closely related. JP-A-63-220238 and JP-A-1-201649 disclose tabular silver halide grains in which dislocation lines are intentionally introduced. It is shown in these patent applications that tabular grains having dislocation lines introduced therein are superior in photographic characteristics such as sensitivity and reciprocity law to tabular grains having no dislocation lines.

The method of introducing dislocation lines into silver halide grains will be described below. In the present invention, it is preferable to introduce dislocation lines into the silver halide grains as follows. That is, a base silver halide grain is prepared, and a silver halide phase containing silver iodide (the above-described silver halide coating shell, a deposition layer, and epitaxial growth) is formed on the base grain. As described above, the higher the silver iodide content of these silver halide phases, the more preferable. The silver iodide content of the base grains is preferably 0 to 15 mol%, more preferably 0 to 12 mol%, and particularly preferably 0 to 10 mol%.

The amount of halogen added to form this high silver iodide content phase on the base grains is preferably 2 to 15 mol% of the silver amount of the base grains, and more preferably 2 to 10 mol%.
Mol%, particularly preferably 2 to 5 mol%. At this time,
This high silver iodide content phase is preferably present in the range of 5 to 80 mol%, more preferably 10 to 70 mol%, particularly preferably 20 to 60 mol%, based on the total amount of silver.
Is to exist within the range of. The high silver iodide content phase may be formed on the base grains at any location, and the base grains may be covered or may be formed only on a specific site.
Further, it is preferable to control the position of the dislocation line in the grain by selecting a specific site and performing epitaxial growth. At that time, the composition of the halogen to be added, the addition method, the temperature of the reaction solution, pAg, the solvent concentration, the gelatin concentration, the ionic strength, etc. may be freely selected and used.

Then, dislocation lines can be introduced by forming a silver halide shell outside these phases. The composition of the silver halide shell may be any of silver bromide, silver iodobromide and silver chloroiodobromide, but silver bromide or silver iodobromide is preferred. In the case of silver iodobromide, the silver iodide content is preferably 0.1 to 12 mol%, more preferably 0.1 to 10 mol%, and most preferably 0.1.
~ 3 mol%. A preferable temperature in the above dislocation line introduction process is 30 to 80 ° C., and more preferably 35 to 80 ° C.
75 ° C, particularly preferably 35 to 60 ° C. Moreover, preferable pAg is 6.4 to 10.5. In the case of tabular grains, the position and the number of dislocation lines for each grain when viewed from the direction perpendicular to the principal plane can be determined from the photograph of the grain photographed with an electron microscope as described above.
Since dislocation lines may or may not be seen depending on the tilt angle of the sample with respect to the electron beam, in order to observe the dislocation lines without omission, the particle images of the same grain at as many sample tilt angles as possible should be observed. It is necessary to find the location. In the present invention, it is preferable to determine the existence position and the number of dislocation lines by changing the tilt angle for the same grain in 5 ° steps using five types of grain photographs using a high-voltage electron microscope.

When dislocations are introduced into the tabular grains in the present invention, the positions thereof can be selected from, for example, the apex portion and the fringe portion of the grains, or the introduction over the entire main plane portion. It is particularly preferable to define the fringe portion. The fringe portion referred to in the present invention refers to the outer periphery of the tabular grain, and in detail, in the distribution of silver iodide from the side to the center of the tabular grain, the silver iodide content at a certain point for the first time from the side is the grain. The point outside the point where the average silver iodide content of the whole is exceeded or below.

In the present invention, it is preferable to introduce dislocation lines into the silver halide grains with high density. When dislocation lines are introduced into the tabular grains, when the number of dislocation lines is counted by the above-mentioned method using an electron microscope, the number of dislocation lines per grain is 10 per grain.
Tabular grains having dislocation lines of not less than this number are preferable, those of not less than 30 are more preferable, and those of not less than 50 are particularly preferable. When dislocation lines are densely present or when dislocation lines are observed intersecting with each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, about 10 and 2
It can be counted as 0 or 30.

The dislocation dose distribution between silver halide grains is preferably uniform. When dislocation lines are introduced into the tabular grains in the present invention, tabular grains having 10 or more dislocation lines per grain in the fringe portion of the grains account for 10 of all grains.
It is preferably 0 to 50% (number), more preferably 100 to 70%, particularly preferably 10%.
It occupies 0 to 90%. In the present invention, when determining the proportion of grains containing dislocation lines and the number of dislocation lines, it is preferable to directly observe the dislocation lines for at least 100 grains, more preferably 200 grains or more, and particularly preferably 300 grains or more. Observe and ask.

Next, a method for producing tabular grains will be described. The tabular grains can be produced by appropriately combining methods known in the art. For example, in an atmosphere having a relatively high pAg value of pBr 1.3 or less, a seed crystal having 40% or more by weight of tabular grains is formed, and a silver and halogen solution is added while maintaining a pBr value of the same or higher. Then, it is obtained by growing seed crystals. It is desirable to add a silver and halogen solution so that new crystal nuclei are not generated in the grain growth process by adding silver and / or halogen. The size of tabular grains includes, for example, temperature control, selection of solvent type and amount, silver salt used during grain growth,
It can be adjusted by controlling the addition rate of the halide and the like.

The emulsion of the present invention is disclosed in JP-A-63-22023.
It can be prepared based on the method described in JP-A-8. The silver halide emulsion of the present invention preferably has a narrow grain size distribution, grain size and / or thickness distribution, and is adjusted through the steps of nucleation-Ostwald ripening and grain growth. JP-A-63-151618 The method described in 1) can be preferably used. During the production of the tabular grains used in the present invention, in order to accelerate the grain growth, the addition rate, the addition amount and the addition concentration of the silver salt solution (eg AgNO ₃ aqueous solution) and the halide solution (eg KBr aqueous solution) are increased. The method is preferably used.
Regarding these methods, for example, British Patent No. 1,33
5,925, U.S. Pat. Nos. 3,672,900, 3,650,757, 4,242,445, JP-A-55-142329, and JP-A-55-158124. Can be

Silver halide solvents are useful in promoting ripening. For example, it is known to have excess halogen ions present in the reactor to accelerate aging.
Therefore, it is clear that mere introduction of a halide salt solution into the reactor can accelerate aging. Other ripening agents can also be used. All of these ripening agents can be added to the dispersion medium in the reactor before the addition of silver and halide salts, and one or more halide salts, silver salts or peptizers can be added. Can also be added and introduced into the reactor. As another variant, the ripening agent can be introduced independently at the addition stage of the halide salt and silver salt.

As ripening agents other than halogen ions, ammonia, amine compounds, thiocyanate salts,
For example, alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used. The use of thiocyanate ripening agents is described in US Pat. No. 2,222,264.
Nos. 2,448,534 and 3,320,069
The teaching can be seen in the issue. US Pat. No. 3,271,15
No. 7, No. 3,574,628, and No. 3,737,
A conventional thioether ripening agent as described in No. 313 can also be used. Alternatively, JP-A-53-82
The thione compounds as disclosed in No. 408 and No. 53-144319 can also be used. The properties of silver halide grains can be controlled by allowing various compounds to be present during the silver halide precipitation formation process. Such a compound may be initially present in the reactor, or may be added together with one or more salts by a conventional method. U.S. Pat. No. 2,448,
No. 060, No. 2,628,167, No. 3,737,3
No. 13, No. 3,772,031, and research
Disclosure, Volume 134, June 1975, 13
452, compounds such as copper, iridium, lead, bismuth, cadmium, zinc, chalcogen compounds such as sulfur, selenium and tellurium, gold and compounds of Group VII noble metals are used during the silver halide precipitation process. The presence of silver halide can control the properties of silver halide. As described in Japanese Examined Patent Publication No. 58-1410, Moisar et al., Journal of Photographic Science, 25, 1977, pp. 19-27, silver halide emulsions are used to form grains during the precipitation process. The inside can be reduced and sensitized.

In the tabular grains used in the present invention,
Silver halides having different compositions may be joined by epitaxial joining, or may be joined with a compound other than silver halide such as silver rhodanide and lead oxide. These emulsion grains are described, for example, in US Pat.
4,684, 4,142,900, 4,45
9,353, British Patent 2,038,792, U.S. Patents 4,349,622, 4,395,478.
Issue No. 4,433,501 Issue 4,463,087
Issue 3, Issue 3,656,962, Issue 3,852,067
And JP-A-59-162540.

The tabular grains used in the present invention are usually chemically sensitized. Chemical sensitization is based on James (TH J
ames) by The Theory of Photographic
Process, 4th edition, published by Macmillan, 1977 (TH
James, The Theory of the Photographic Process, 4
ed, Macmillan, 1977) 67-77 and using active gelatin, and Research Disclosure 120, April 1974, 12008; Research Disclosure, 3
Volume 4, June 1975, 13452, U.S. Pat. No. 2,6.
42,361, 3,297,446, 3,77
No. 2,031, No. 3,857,711, No. 3,90
1,714, 4,266,018 and 3,90
4,415, and British Patent No. 1,315,755
, PAg 5-10, pH 5-8, and temperature 30-80 ° C., sulfur, selenium, tellurium,
It can be carried out using gold, platinum, palladium, iridium or a combination of these sensitizers. Chemical sensitization is optimally carried out in the presence of gold and thiocyanate compounds. Further, for example, sulfur-containing compounds or hypo, as described in US Pat. Nos. 3,857,711, 4,266,018 and 4,054,457,
It is carried out in the presence of a sulfur-containing compound such as a thiourea compound or a rhodanin compound. It is also possible to carry out chemical sensitization in the presence of a chemical sensitization aid. The chemical sensitization aids used include compounds known to suppress fog and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine and azapyrimidine. Examples of chemical sensitization aid modifiers are described in US Pat. Nos. 2,131,038 and 3,4.
11,914, 3,554,757, JP-A-58.
-1252626 and Duffin, "Photoemulsion Chemistry", 1
38-143. In addition to chemical sensitization,
Alternatively, it may be reduction sensitized, for example with hydrogen, as described in US Pat. Nos. 3,891,446 and 3,984,249. Further, as described in US Pat. Nos. 2,518,698, 2,743,182 and 2,743,183, a reducing agent such as stannous chloride, thiourea dioxide and polyamine is used. Alternatively, reduction sensitization can be achieved by treatment with low pAg (eg, less than 5) and / or high pH (eg, greater than 8). Further, the color sensitization can be improved by the chemical sensitization method described in U.S. Pat. Nos. 3,917,485 and 3,966,476. It is particularly preferable to use the selenium sensitization in combination with the gold / sulfur sensitization.

Further, JP-A-61-3134 and 61-3
The sensitizing method using an oxidizing agent described in JP-A No. 136 can also be applied. The emulsion comprising tabular grains of the present invention,
The tabular grains preferably account for 50% or more of the projected area of all silver halide grains, more preferably 70% or more, and most preferably 90% or more.
The emulsion consisting of the tabular grains of the present invention has a conventional silver halide grain chemically sensitized in the same silver halide emulsion layer (hereinafter, referred to as
It can be used in combination with an emulsion comprising non-tabular grains). Particularly in the case of a color photographic light-sensitive material, tabular grain emulsions and non-tabular grain emulsions can be used in different emulsion layers and / or in the same emulsion layer. Here, the non-tabular grains include, for example, regular grains having regular crystal bodies such as cubes, octahedra, and tetradecahedrons, and grains having irregular crystal shapes such as spherical and potato-like grains. And so on. The silver halide of these non-tabular grains includes silver bromide, silver iodobromide,
Any of silver iodochlorobromide, silver chlorobromide and silver chloride may use silver halide. A preferred silver halide is silver iodobromide or silver iodochlorobromide containing 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide containing 2 to 25 mol% silver iodide.

The particle size of the non-tabular grains used here is 0.
It may be fine particles of 1 micron or less or large size grains having a projected area diameter of up to 10 microns, and may be a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. Two or more kinds of silver halide emulsions formed separately may be mixed and used. The silver halide emulsion having a layered structure of three phases or more having a relative standard deviation of the grain size distribution of 20% or less and different iodine contents will be described below.

The size of silver halide grains described below is represented by a projected area diameter. Here, the projected area diameter means the diameter of a circle having an area equal to the projected area of particles. The size of the silver halide grains of the present invention is preferably 0.1 to 2.0 μ, more preferably 0.1 to 1.0 μ. The ratio of the projected area to the thickness is less than 10, but the thickness here means the shortest length of the diameter passing through the center of gravity of the particle. When the inner core of the present invention is composed of silver iodobromide, it is preferably a homogeneous solid solution phase. Here, “homogeneous” means that in the distribution of the silver iodide content, 95 mol% of silver halide in the inner nucleus is
This means that the average silver iodide content falls within ± 40%. As the halogen composition of the internal nucleus, the average content of iodine is preferably 10 mol% or less, more preferably 0 to 5 mol%, and particularly preferably 0 to 3 mol%. The ratio of the silver of the inner core to the silver of the whole particle is preferably 5% or more, more preferably 10 to 95%.
Is. The silver iodide content of the layer which is not the outermost layer and which coats the inner core (hereinafter referred to as the intermediate coating layer) has a silver iodide content of 1 from that of the outermost layer.
More than mol% higher. Further, the silver iodide content of the intermediate coating layer is 1 to 100 mol%, and the silver content of the coating layer is 0.01% to 90% with respect to the total amount of silver, but preferably 0. It is from 01% to 80%. If the outermost coating layer consists of silver iodobromide, it need not be homogeneous, but it is more preferred that it be homogeneous silver iodobromide. Further, the second coating layer needs to sufficiently cover the first coating layer, and for this reason, the average thickness of the outermost coating layer is preferably 0.02 μ or more, but more preferably 0.
It is at least 04μ. The silver iodide content of the outermost coating layer is 10
It is not more than mol%, preferably 0 to 3 mol%, more preferably 0 to 1 mol%. The ratio of silver in the outermost coating layer to silver in the entire grain is preferably 5 to 90 mol%.

The size distribution of the silver halide grains of the present invention is monodisperse. Here, the term “monodisperse” means that the relative standard deviation of the particle size distribution (the standard deviation of the particle size distribution divided by the value of the average particle size) is preferably 20% or less. It is more preferably 15% or less.
More preferably, it is 10% or less. In the emulsion layer containing the silver halide grains of the present invention, the ratio of the grains contained in the layer may be arbitrarily selected, but the silver amount is preferably 40% or more based on all the silver halide grains. , Particularly preferably 90% or more.

Next, the method for producing the silver halide emulsion of the present invention will be described. That is, generally, after forming a nucleus (internal nucleus) made of silver bromide or silver iodide (iodine content of 10 mol% or less), silver iodobromide is formed on the nucleus by a halogen substitution method or a coating method. Alternatively, one or more intermediate coating layers made of silver iodide are formed, and the intermediate coating layers are further formed,
In the method for producing a structured silver halide grain having three or more layers, in which an outermost coating layer composed of silver iodobromide or silver bromide having a halogen composition different from that of the intermediate coating layer is provided, the iodine content of the intermediate coating layer is adjusted to the maximum. It is manufactured so that it has at least one layer higher than the outer layer by 1 mol% or more inside the outermost layer.

Details will be described below. First, the inner nucleus of the silver halide grain of the present invention is described by P. Glafkides, Chimie e.
t Physigue Photographigue (Published by Paul Montel, 1967
), GF Duffin Photographic Emulsion Chem
istry (published by The Focal Press, 1966), VL Zelikm
by an et al Making and Coating Photographic Emuls
ion (published by The Focal Press, 1964) and the like. That is, the acidic method,
A neutral method, an ammonia method, or the like may be used, and a method of reacting the soluble silver salt and the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used.
As one form of the double jet method, a method of keeping pAg constant in a liquid phase where silver halide is produced, that is, a so-called control double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained. Two or more kinds of silver halide emulsions formed separately may be mixed and used. When preparing the inner nucleus of the silver halide grain,
It is preferable that the halogen composition is uniform. When the inner core is silver iodobromide, it is preferable to use the double jet method or the control double jet method.

The pAg for preparing the inner core is
Although it varies depending on the reaction temperature and the type of silver halide solvent, it is preferably 7 to 11. Further, it is preferable to use a silver halide solvent because grain formation time can be shortened. For example, a commonly known silver halide solvent such as ammonia or thioether can be used. The shape of the inner core is preferably flat, spherical, or twinned.
An octahedron, a cube, a tetrahedron or a mixed system can also be used. The inner core may be polydisperse or monodisperse, but monodisperse is more preferable. Here, “monodisperse” has the same meaning as described above.

Further, in order to make the grain size uniform, as described in British Patent No. 1535016, Japanese Patent Publication Nos. 48-36890, 52-16364, etc., the rate of addition of silver nitrate or an aqueous solution of an alkali halide is controlled to effect grain growth. How to change it according to the speed,
It is preferable to grow rapidly within a range not exceeding the critical supersaturation degree by using a method of changing the concentration of the aqueous solution as described in US Pat. No. 4,242,445 and JP-A-55-158124. These methods do not cause re-nucleation and each silver halide grain is coated uniformly, and therefore, they are preferably used also when introducing a coating layer described later. In the process of forming the inner nucleus of the silver halide grain or physical ripening, cadmium salt, zinc chloride, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt,
An iron salt or an iron complex salt may coexist. The intermediate coating layer of the silver halide grains of the present invention can be provided by a usual halogen substitution method, a method of coating with silver halide, etc. after subjecting the formed inner core to a desalting step, if necessary.

As the halogen substitution method, for example, an aqueous solution mainly containing an iodo compound (preferably potassium iodo) after the formation of the internal nucleus, preferably at a concentration of 10
% Or less aqueous solution. At this time, the iodine compound is added in an amount of 0.01 to 30 mol% based on the number of moles of silver in the entire grains. Further, at this time, the pAg is preferably 5 to 12. For details, see U.S. Patent Nos. 2,592,250 and 4,750,020.
It can be carried out by the method described in the specification of the publication, JP-A-55-127549, or the like. At this time, in order to reduce the difference in iodine distribution between the particles of the first coating layer, it is desirable to adjust the concentration of the aqueous iodine compound solution to 10 ^-2 mol% or less and to add it for 10 minutes or more. As a method for newly coating the inner nucleus with silver halide, for example, simultaneous addition of an aqueous solution of halide and an aqueous solution of silver nitrate, that is, a simultaneous mixing method and a control double jet method can be performed. For details, JP-A-53-22408, JP-B-43-13162, J. Photo. Sci., 24, 198
(1976) and the like. At this time, 0.01 to 30 mol% of silver nitrate based on the number of moles of silver in the whole of the completed grains, or an equimolar amount or more (up to about twice the amount) of an iodine compound and a halogen containing silver bromide if necessary. Aqueous chloride solution is added. The pAg for forming the intermediate coating layer varies depending on the reaction temperature and the type and amount of the silver halide solvent, but the above-mentioned ones are preferably used in the same manner. As a method of forming the intermediate coating layer, a simultaneous mixing method or a control double jet method is more preferable.

The outermost coating layer of the silver halide grain of the present invention has a silver halide having a halogen composition different from the halogen composition of the intermediate coating layer on the outside of the inner core having the intermediate coating layer on the surface. It can be provided by a method of coating by a double jet method or a double jet method. Regarding these methods, the method of providing the above-mentioned intermediate coating layer is similarly used. When introducing the second coating layer, since the halogen composition of the outermost coating layer is different from the halogen composition of the intermediate coating layer, the outermost coating layer may be difficult to precipitate on the surface of the intermediate coating layer. ,
It is necessary to take into account changes in critical supersaturation. Further, it is preferable to increase the number of moles added per unit time as the total surface area of the particles increases. When the outermost coating layer is silver bromide, a method of adding an aqueous silver nitrate solution in the presence of an inner core having a bromide and an intermediate coating layer in advance (one-side mixing method) can also be used. The halogen composition of the outermost coating layer is preferably uniform.

The characteristics of the grain are as follows: (1) The inner core has a substantially silver bromide or iodine content of 1;
Consists of 0% or less of silver iodobromide (2) The outermost layer has a substantially silver bromide or iodine content of 1
(3) At least one layer having an iodine content of 1 mol% or more higher than that of the outermost layer is present inside the outermost layer (3) Relative standard of grain size distribution used in the present invention Chemical sensitization of a silver halide emulsion having a layered structure of three or more phases having a deviation of 20% or less and different iodine contents is performed according to the above description, and the selenium sensitizer and the gold / sulfur sensitizer are used. The combination of feelings is particularly preferable.

Regarding the iodine content of the first coating layer of the silver halide grain of the present invention, for example, JI Goldstein, DB Williams
“X-ray analysis in TEM / ATEM” Scanning Electron Microscopy (1977), Volume 1 (IIT Research Institute), page 651 (March 1977) In the preparation of the silver halide grains of the present invention, soluble salts are prepared from the emulsion after precipitation formation or physical ripening of the second coating layer or, if necessary, from the emulsion after internal nucleation or after formation of the first coating layer. In order to remove the gel, a Nudel water washing method in which gelatin is gelled may be used. Inorganic salts, anionic surfactants, anionic polymers (eg polystyrene sulfonic acid), or gelatin derivatives (eg acylated gelatin) may be used. , Carbamoylated gelatin, etc.) precipitation method (flocculation)
May be used.

In the present invention, among the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, at least the layer adjacent to the green-sensitive emulsion layer preferably contains yellow colloidal silver. Also,
When the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer are composed of a plurality of layers having different sensitivities, the yellow colloidal silver-containing layer may be adjacent to any one of them, but the lowest sensitivity Adjacent to the layer is a layer containing yellow colloidal silver. The maximum absorption wavelength of colloidal silver used is 400
nm to 500 nm, more preferably 430 nm
To 460 nm yellow is preferable. By including yellow colloidal silver in the layer adjacent to the light-sensitive emulsion layer in this way, the development activity of the light-sensitive emulsion layer can be enhanced, and the sensitized width of sensitized development can be expanded by extending the development time. This is because it is possible to increase the magnitude of the interlayer effect that emphasizes the vividness of color reproduction. These are preferably carried out in a silver halide color reversal photographic light-sensitive material, but when the above is carried out, the maximum density which is an important characteristic of a photographic image is lowered, so that the light-sensitive emulsion layer adjacent to the yellow colloidal silver-containing layer is formed. Since it is necessary to increase the coating silver amount and the performance change of the photosensitive emulsion layer tends to be emphasized, the improvement effect by combining the emulsion of the present invention and the spectral sensitizing dye is the yellow colloid as described above. Since it greatly develops in a system in which the silver-containing layer is placed adjacent to the light-sensitive emulsion layer, the effect of increasing the progress of the original sensitized development of the yellow colloidal silver and increasing the chroma, pressure, It can be put to practical use without deteriorating raw storability, latent image storability and residual color.

Preparation of various types of colloidal silver is described, for example, in Wi
Collier by Weiser, ley & Sons, New York, 1933.
dal Elements (yellow colloidal silver produced by Carey Lea's dextrin reduction method) or DE 1096193 (brown and black colloidal silver) or US Pat. No. 268860.
1 (blue colloidal silver). Among these, yellow colloidal silver having a maximum absorption wavelength of 400 nm to 500 nm was found to have the effect of imparting particularly sensitized developability.

In the present invention, when yellow colloidal silver is added for the purpose of increasing the above-mentioned interlayer effect and correcting the color balance of the sensitized development processing, the yellow sensitizing silver is not added to the emulsion layer, but the blue sensitizing property is obtained. It must be added to a layer adjacent to the emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer. If yellow colloidal silver is added to the emulsion layer, unnecessary fog is formed during storage of the light-sensitive material or during development, which is not preferable. Even if the yellow colloidal silver is not added to the color-sensitive layer and is added to the non-adjacent layer via the intermediate layer, the effect of improving the developing activity is not exhibited. In the present invention, when the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer are composed of two or more layers having different sensitivities and spectral sensitivities, the yellow colloidal silver-containing layer should be adjacent to the lowest sensitive layer of each color-sensitive layer. Is highly preferred. Generally, the layer with high sensitivity is preferentially developed, but by placing the yellow colloidal silver layer adjacent to the lowest sensitive layer, the development progress between the highest sensitive layer and the lowest sensitive layer can be balanced and increased. It is possible to reduce the gradation change during the sensitive development processing. Further, a remarkable effect appears when the total coated silver amount of the light-sensitive material is 20 mg / m ² or more.

It is extremely unpredictable that the effect of improving the development progress by incorporating yellow colloidal silver in the layer adjacent to the photosensitive layer changes depending on the constitution of the color-sensitive layer of the photosensitive material and the coating silver amount. Was that. However, such a phenomenon can be understood considering that the reason why the development of the relatively insensitive layer is likely to be delayed is that the halogen ions released by the development of the relatively insensitive layer are considered. That is, the larger the coating amount of silver halide that delays the development of the low-sensitivity layer, and the larger the number of layers of the high-sensitivity layer relative to the low-sensitivity layer, the more the yellow colloidal silver contained in the adjacent layer of the low-sensitivity layer. Greatly improves development progress. In the present invention, the preferable amount of yellow colloidal silver added is 0.001 to 0.4 g / m ² per each added layer. Also 0.003
To 0.3 g / m ² is more preferable. In the present invention, with respect to the combined use of yellow colloidal silver as described above, for example, the descriptions in Japanese Patent Application No. 4-306241 and its cited references can be referred to.

The combined use of the emulsion of the present invention and the spectral sensitizing dye is preferably used in combination with silver halide grains whose surface or inside is further covered. The surface-covered emulsion is the same as the yellow colloidal silver-containing layer adjacent to the above-mentioned light-sensitive emulsion layer in order to enhance the developing activity of the light-sensitive emulsion layer. By using a combination of a sensitizing dye and a spectral sensitizing dye, the balance of each color-sensitive layer during sensitized development can be controlled and the sensitized material with improved saturation can be used for pressure resistance, raw storability, and latent image storability. And it can be obtained without deteriorating the residual color. An internal fog emulsion is also used to enhance the developing activity of the photosensitive emulsion layer to which it is added. In the case of an internally fogged emulsion, the timing of increasing the development activity from the start of development can be changed by adjusting the shell thickness and the halogen composition. Therefore, unlike the case of surface fog emulsion or yellow colloidal silver, the maximum densities in the case of standard development time can be largely changed and the sensitization width in sensitized development with extended development time can be increased. , The timing of development activity improvement by adding the internal fog emulsion is not simply determined by the shell thickness and halogen composition of the internal fog emulsion,
Dissolution associated with the development of a light-sensitive emulsion in close proximity.The dissolution action of the internal fog emulsion shell by physical development, the initiation of development by the halogen conversion of the internal fog emulsion shell by the iodine ions released from the silver iodobromide emulsion that has started development. In particular, there is a case where the performance change of the photosensitive emulsion in the same layer is magnified because it is strongly affected by the acceleration effect of the above. The surface or inside of the silver halide grain is a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed portion and the exposed portion of the light-sensitive material. The silver halides forming the inner nucleus of the silver halide grain whose inside is covered may have the same halogen composition or different halogen compositions. As the silver halide grains whose surface or inside is covered, any of silver iodobromide, silver bromide, silver chloride, silver chlorobromide and silver chloroiodobromide can be used. The grain size of the silver halide grains covered with these surfaces or inside is not limited, but the average grain size is 0.01 to 0.75 μm, particularly 0.05 to
0.6 μm is preferable. Also, a polydisperse emulsion may be used,
Monodispersion (wherein at least 95% of the weight or number of silver halide grains has a grain size within ± 40% of the average grain size) is preferred. These operations are preferably carried out in a silver halide color reversal photographic light-sensitive material. Regarding the combined use of the above-described surface- or inside-covered silver halide grains in the practice of the present invention, see, for example, the publications of Japanese Examined Patent Publication No. 59-35011 and Japanese Examined Patent Publication No. 1-38296 and the references thereof. You can

In the present invention, internal latent image type silver halide grains chemically sensitized to a depth of less than 0.02 micrometer from the grain surface can be preferably used in combination. With such a constitution, the graininess is improved, and a silver halide photographic light-sensitive material having more excellent image quality can be obtained. This is because the internal latent image type emulsion is not exposed to the grain surface at the latent image position, so that it is less susceptible to intrinsic desensitization by the sensitizing dye, and the sensitivity / sensitivity especially when spectrally sensitized This is because the grain ratio is excellent. In using the internal latent image type silver halide grains in the present invention, for example, US Pat.
The 12 specifications and the references cited therein can be referred to.

The application of the present invention is not particularly limited, and the present invention can be applied to black and white and color photographic light-sensitive materials, still and movie photographic light-sensitive materials, direct positive photographic light-sensitive materials and any other silver halide photographic light-sensitive materials. Although applicable,
Preferably, a silver halide color negative photographic light-sensitive material, and a silver halide color reversal photographic light-sensitive material (a negative-type silver halide emulsion is used, and after black and white development after exposure, residual silver halide grains are fogged for color development. Method). The present invention is more preferably used for a silver halide color reversal photographic light-sensitive material. Since the silver halide color reversal photographic light-sensitive material is directly used for appreciation of the light-sensitive material after development processing, variations in emulsion performance are easily perceived by an observer, and the effect of applying the present invention is remarkable. In particular, the residual color of the sensitizing dye is originally colorless and transparent after development by sufficient exposure (in the case of a transparent support, it is white in the case of a reflective support, but in any case, since it has a high lightness, it has a tint. The deviation is easily recognized by the human eye.) The coloring is uniformly left on the portion that should be recognized, so that the improvement effect of the present invention is great.

The silver halide photographic light-sensitive material of the present invention can be carried out in the same manner as a normal silver halide photographic light-sensitive material except the above points. Regarding the silver halide photographic emulsion of the present invention and various techniques and inorganic / organic materials which can be used for the silver halide photographic light-sensitive material using the same, Research Disclosure No. 3081 is generally used.
19 (1989) can be used.
In addition to this, more specifically, for example, regarding the technology and inorganic / organic materials that can be used for color photographic light-sensitive materials to which the silver halide photographic emulsion of the present invention can be applied,
It is described in European Patent No. 436,938A2, below, and in the patents cited below.

Item This section 1) Layer constitution Page 146, line 34 to page 147, line 25 2) Silver halide emulsion Page 147, line 26 to page 148, line 12 3) Yellow coupler No. Page 137, line 35 to page 146, line 33, page 1 49, line 21 to line 23 4) Magenta coupler, page 149, line 24 to line 28; European Patent No. 421,453A1 Page 3, line 5 to page 25, line 55 5) Cyan coupler Page 149, line 29 to line 33; European Patent No. 432,804A2, page 3, line 28 to page 40, line 2 6 ) Polymer coupler, page 149, lines 34 to 38; EP 435,334A2, page 113, line 39 to page 123, line 37 7) Colored coupler, page 53, line 42 to 137. 34th line, page 149, lines 39-45 ) Other functional couplers from page 7, line 1 to page 53, line 41, page 149, line 46 to page 150, line 3; European patent 435,334A2, page 3, line 1 to Page 29, 50th line 9) Antiseptic / mildew agent Page 150, 25th line to 28th line 10) Formalin Page 149, 15th line to 17th line Scavenger 11) Other additives Page 153, 38th line ~ Line 47; page 75 line 21 to page 84 line 56, page 27 line 40 to page 37 line 40 of European Patent 421,453A1 12) Dispersion method page 150 line 4 -24th line 13) Support page 150 line 32th line-34th line 14) Film thickness / film physical property page 150 line 35th line-49th line 15) Color development step page 150 line 50th line-151st 47th line 16) Desilvering process, page 151, line 48 to page 152, line 53 17) Automatic processor, page 152 Line 4 - page 153, line 2 18) washing and stabilizing steps page 153, line 3 to 37 row

[0074]

The present invention will be described in more detail based on the following examples. The contents of the compounds indicated by the symbols in Examples 1 to 4 are summarized in Example 4. Example 1 (1) Preparation of emulsion a. Emulsion 1 7 g of distilled water 1036 cc in which 0.7 g of KBr, 30.6 g of ossein gelatin and 4.5 g of ammonium nitrate were dissolved
Keep at 0 ° C and add 22c of NaOH (1N) aqueous solution to this solution.
After adding c, 220 cc of 10% silver nitrate aqueous solution and 7% KBr
Aqueous solution with double jet silver potential (SCE) + 60mV
It was added in 7 minutes while keeping the above. Next, 420 cc of a 20% silver nitrate aqueous solution and 13.3% of KBr and KI, respectively,
An aqueous solution containing 0.98% was added over 37 minutes with the double jet kept at +65 mV. Thirty minutes after starting this addition, the pH was adjusted to 3.2 with sulfuric acid (1N). Soluble salts were removed from this by a conventional flocculation sedimentation method, and then inactivated ossein gelatin 23
g and distilled water to make the total volume 700 ml
Was adjusted to 6 and dispersed, and potassium thiocyanate, sodium chloroaurate tetrahydrate, sodium thiosulfate and sodium benzenesulfonate were respectively 52 mg, 2 mg and 2.
Add 2 mg and 2.5 mg, pAg 8.5, temperature 65 ℃
The optimum chemical sensitization was carried out in. The term "optimally" refers to chemical sensitization that maximizes the sensitivity when exposed for 1/50 seconds after chemical sensitization. After completion of the chemical sensitization, 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene and phenylmercaptotetrazole were added, and then 5 cc of a 1% KI aqueous solution was added. Further, as spectral sensitizing dyes, S-4 was 1 * 10 ^-3 mol / molAg and S-5 was 2.
5 * 10 ⁻⁴ mol / molAg was added (the amount of this sensitizing dye is the amount that gives the highest sensitivity). The silver halide grains obtained above had an average diameter of 0.37 μm, a variation coefficient of the size distribution (the standard deviation of the distribution divided by the average value and multiplied by 100) 8%, an average silver iodide content of 4 mol%, Rounded tetradecahedral AgB with 20% variation coefficient of silver iodide content distribution
It was rI particles.

B. Emulsions 2 to 12 As shown in Table 1, 15% of the amount of sodium thiosulfate used for chemical sensitization in the preparation of Emulsion 1 above is equimolar with diphenylpentafluorophenylphosphine selenide (selenium sensitizer 17) or Emulsions 2 and 3 were obtained by substituting potassium selenocyanide (KSeCN) and optimally performing gold-sulfur-selenium chemical sensitization. The comparative spectral sensitizing dye S-5 used in Emulsions 1-3 was replaced with equimolar amounts of S-100 (Comparative Example), SS-3 (Comparative Example), and the inventive spectral sensitizing dye SS-22. Others are the same as Emulsions 4 to 12
Was prepared.

(2) Preparation of coating sample Magenta coupler: 1- (2,4,6-trichlorophenyl) -3- {3- (2,4-di-t-aminophenoxyacetamide) was added to the above emulsion. Benzamido} -5-pyrazolone, tricresyl phosphate, ethyl acetate, and a surfactant were added to emulsify and disperse the coupler solution in a gelatin aqueous solution, and polyvinylbenzene sulfonate as a thickener and vinyl as a hardening agent Sulfone compounds,
An emulsion coating solution was prepared by adding a tetrazaindene compound as a stabilizer. Subsequently, these coating solutions are uniformly coated on an undercoated triacetyl cellulose support, and then a surface protective layer mainly composed of an aqueous gelatin solution is coated thereon to obtain coating samples 101 to 101 containing emulsions 1 to 12. 112 was produced. At this time, the coating silver amount was 1.0 g / m ² , the magenta coupler coating amount was 1.0 g / m ² , and the gelatin coating amount of the protective layer was 2.0 g / m ² .

(3) Evaluation of Coated Samples A white light source having a color temperature of 4800K was used for the above coated samples.
Wedge exposure of 000 lux for 1/50 second was performed through a yellow filter, and the color negative development processing shown below was performed to measure magenta density to determine sensitivity and fog.
The sensitivity was shown as a relative value when the reciprocal of the exposure amount required to give a density of fog + 0.5 was obtained and the sensitivity of Sample 101 was 100. Further, in order to evaluate the raw storability, a change in fog and a decrease in sensitivity when the above sensitometry was carried out after the coated sample was incubated at a temperature of 40 ° C. and a relative humidity of 60% for 60 days were determined as follows. (Δ fog) = (fog density after raw storage) − (Fresh fog density) (Δ sensitivity) = log ₁₀ {(sensitivity after raw storage) / (Fresh sensitivity)} In order to evaluate residual color, After performing the tomometry exposure, the color reversal development processing described below was performed to examine the tint of the developed sample with a sufficiently large exposure amount. For the evaluation of residual color, the unexposed sample was used as a black and white developer, MAA-1.
It was developed with a developing solution at 20 ° C. for 15 minutes, and the sample after washing with fixing water was also visually observed. Further, in order to evaluate the latent image storability, the sample subjected to the above-mentioned sensitometric exposure was stored at a temperature of 25 ° C. and a relative humidity of 60% for 7 days, and then subjected to the above-mentioned color negative development treatment to examine the change in sensitivity. I asked. (Δ sensitivity) = log ₁₀ {(sensitivity after latent image storage) / (Fresh
Sensitivity)} Further, in order to evaluate the pressure property, after bending the sample at a constant bending angle, the color negative development process described above was performed, and the density change due to the bending of the unexposed part where the density change was most remarkable The changes were compared, and three-stage evaluation was performed as follows. ◎ (especially good) ○ (good) × (concentration change is large and not possible). The results are summarized in Table 4.

(Color negative development processing conditions)

Next, the composition of the treatment liquid will be described. (Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1. 5 mg Hydroxylamine sulfate 2.4 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 Water was added to 1.0 liter pH (potassium hydroxide and sulfuric acid Adjusted by) 10.05

(Bleach) (Unit: g) Ethylenediaminetetraacetic acid sodium ferric trihydrate 100.0 Ethylenediaminetetraacetic acid disodium salt 10.0 3-Mercapto-1,2,4-triazole 0.03 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5 ml Water was added to 1.0 liter pH (adjusted with ammonia water and nitric acid) 6.0

(Fixer) (Unit: g) Ethylenediaminetetraacetic acid disodium salt 0.5 Ammonium sulfite 20.0 Ammonium thiosulfate aqueous solution (700 g / l) 295.0 ml Acetic acid (90%) 3.3% Water was added 1 0.0 liter pH (adjusted with aqueous ammonia and acetic acid) 6.7

(Stabilizing Solution) (Unit: g) p-Nonylphenoxypolyglycidol (Glycidol Average Degree of Polymerization 10) 0.2 Ethylenediaminetetraacetic Acid 0.05 1,2,4-Triazole 1.3 1,4-bis (1 , 2,4-Triazol-1-ylmethyl) piperazine 0.75 Hydroxyacetic acid 0.02 Hydroxyethylcellulose (Daicel Chemistry HEC SP-2000) 0.1 Gentamicin 0.01 Water was added to 1.0 liter pH 8.5

(Color reversal development processing conditions) (Processing step) Processing step time Temperature Tank capacity Replenishment amount Black and white development 6 minutes 38 ° C 12l 2.2l / m ² First water wash 2〃 38〃 4〃 7.5〃 inverting 2〃 38〃 4〃 1.1〃 color development 6〃 38〃 12〃 2.2〃 adjustment 2〃 38〃 4〃 1.1〃 bleach 6〃 38〃 12〃 0.22〃 4 38〃 8〃 1.1〃 Second water washing 4〃 38〃 8〃 7.5〃 Security 1〃 25〃 2〃 1.1〃

The composition of each treatment liquid was as follows. (Black-and-white development) Mother liquor Replenisher Nitrilo-N, N, N-trimethylenephosphonic acid / 5-sodium salt 2.0 g 2.0 g Sodium sulfite 30 g 30 g Hydroquinone potassium monosulfonate 20 g 20 g Potassium carbonate 33 g 33 g 1-phenyl- 4-Methyl-4-hydroxymethyl-3-pyrazolidone 2.0 g 2.0 g potassium bromide 2.5 g 1.4 g potassium thiocyanate 1.2 g 1.2 g potassium iodide 2.0 mg-water added 1000 ml 1000 ml pH 9.60 9.60 (pH was adjusted with hydrochloric acid or potassium hydroxide.)

(Inversion Solution) Mother Liquor Replenisher Nitrilo-N, N, N-trimethylenephos Same as mother liquor Phosphonic acid / 5 sodium salt 3.0 g Stannous chloride dihydrate 1.0 g p-Aminophenol 0. 1 g sodium hydroxide 8 g glacial acetic acid 15 ml Water was added to 1000 ml pH 6.00 (pH was adjusted with hydrochloric acid or sodium hydroxide).

(Color developer) Mother liquor Replenisher Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 2.0 g 2.0 g Sodium sulfite 7.0 g 7.0 g Trisodium phosphate 12-hydrate 36 g 36 g Potassium bromide 1.0 g-Potassium iodide 90 mg-Sodium hydroxide 3.0 g 3.0 g Citrazine acid 1.5 g 1.5 g N-ethyl- (β-methanesulfonamidoethyl) -3-methyl-4- Aminoaniline sulfate 11 g 11 g 3,6-dithia-1,8-octanediol 1.0 g 1.0 g Water was added to 1000 ml 1000 ml pH 11.80 12.00 pH was adjusted with hydrochloric acid or potassium hydroxide.

(Preparation liquid) Mother liquor Replenishing liquid Ethylenediaminetetraacetic acid ・ 2 sodium salt Same as mother liquor ・ Dihydrate 8.0 g Sodium sulfite 12 g 1-Thioglycerin 0.4 ml Sorbitan ester 0.1 g

[0088]

[Chemical 9]

Water was added to 1000 ml pH 6.20 (pH was adjusted with hydrochloric acid or sodium hydroxide).

(Bleaching solution) Mother liquor Replenishing solution Ethylenediaminetetraacetic acid ・ sodium salt ・ dihydrate 2.0 g 4.0 g Ethylenediaminetetraacetic acid ・ Fe (III) ・ Ammonium ・ dihydrate 120 g 240 g Potassium bromide 100 g 200 g Ammonium nitrate 10 g 20 g Water was added to 1000 ml 1000 ml pH 5.70 5.50 (pH was adjusted with hydrochloric acid or sodium hydroxide).

(Fixer) Mother liquor Replenisher Ammonium thiosulfate 8.0 g Same sodium sulphite 5.0 g Sodium bisulfite 5.0 g Water was added to 1000 ml pH 6.60 The pH was adjusted with hydrochloric acid or aqueous ammonia.

(Stabilizer) Mother liquor Replenisher Formalin (37%) 5.0 ml Same as mother liquor Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.5 ml Water added 1000 ml Without pH adjustment

[0093]

[Table 4]

From Table 4, the emulsion of the present invention was evaluated for sensitivity, raw storability,
It can be seen that the residual color, latent image storability and pressure resistance are excellent. For example, samples 102 and 103 using a selenium sensitizer for sample 101 have high sensitivity and good latent image storability, but the raw storability and pressure property are deteriorated. Samples 104 to 106 in which the sensitizing dye was changed to S-100 for the purpose of improving the raw storability had excellent raw storability and excellent pressure resistance, and samples 105 and 10 using the selenium sensitizer.
Sample No. 6 has high sensitivity, and has good latent image storability deteriorated by changing the sensitizing dye, but Sample 1 using the sensitizing dye S-100
In each of Nos. 04 to 106, the residual color is significantly deteriorated.
Samples 110 to 11 using the sensitizing dye SS-22 of the present invention
Sample No. 2 has a good residual color, excellent raw storability, and good pressureability, but the latent image storability is deteriorated in Sample 110 containing no selenium sensitizer. On the other hand, the samples 111 and 112 of the present invention using the sensitizing dye of the present invention and the selenium sensitizer have high sensitivity and good latent image storability. Sample 107 using the sensitizing dye SS-3 of Comparative Example
Although ~ 109 has a good residual color, the degree of improvement in raw storability and pressure resistance is insufficient. The polarographic half-wave oxidation potential (Eox ^1/2 ) of the sensitizing dye in the phase discrimination second harmonic AC voltammetry method according to the method quoted in the text of the sensitizing dye used above is 0.585 V _VS SCE ( S-
5), 0.90V _VS SCE (S-100), 0.65V
_VS SCE (SS-3), 0.78V _VS SCE (SS-2
2).

Sensitizing dye S-100 having poor residual color
The sensitizing dyes S-5, SS-3, and SS-22 except for are all benzimidazolocarbocyanine compounds,
Polarographic half-wave oxidation potential (Eox) of sensitizing dyes measured by phase discrimination second harmonic AC voltammetry
^The more noble ( ^1/2 ) is, the more the raw storage stability and the pressure property tend to be improved, but the sensitizing dye SS-22 of the present invention, which has been sufficiently improved, has a polarographic half-wave oxidation potential of 0. .7
It was more precious than V vs SCE. As described above, although it is expected that it will be extremely difficult to satisfy all of the various performance items, the comparatively simple combination of the sensitizing dye and the selenium sensitization as in the present invention is used. The achievement of the object of the invention is truly surprising. In the evaluation of the residual color, it was difficult to distinguish the color negative developing sample from the color developing dye of the coupler, which was difficult to understand, while the MAA-1 black and white developing sample and sufficient exposure were given. With respect to the sample which was subjected to the color reversal development process after the heating, the difference could be immediately judged by visual observation of the sample.

Example 2 Preparation of Emulsion 1) Preparation of Comparative Tabular Emulsion V 10 g of potassium bromide and 25 g of inert gelatin were dissolved in 3.7 liters of distilled water while stirring well.
A 14% aqueous solution of potassium bromide and an aqueous solution of 20% silver nitrate were added thereto at a constant flow rate for 1 minute at 50 ° C. by the double jet method.
0.0% consumed). After that, an aqueous gelatin solution (1
7%, 300 cc) was added and the temperature was raised to 75 ° C. and aged for 10 minutes, then 35 cc of 25% NH ₃ aqueous solution was added,
After holding for 1 minute, 510 cc of 1N H ₂ SO ₄ was added to neutralize. Furthermore, 20% potassium bromide aqueous solution containing potassium iodide and 33% silver nitrate aqueous solution were added by the double jet method over 80 minutes so that the addition amount of potassium iodide was 12.5 g. During this time the temperature is 75
The pAg was kept at 8.degree. The amount of silver nitrate used in this emulsion is 425 g. Then, after desalting by an ordinary flocculation method, gold / sulfur sensitization was optimally performed using sodium chloroaurate and sodium thiosulfur, and a tabular AgBrI (AgI = 2.0 mol%) emulsion for comparison was used. V was prepared.

2) Preparation of Tabular Emulsion W Containing Rearrangement While thoroughly stirring an aqueous solution prepared by dissolving 10 g of potassium bromide and 25 g of inert gelatin in 3.7 liters of distilled water,
A 14% aqueous solution of potassium bromide and an aqueous solution of 20% silver nitrate were added thereto at a constant flow rate for 1 minute at 50 ° C. by the double jet method.
0.0% consumed). After that, an aqueous gelatin solution (1
7%, 300 cc) was added and the temperature was raised to 75 ° C. and aged for 10 minutes, then 35 cc of 25% NH ₃ aqueous solution was added,
After holding for 1 minute, 510 cc of 1N H ₂ SO ₄ was added to neutralize. Further, a 20% potassium bromide aqueous solution and a 33% silver nitrate aqueous solution were added by the double jet method over 40 minutes (this addition (II) consumed 40% of the total silver amount). During this period, the temperature was kept at 75 ° C. and the pAg was kept at 8.40. The pH at this time was 5.8. Reduce the temperature to 50 ° C and add potassium bromide to adjust the pAg to 9.4,
830 ml of 1% aqueous potassium iodide solution was added over 120 seconds followed by the rest of addition (II) over 50 minutes. This addition consumed 50% of the total silver. The amount of silver nitrate used in this emulsion was 425 g.
Then, after desalting by a normal flocculation method, gold and sodium chloroaurate and sodium thiosulfur are used to
Optimum sulfur sensitization, and flat AgBrI (AgI
= 2.0 mol%) Emulsion W was prepared.

In each of the emulsions V and W prepared as described above, tabular silver halide grains having an aspect ratio of 2 or more account for 99.7% of the projected area of all grains, and the aspect ratio is 3
The above tabular silver halide grains account for 9% of the projected area of all grains.
The spherical equivalent diameter of 3 was 0.8 μm, the average particle diameter / particle thickness ratio was 6, the flatness was 28, the average equivalent circle diameter was 1.3 μ, and the variation coefficient of equivalent circle diameter was 12%. . When dislocations were observed by the method described in Example I- (2) of JP-A-63-220238, dislocations were not observed in emulsion V and 90% or more in emulsion W. 10 or more dislocation lines were observed in the grains of.

3) Preparation of Emulsions 201 to 206 The amounts of the spectral sensitizing dye S-4 and the comparative spectral sensitizing dye S-5 were optimized in the above emulsion V at a temperature of 60 ° C. so that the sensitivity was maximized. To prepare an emulsion, which was designated as emulsion 201. At this time, the addition amount of S-4 and S-5 is 4 ×, respectively.
It was 10 ⁻⁴ mol / molAg and 2 × 10 ⁻⁴ mol / molAg. Next, an emulsion 202 was prepared by adding the spectral sensitizing dye S-4 and the spectral sensitizing dye S-5 of the comparative example to the above emulsion W at a temperature of 60 ° C. At this time, the amounts of S-4 and S-5 were optimized so that the sensitivity was maximized.
Has a small intrinsic desensitization with respect to Emulsion V containing no dislocation, and therefore, the sensitivity was maximized when a larger amount of the spectral sensitizing dye was added than in Emulsion 201. Emulsion 202 S-4 and S-5
The addition amount of each is 6 × 10 ^-4 mol / molAg, 3 × 10 ^-4
It was mol / molAg. Emulsions 203 and 204 were prepared by replacing spectral sensitizing dye S-5 with Emulsions 201 and 202 by equimolar spectral sensitizing dye S-100 of Comparative Example. Emulsions 205 and 206 were prepared by substituting equimolar amounts of the spectral sensitizing dye S-5 with the spectral sensitizing dye SS-22 of the present invention for the emulsions 201 and 202.

4) Emulsions 207 to 212 In the preparation of the above emulsions V and W, selenium sensitizer 17 was used in an amount of 15 mol% with respect to the amount of thiosulfuric acid or the like to optimize the gold.
Emulsions X and Y were prepared in the same manner as Emulsions V and W except that they were sensitized with sulfur-selenium. Spectral sensitizing dyes were added in the same manner as in Emulsions 201 to 206 to prepare Emulsions 207 to 212, respectively. Coating samples of the above emulsions 201 to 212 were prepared in the same manner as in Example 1 and evaluated. The results are shown in Table 5.

[0101]

[Table 5]

From the results shown in Table 5, it can be seen that the emulsion of the present invention is excellent in sensitivity, fog, raw retention, residual color, latent image storability and pressure resistance. First, when comparing the samples 201 to 206 for the combination of the tabular emulsion containing dislocations and the sensitizing dye, the sample 202 using the tabular plate containing dislocations with the sensitizing dye S-5 has the sensitivity and pressure property. , The latent image storability is excellent, but the raw storability is deteriorated. On the other hand, the sample 204 in which the sensitizing dye is S-100 has a better raw storability,
The residual color is significantly deteriorated. On the other hand, the sensitizing dye S of the present invention
It can be seen that the sample 206 using S-22 is excellent in raw storability and residual color and is also excellent in sensitivity, pressure property and latent image storability. Improving latent image preservation by introducing dislocations as described above,
And, the significant improvement in raw storage stability by the combination with the dye of the present invention was totally unexpected. Further, the results of applying selenium sensitization thereto are shown in Samples 207 to 212. Compared to the sample 202 using a sensitizing dye S-5 and a flat plate containing dislocations, the sample 208 to which selenium sensitization was applied also has improved sensitivity and latent image storability, but deteriorates raw storability and pressure property. On the other hand, the sample 212 in which SS-22 is used as the sensitizing dye has improved raw storage property and pressure property, and is higher in sensitivity and latent image storage property than the sample 206 of the present invention which is not selenium-sensitized. It is excellent in raw storage stability, residual color, and pressure, and is very preferable.

Example 3 Its Preparation in (1) a. Emulsion 301 KBr 0.7 g, ossein gelatin 30.6 g, ammonium nitrate 4.5 g dissolved distilled water 1036 cc 7
Keep at 0 ° C and add 22c of NaOH (1N) aqueous solution to this solution.
After adding c, 220 cc of 10% silver nitrate aqueous solution and 7% KBr
Aqueous solution with double jet silver potential (SCE) + 60mV
Was added for 7 minutes while maintaining the above [Addition I] Then, 280 cc of 1.5% KI aqueous solution was added by a single jet for 3 minutes. Next, 420 cc of a 20% silver nitrate aqueous solution and an aqueous solution containing 14% of KBr were added over 37 minutes while maintaining a +65 mV by a double jet. 30 minutes after starting this addition, use sulfuric acid to adjust the pH.
Adjusted to 3.2. After removing the soluble salt by the usual flocculation sedimentation method, 23 g of inactive ossein gelatin and distilled water were added to adjust the total amount to 700 ml, the pH was adjusted to 6, and the mixture was dispersed. Sodium aurate, sodium thiosulfate and sodium benzenesulfonate 52 mg, 2 mg,
2.2 mg and 2.5 mg were added, pAg 8.5, temperature 6
Optimal chemical sensitization was performed at 5 ° C. After completion of the chemical sensitization, 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene and phenylmercaptotetrazole were added, and then 5 cc of a 1% KI aqueous solution was added. Furthermore, when S-4 and S-5 were added as spectral sensitizing dyes in an amount that maximizes the sensitivity, S-4 was 1.5 × 10 ⁻³ mol / molAg,
S-5 was 3.7 × 10 ⁻⁴ mol / molAg. The silver halide grains obtained above had a rounded tetrahedron with an average value of 0.37 μ, a size variation coefficient of 16%, an average silver iodide content of 4 mol%, and a variation coefficient of the silver iodide content distribution of 20%. The particles were AgBrI particles. Emulsion 301 had a larger amount of dye added to obtain the highest sensitivity as compared with Emulsion 1.

B. Emulsion Emulsion 30 was prepared by substituting 15% of the amount of sodium thiosulfate used for chemical sensitization in the preparation of Emulsion 301 above with equimolar selenium sensitizer shown in Table 6 for optimum chemical sensitization.
2,303 were obtained. The comparative spectral sensitizing dye S-5 used in Emulsions 301 to 303 was equimolar to S-100 (Comparative Example),
And Emulsions 304 to 309 were prepared in the same manner except that the spectral sensitizing dye SS-22 of the present invention was substituted. c. Emulsion 310 After addition I of emulsion 310, 20% silver nitrate aqueous solution 300c
+65 mV with double jet for 26 minutes in an aqueous solution containing 13.1% and 1.4% of c, KBr and KI respectively.
It was added while keeping. Next, 20% silver nitrate aqueous solution 120
An aqueous solution containing cc and 14.0% of KBr was added over 11 minutes while maintaining a +65 mV with a double jet. Four minutes after the start of this addition, the pH was adjusted to 3.2 with sulfuric acid. After the flocculation, the emulsion 301 was prepared in the same manner. The silver halide grains obtained as described above were rounded with an average diameter of 0.37 μm, a size distribution variation coefficient of 11%, an average silver iodide content rate of 4 mol%, and a silver iodide content rate variation coefficient of 20%. It was a tetrahedral AgBrI particle.

D. 311 to 315 In the preparation of the above emulsion 310, 15% of the amount of sodium thiosulfate used for the chemical sensitization was replaced with an equimolar selenium sensitizer shown in Table 7, and the chemical sensitization was optimally performed.
1, 312 were obtained. The comparative spectral sensitizing dye S-5 used in Emulsions 310 to 312 was equimolar to the spectral sensitizing dye S of the present invention.
Emulsions 313-31 in the same manner except that S-22 was substituted.
5 was prepared.

E. Emulsion 316 After addition 1 of emulsion 301, the temperature was raised to 60 ° C., and then 300 cc of 20% silver nitrate aqueous solution and KBr and KI were respectively added to 13.
After adding an aqueous solution containing 3% and 1.0% over 30 minutes while maintaining +65 mV with a double jet, 1.5%
76 cc of KI aqueous solution was added by a single jet. Subsequently, 120 cc of 20% AgNO ₃ aqueous solution and 14% KBr
The aqueous solution was added with a double jet. After 4 minutes from the start of the addition, the pH was adjusted to 3.2 with H ₂ SO ₄ (1N). After the flocculation, the emulsion 301 was prepared in the same manner. The silver halide grains obtained above had an average diameter of 0.37 μm, a size distribution variation coefficient of 7%, an average silver iodide content rate of 4 mol%, and a silver iodide content rate variation coefficient of 20.
% Of rounded tetradecahedral AgBrI particles.
In the preparation of the above emulsion 316, 15% of the amount of sodium thiosulfate used for chemical sensitization was replaced with an equimolar selenium sensitizer shown in Table 7 to perform optimum chemical sensitization, and then emulsion 31
7, 318 were obtained. The comparative spectral sensitizing dye S-5 used in Emulsions 316-318 was equimolar to the inventive spectral sensitizing dye S.
Emulsion 3 in the same manner except that S-3 and SS-22 were used instead.
19-321 were prepared.

(2) Preparation of coating sample Magenta coupler: 1- (2,4,6-trichlorophenyl-3- {3- (2,4-di-t-aminophenoxyacetamide) benzamide was added to the above emulsion. } -Pyrazolone, tricresyl phosphate, ethyl acetate, and a surfactant are added to emulsify and disperse a coupler solution dispersion in an aqueous gelatin solution, and polyvinyl benzene sulfonate is used as a thickener and vinyl sulfone is used as a hardening agent. A series of compounds and a tetrazaindene compound as a stabilizer were added to prepare emulsion coating solutions, which were then uniformly coated on an undercoated triacetyl cellulose support, and then an aqueous gelatin solution was mainly prepared. Coating samples 301 to 321 containing emulsions 301 to 321
Was produced. At this time, the coating silver amount was 1.0 g / m ² , the magenta coupler coating amount was 1.0 g / m ² , and the gelatin coating amount of the protective layer was 2.0 g / m ² .

(3) Evaluation of Coating Samples A white light source having a color temperature of 4800K was used for the above coating samples.
Wedge exposure of 000 lux for 1/50 second was performed through a yellow filter, and the color negative development processing shown below was performed to measure the density, and the sensitivity and fog were determined. Moreover, in order to evaluate the raw storability, the coated sample was treated at a temperature of 40 ° C. and a relative humidity of 60.
The change in fog and the decrease in sensitivity when the above sensitometry was carried out after 60% incubation for 60 days were examined. In order to evaluate the residual color, the above sensitometric exposure was carried out, and then the color reversal development treatment shown in Example 1 was carried out to examine the tint of the developed sample at a sufficiently large exposure amount. To evaluate the residual color, the unexposed sample was developed with MAA-1 developer, which is a black and white developer, at 20 ° C. for 15 minutes, and the sample after fixing water washing was visually observed. Further, in order to evaluate the storability of the latent image, the sample subjected to the sensitometric exposure was stored at a temperature of 25 ° C. and a relative humidity of 60% for 7 days and then subjected to the color negative development treatment described above to examine the change in sensitivity. Further, in order to evaluate the pressure property, the sample was bent at a constant bending angle, and then the color negative development treatment was performed to examine the change in density due to the bending. The results are summarized in Tables 6 and 7.

[0109]

[Table 6]

[0110]

[Table 7]

From Tables 6 and 7, it can be seen that the present invention is excellent in emulsion sensitivity, raw storability, pressure resistance, residual color and latent image storability. For example, sample 301 in which only the particle structure of the present invention is used for sample 101 has high sensitivity, but the raw storability deteriorates. Further, although the sensitivity of the samples 302 and 303 using the selenium sensitizer is higher than that of the sample 301, the raw storage stability and the pressure property are further deteriorated. Sample 3 in which the sensitizing dye was changed to S-100 for the purpose of improving the raw storage stability
Nos. 04 to 306 were excellent in raw storability and had excellent pressure resistance, and samples 305 and 30 using a selenium sensitizer.
No. 6 has a high sensitivity, but all of the samples 304 to 306 using the sensitizing dye S-100 have remarkably deteriorated residual color. Sample 307 using the sensitizing dye SS-22 of the present invention
Each of No. 309 also has a good residual color, has greatly improved raw storability, and has good pressure property. Further, the samples 308 and 309 subjected to selenium sensitization are more preferable because the sensitivity is higher and the latent image storability is further improved. The same applies to Samples 310 to 321 having different particle structures.
3 to 315 and 319 to 321 are samples 310 to 3 respectively.
12, 316 to 318, the raw storability is greatly improved, and the effect is larger than that of the samples 101 to 103 and 110 to 112. Sample 3 using a selenium sensitizer
11, 312, 317, and 318 have high sensitivity, and both the sensitivity change of raw preservation and the sensitivity change of latent image preservation are improved,
More preferable. As described above, the latent image storability is improved by the particle structure, the residual color is small by the combination with the dye of the present invention, the raw storability is significantly improved, and the latent image storability is further improved by the combination with the selenium sensitization. All of the improvements, etc., are unexpected and are extremely favorable results. Further, when the samples 307, 313, and 319 are observed focusing on the pressure property,
Both are at a good level, but the smallest size 319 of the particle size distribution has the least increase / decrease feeling due to pressure, and becomes slightly worse as the distributions 313 and 307 become wider. Samples 308, 314, 320 and Sample 309,
The same applies to 315 and 321. The smallest particle size distribution 320 and 321 has the best pressure property.

Example 4 The effect of producing a multilayer color light-sensitive material using the emulsion of the present invention is shown below. Preparation of Sample 401 A sample 401 was prepared by preparing a multilayer color light-sensitive material consisting of each layer having the following composition on a cellulose triacetate film support having a thickness of 127 μ, which was undercoated. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the described use.

First layer: antihalation layer Black colloidal silver 0.20 g Gelatin 1.9 g UV absorber U-1 0.04 g UV absorber U-2 0.1 g UV absorber U-3 0.1 g Ultraviolet absorber U-4 0.1 g Ultraviolet absorber U-5 0.1 g High boiling point organic solvent Oil-1 0.1 g Microcrystalline solid dispersion of dye E-1 0.05 g

Second layer: intermediate layer Gelatin 0.40 g Compound Cpd-C 5.0 mg Compound Cpd-J 5.0 mg Compound Cpd-K 3.0 mg High boiling point organic solvent Oil-3 0.1 g Dye D-40 .4 mg Third layer: intermediate layer Finely grained silver iodobromide emulsion (average particle size 0.06 μm, coefficient of variation 18%, AgI content 1.5 mol%) with surface and internal fog Silver amount 0.05 g Yellow colloidal silver Silver content 0.03g Gelatin 0.4g

Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A Silver amount 0.4 g Emulsion B Silver amount 0.1 g Gelatin 0.8 g Coupler C-1 0.15 g Coupler C-2 0.05 g Coupler C -3 0.05 g Coupler C-9 0.05 g Compound Cpd-C 5.0 mg Compound Cpd-J 5.0 mg High boiling point organic solvent Oil-2 0.1 g Additive P-1 0.1 g Fifth layer: Medium sensitivity red-sensitive emulsion layer Emulsion B Silver amount 0.2 g Emulsion C Silver amount 0.3 g Gelatin 0.8 g Coupler C-1 0.2 g Coupler C-2 0.05 g Coupler C-3 0.2 g Coupler C-9 0.05 g High boiling point organic solvent Oil-2 0.1 g Additive P-1 0.1 g

Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.4 g Gelatin 1.1 g Coupler C-1 0.3 g Coupler C-2 0.1 g Coupler C-3 0.7 g Coupler C-9 0.1 g Additive P-1 0.1 g Seventh layer: Intermediate layer Gelatin 0.6 g Additive M-1 0.3 g Color mixing inhibitor Cpd-L 2.6 mg Compound Cpd- I 2.6 mg Compound Cpd-J 2.6 mg High boiling point organic solvent Oil-1 0.1 g UV absorber U-1 0.1 g UV absorber U-5 0.1 g Dye D-5 0. 015g Dye D-6 0.030g Dye D-7 0.008g

Eighth layer: Intermediate layer Gelatin 1.0 g Additive P-1 0.2 g Color mixture inhibitor Cpd-C 0.1 g Color mixture inhibitor Cpd-A 0.1 g Layer 9: Low sensitivity green Sensitive emulsion layer Emulsion E Silver amount 0.1 g Emulsion 1 Silver amount 0.4 g Gelatin 0.5 g Coupler C-4 0.10 g Coupler C-7 0.05 g Coupler C-8 0.10 g Compound Cpd-B 0 0.03g Compound Cpd-E 0.02g Compound Cpd-F 0.02g Compound Cpd-D 0.02g Compound Cpd-J 0.01g Compound Cpd-L 0.02g High boiling point organic solvent Oil-1 0.1 g High boiling point Organic solvent Oil-2 0.1 g

Layer 10: Medium-speed green-sensitive emulsion layer Emulsion G Silver amount 0.3 g Emulsion H Silver amount 0.1 g Gelatin 0.6 g Coupler C-4 0.07 g Coupler C-7 0.05 g Coupler C -8 0.05 g Compound Cpd-B 0.03 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-D 0.05 g Compound Cpd-L 0.05 g High boiling point organic solvent Oil-2 0.01 g 11th layer: High-sensitivity green-sensitive emulsion layer Emulsion I Silver amount 0.5 g Gelatin 1.0 g Coupler C-4 0.2 g Coupler C-7 0.1 g Coupler C-8 0.05 g Compound Cpd-B 0.08 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-D 0.02 g Compound Cpd-K 5.0 mg Compound Cpd-L 0.02 g High boiling point organic solvent O il-1 0.02g High boiling point organic solvent Oil-2 0.02g

Twelfth layer: intermediate layer Gelatin 0.6 g Compound Cpd-L 0.05 g High boiling point organic solvent Oil-1 0.05 g Dye D-5 0.001 g Dye D-2 0.34 g Dye D-30 .02 g Thirteenth layer: Yellow filter layer Yellow colloidal silver Silver amount 0.07 g Gelatin 1.1 g Color-mixing inhibitor Cpd-A 0.01 g Compound Cpd-L 0.01 g High boiling point organic solvent Oil-1 0.01 g Dye E -2 microcrystalline solid dispersion 0.02 g 14th layer: intermediate layer gelatin 0.6 g

Fifteenth layer: low-sensitivity blue-sensitive emulsion layer Emulsion J Silver amount 0.2 g Emulsion K Silver amount 0.3 g Emulsion L Silver amount 0.1 g Gelatin 0.8 g Coupler C-5 0.2 g Coupler C-6 0.2 g Coupler C-10 0.4 g Compound Cpd-I 0.02 g 16th layer: Medium speed blue sensitive emulsion layer Emulsion L Silver amount 0.1 g Emulsion M Silver amount 0.4 g Gelatin 0.9 g Coupler C-5 0.3 g Coupler C-6 0.1 g Coupler C-10 0.1 g

Seventeenth layer: High-sensitivity blue-sensitive emulsion layer Emulsion N Silver amount 0.4 g Emulsion O Silver amount 0.2 g Gelatin 1.2 g Coupler C-5 0.1 g Coupler C-6 0.6 g Coupler C-10 0.1 g High boiling point organic solvent Oil-2 0.1 g Compound Cpd-I 0.02 g 18th layer: 1st protective layer Gelatin 0.7 g Ultraviolet absorber U-1 0.04 g Ultraviolet absorption Agent U-2 0.01 g Ultraviolet absorber U-3 0.03 g Ultraviolet absorber U-4 0.03 g Ultraviolet absorber U-5 0.05 g High boiling organic solvent Oil-1 0.02 g Formalin scavenger Cpd-H 0 0.2 g Dye D-3 0.22 g

19th layer: 2nd protective layer Colloidal silver Silver amount 0.1 mg Fine grain silver iodobromide emulsion (average particle size 0.06 μm, AgI content 1 mol%) Silver amount 0.1 mg Gelatin 0.4 g 20 layers: Third protective layer Gelatin 0.4 g Polymethylmethacrylate (average particle size 1.5 μ) 0.1 g Methyl methacrylate / acrylic acid 4: 6 copolymer (average particle size 1.5 μ) 0.1 g Silicone oil 0.03 g Surfactant W-1 3.0 mg Surfactant W-2 0.03 g

In addition to the above composition, additives F-1 to F-8 were added to all emulsion layers. Furthermore, in each layer,
In addition to the above composition, a gelatin hardening agent H-1 and coating and emulsifying surfactants W-3, W-4, W-5 and W-6 were added. Further, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol and phenethyl alcohol were added as antiseptic and antifungal agents. Examples 1-3
And the structural formulas of the compounds used for Sample 401 are shown below.

[0124]

[Chemical 10]

[0125]

[Chemical 11]

[0126]

[Chemical 12]

[0127]

[Chemical 13]

[0128]

[Chemical 14]

[0129]

[Chemical 15]

[0130]

[Chemical 16]

[0131]

[Chemical 17]

[0132]

[Chemical 18]

[0133]

[Chemical 19]

[0134]

[Chemical 20]

[0135]

[Chemical 21]

[0136]

[Chemical formula 22]

[0137]

[Chemical formula 23]

The silver iodobromide emulsions used in Sample 401 are shown in Tables 8 and 9 (Table 9 shows the spectral sensitization conditions). The emulsion 1 used for the ninth layer is the same as the emulsion 1 of Example 1.

[0139]

[Table 8]

[0140]

[Table 9]

(Preparation of Samples 402 to 406) Emulsion 1 used in the ninth layer was prepared as emulsions 2, 4, 5, 10 and 1 having the same coating silver amount.
Samples 402 to 406 were prepared in the same manner as Sample 401, except that the emulsion No. 1 (the same as the emulsion prepared in Example 1) was replaced. (Preparation of Samples 411 to 416) Yellow colloidal silver was added to the eighth layer so that the coating silver amount was 0.03 g, and the emulsion coating amount of the ninth layer was multiplied by 1.15 to bring the magenta concentration close to the original. Samples 411 to 4 similar to Samples 401 to 406
16 was created. (Preparation of Samples 421 to 426) Fine grained silver iodobromide emulsion with the ninth layer internally fogged (average grain size 0.07 μm, coefficient of variation 18)
%, AgI content 1.0 mol%) and the amount of silver coated is 0.05 g
Samples 421 to 426 were prepared in the same manner as Samples 401 to 406, except that the addition was carried out as described above.

The above samples were evaluated for sensitivity, raw storability, residual color, latent image storability and pressure resistance. A white light source with a color temperature of 4800K was used for the above coated samples
Wedge exposure of 0 lux for 1/50 seconds was performed, and Example 1 was performed.
The color reversal development process shown in (1) was performed and the magenta density was measured to obtain the sensitivity and the maximum density Dmax. For the sensitivity, the reciprocal of the exposure amount required to give a density of minimum density +0.5 obtained by giving sufficient exposure is obtained, and the sensitivity of the sample 401 is set to 10
It was shown as a relative value of 0. Further, in order to evaluate the raw storability, Dm when the above-mentioned sensitometry was carried out after the coated sample was incubated at a temperature of 40 ° C. and a relative humidity of 60% for 60 days.
The change in ax and the decrease in sensitivity were determined as follows. (ΔDmax) = (Dmax after raw storage) − (Dmax of fresh) (Δ sensitivity) = log ₁₀ {(sensitivity after raw storage) / (Fresh sensitivity)} In order to evaluate the residual color, the above sensitometry After exposure, color reversal development processing was performed to examine the tint of the developed sample with a sufficiently large exposure amount. Further, in order to evaluate the latent image storability, the sample subjected to the sensitometric exposure was stored at a temperature of 25 ° C. and a relative humidity of 60% for 7 days, and then the color reversal development process was performed to examine the change in sensitivity. Asked. (Δ sensitivity) = log ₁₀ {(sensitivity after latent image storage) / (Fresh
Sensitivity)} Further, in order to evaluate the pressure property, after bending the sample at a constant bending angle, the color reversal development processing was performed, and the density due to the bending of the unexposed part where the density change was most remarkable The changes were compared and a three-stage evaluation was performed as follows. ◎ (especially good) ○ (good) × (concentration change is large and not possible). Tables 10 and 11 show the results of sensitized development in which the development time of the first black and white development is extended from 6 minutes to 11 minutes, as is often done in the development of color reversal light-sensitive materials. Sensitivity is the same as above, minimum density +0.5
The value was obtained as the reciprocal of the exposure amount giving the magenta density, and the increase in sensitivity due to sensitized development was obtained as follows. (Δsensitivity) = log ₁₀ {(sensitivity for 11 minutes of black and white development) / (sensitivity for 6 minutes of black and white development)} The larger the Δ sensitivity, the more preferable. The results are summarized in Tables 10 and 11.

[0143]

[Table 10]

[0144]

[Table 11]

From Tables 10 and 11, the emulsions of the present invention were found to have sensitivity,
It can be seen that it is excellent in raw storability, residual color, latent image storability, and pressure resistance. For example, the sample 402 using the selenium sensitizer for the sample 401 has high sensitivity and good latent image storability, but the raw storability and pressure property are deteriorated. Samples 403 and 404 in which the sensitizing dye is changed to S-100 for the purpose of improving the raw storage stability have excellent raw storage stability and good pressure resistance, and the sample 404 using the selenium sensitizer has high sensitivity. And the latent image keeping property deteriorated by the change of the sensitizing dye is also good, but the samples 403, 4 using the sensitizing dye S-100
In No. 04, the residual color is significantly deteriorated, and the sensitivity increase due to the sensitized development is also small. Samples 405 and 406 using the sensitizing dye SS-22 of the present invention both have good residual color, excellent raw storability, and good pressure property, but in the sample 405 not using the selenium sensitizer. The latent image keeping property is deteriorated. The sample 406 of the present invention using the sensitizing dye of the present invention and the selenium sensitizer has high sensitivity and good latent image storability, and has little adverse effect on sensitivity increase due to sensitized development.

As can be seen from Tables 10 and 11, this means that yellow colloidal silver was applied to the eighth layer, which is the layer adjacent to the emulsion layer (the ninth layer) containing the emulsion of the present invention, so that the coated silver amount was 0.03 g. It was added as described above, and it is more conspicuous in Samples 411 to 416 in which the emulsion coating amount of the ninth layer was multiplied by 1.15 to approximate the magenta density. For example, comparing Samples 401 and 411, by adding yellow colloidal silver to the eighth layer, the sensitivity increase due to sensitized development becomes large, which is preferable, but ΔDmax and Δsensitivity due to raw storage stability deteriorate. When the same comparison is carried out for Samples 402 and 412, in Sample 412 in which yellow colloidal silver was added to the eighth layer with the sensitizing dye being S-5 and a selenium sensitizer was used in combination, the raw storage stability was further deteriorated. Sample 4 using sensitizing dye S-100
In Nos. 13 and 414, in order to compensate the development acceleration (magenta concentration) of the ninth layer due to the addition of yellow colloidal silver to the eighth layer, the emulsion coating amount of the ninth layer was increased by 1.15 times, and the residual color was further deteriorated. Will end up. In Sample 415, the deterioration of the latent image keeping property due to the use of the sensitizing dye of the present invention becomes more remarkable. In Sample 416, compared with Sample 415, the sensitization of Fresh sensitization and the improvement of latent image storability are remarkable due to the combined use of the selenium sensitizer.
In addition, the sensitivity is greatly increased by the sensitized development, which is very preferable.

The following can be further understood from Tables 10 and 11. That is, the effect of the present invention becomes more remarkable by adding the internally fogged fine grain silver iodobromide emulsion to the emulsion layer (the ninth layer) containing the emulsion of the present invention, and the sensitized development by the internally fogged fine grains. It is possible to provide a very excellent light-sensitive material in combination with the effect of increasing sensitivity. For example, comparing Samples 401 and 421, it is preferable to add the internally fogged fine particles to the ninth layer because the sensitivity increase due to the sensitized development becomes large.
ΔDmax and Δ sensitivity are deteriorated due to raw storability.
When the same comparison is made with respect to Samples 402 and 422, in Sample 422 in which the sensitizing dye is internally fogged on the 9th layer as it is in S-5 and fine particles are added and a selenium sensitizer is used in combination, the raw storability is further deteriorated. In Sample 423 using the sensitizing dye S-100, the latent image storability is deteriorated as compared with Sample 403 in which internal fogging fine particles are not added to the ninth layer. Further, in the samples 423 and 424, the residual color is bad like the samples 403 and 404. In Sample 425, the latent image storability is deteriorated more markedly by using the sensitizing dye of the present invention. Sample 4
In No. 26, compared with Sample 425, Fr by using a selenium sensitizer together
esh Sensitization of sensitivity and improvement of latent image storability are remarkable, and sensitivity increase by sensitized development is also large, which is very preferable.

Fine grained silver iodobromide emulsion whose surface was fogged in place of the yellow colloidal silver added to the eighth layer of Samples 411 to 416 (average grain size: 0.05 μm, variation coefficient: 22%, AgI content: 0.5 mol%) ) Was added so that the coated silver amount was 0.06 g and the emulsion coating amount of the ninth layer was 1.15 times, the same results as those of samples 411 to 416 in Table 10 were obtained. .

Comparisons similar to those carried out in Tables 10 and 11 were carried out by using the emulsion of Example 2 in which the combination of the sensitizing dye of the present invention and the tabular grains containing dislocations, and the excellent effect of the combination of selenium sensitization. I understand. Tables 10 and 11
By using the emulsion of Example 3 in the same comparison as that of Example 3, the excellent action and effect of the combination of the sensitizing dye of the present invention and the monodisperse multi-structured grains and the combination of selenium sensitization can be seen.

The above-mentioned Example 4 showed the excellent effect of the silver halide color reversal photographic light-sensitive material for daylight light sources according to the present invention. Water-soluble dye D-7 was added to the eighth layer so that the coating amount was 0.01 g / m ² , and
By changing the emulsions J, K, L, M, N and O of the 16th and 17th layers as follows, the excellent effect of the silver halide color reversal photographic material for tungsten light source can be seen. 15th layer Emulsion J → Emulsion M Emulsion K → Emulsion M 16th layer Emulsion L → Emulsion N Emulsion M → Emulsion O 17th layer Emulsion N, O → Polydispersed twin grains (average aspect ratio 1.8, average equivalent spherical diameter 1.8) μm, coefficient of variation 23
%, AgI content 1.2mol%)

[0151]

The silver halide photographic light-sensitive material of the present invention comprises
It has an excellent effect that it has a high sensitivity, little residual color after development processing, and little change in performance when pressure is applied to the light-sensitive material and performance change due to storage before and after exposure.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tadashi Ikeda 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo Film Co., Ltd.

Claims (9)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
The silver halide emulsion contained in the silver halide emulsion layer is chemically sensitized with at least one selenium sensitizer, and has a polarographic half-wave oxidation potential of 0.7 V _VS SC.
A silver halide photographic light-sensitive material, which is spectrally sensitized with a benzimidazolocarbocyanine compound which is more noble than E and less noble than 1.1V _VS SCE. 2. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
The silver halide emulsion contained in at least one emulsion layer is a tabular silver halide grain having an aspect ratio of 2 or more,
50% or more of the projected area of all silver halide grains in the emulsion 1
The tabular silver halide grains account for at most 100%, the tabular silver halide grains have at least 10 dislocation lines per grain, and the polarographic half-wave oxidation potential is 0.7 V _VS SC.
A silver halide photographic light-sensitive material, which is spectrally sensitized with a benzimidazolocarbocyanine compound which is more noble than E and less noble than 1.1V _VS SCE. 3. The silver halide photographic light-sensitive material according to claim 2, wherein the silver halide emulsion is chemically sensitized with at least one selenium sensitizer. 4. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
The silver halide emulsion contained in at least one emulsion layer is a silver halide emulsion having a relative standard deviation of the grain size distribution of 20% or less and a layered structure of three or more phases having different iodide contents. Moreover, the polarographic half-wave oxidation potential is more noble than 0.7V _VS SCE and 1.1V _VS SCE.
A silver halide photographic light-sensitive material, which is spectrally sensitized with a more base benzimidazolocarbocyanine compound. 5. The silver halide photographic light-sensitive material according to claim 4, wherein the silver halide emulsion is chemically sensitized with at least one selenium sensitizer. 6. The silver halide according to claim 1, wherein the layer adjacent to the silver halide emulsion layer containing the silver halide emulsion contains yellow colloidal silver. Photographic material. 7. A silver halide emulsion layer containing a silver halide emulsion or a layer adjacent thereto containing a silver iodobromide emulsion whose surface and / or interior is covered. The silver halide photographic light-sensitive material described in 3, 4, 5 or 6. 8. The silver halide photographic light-sensitive material is a silver halide color reversal photographic light-sensitive material for a daylight light source or a tungsten light source.
The silver halide photographic light-sensitive material described in 3, 4, 5, 6 or 7. 9. In a silver halide photographic light-sensitive material, a benzimidazolocarbocyanine compound represented by the following general formula (S
−1) is represented by
The silver halide photographic light-sensitive material described in 3, 4, 5, 6, 7 or 8. [Chemical 1] In the general formula (S-1), V ₁ , V ₂ , V ₃ and V ₄
Represents a hydrogen atom or an electron-withdrawing group, V ₁ , V ₂ , V
_At least two or more of the substituents represented by ₃ and V ₄ are electron withdrawing groups. R ₁₁ is-(CH ₂ )
_s (CF _{2) m} H or _{- (CH 2) s (CF} 2) m F
Represents a group represented by, s represents an integer of 0 to 3, and m represents an integer of 1 to 8. R ₁₂ , R ₁₃ and R ₁₄
May be the be the same or _{different, - (CH 2) p (} CF
₂ ) _q H group or — (CH ₂ ) _p (CF ₂ ) _q F group, an optionally substituted alkyl group or alkenyl group having 10 or less carbon atoms, and R ₁₂ , R ₁₃ or R ₁₄
At least one of them is a group having a sulfo group or a carboxy group. p represents an integer of 0 to 3, and q represents an integer of 1 to 8. X ₁₁ represents a counter ion necessary for neutralizing the charge. n ₁₁ represents 0 or 1,
It is 0 in the case of an inner salt.