JPS62178947A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain green or red spectral sensitivity higher than the sensitivity of a photosensitive material by a known technique without increasing the particle volume of silver halide by having silver halide particles spectrally sensitized by a specific sensitizing dye. CONSTITUTION:This photosensitive material has the silver halide emulsion layer which consists substantially of silver bromide or silver iodobromide on at least the surface of the silver halide particles, has a (110) crystal plane on the surface of the silver halide particles and has the silver halide particles spectrally sensitized by at least one kind of the sensitizing dye expressed by the formula I and one kind of the sensitizing die expressed by the formula II. In the formulas, R1-R3 denote an alkyl group, etc., R6 denotes a halogen atom, etc., R4 denotes a hydrogen atom, etc., R5, R7 denote respectively a hydrogen atom, halogen atom, etc., X1<-> denotes an anion, q denotes 1 or 2, R denotes a lower alkyl group, etc. Z1, Z2 denote benzothiazole nucleus, etc., l-n denote 1 or 2, R9, R10 denote an alkyl group, X2<-> denotes an anion, r denotes 1 or 2.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a silver halide photographic material, and more particularly to a highly sensitive silver halide photographic material spectrally sensitized with a sensitizing dye.

[Conventional technology]

In recent years, the requirements for 7-silver lodenide photographic light-sensitive materials for photography have become increasingly strict, and the requirements for photographic performance such as high sensitivity, excellent graininess, high sharpness, low or high optical density, and sufficiently high optical density have become increasingly strict. Increasingly high water rates are being required in the industry, and from the viewpoint of resource conservation, it is necessary to reduce the amount of silver halide used (silver saving). In response to such requirements, techniques are known for increasing the sensitivity of silver lodenide emulsions by increasing the volume of silver halide grains or increasing the amount of silver halide. As a highly sensitive emulsion, a silver iodobromide emulsion containing 0 to 10 mol % of iodine is well known. Conventional methods for preparing these emulsions include ammonia method, neutral method, acidic method, etc. under pH conditions; It has been known. Based on these known techniques, technical means have been elaborately studied and put into practical use for the purpose of achieving higher sensitivity, improved graininess, higher sharpness, and lower fog. Regarding the silver iodobromide emulsions that are the object of the present invention, research has been carried out on emulsions in which not only the crystal habit and grain size distribution but also the iodine content distribution within each silver halide grain is controlled. In order to achieve the above-mentioned photographic performance such as high sensitivity, excellent graininess, high sharpness, low fringe density, and sufficiently high covering power, the quantum efficiency of silver halide has been improved and chemical A monodisperse emulsion is known that aims to efficiently achieve high sensitivity while maintaining a low thermal resistance during ripening, and is disclosed in Japanese Patent Application Laid-Open No. 54-4852, etc. face and /' or (111)
Silver iodobromide monodispersed emulsions having crystal planes are known. Further, JP-A-60-222842 discloses that low bulge can be achieved by using a silver iodobromide emulsion having a (110) crystal plane. This is the necessary increase when applying silver halide emulsions to photosensitive materials! 81 Related technologies are also described in each of the above-mentioned documents, and these t God 1? J outside t
A large number of techniques have been disclosed based on the 1-minute FfMh6tah-Takatsuki Kita 1ω halogen emulsion. However, there is a demand for the development of a technology that can achieve even higher sensitivity and silver savings than these known technologies.

[Purpose of the invention]

An object of the present invention is to provide a photosensitive material with high sensitivity, another object of the present invention is to provide a photosensitive material with reduced silver content, and a still further object of the invention is to provide a photosensitive material with reduced silver content. An object of the present invention is to provide a silver halide emulsion with high sensitivity.

[Structure of the invention]

The object of the present invention is to provide silver halide grains having at least the surface thereof substantially made of silver bromide or silver iodobromide, and having a (110) crystal face on the surface of the silver halide grains, and having the following general formula [1 ) and at least one sensitizing dye represented by the following general formula [IT]! No. with 1 particle
This is achieved by a silver halide photographic material characterized by having a silver lodenide emulsion layer. General formula [I] k. R3 In the formula, Y represents -N-1-〇- or -S-, and R3 represents an alkyl group. R,, R2 and R1 each represent an alkyl group or an alkenyl group, and RG is a norodenyl group, an acyl group, an acyloxy group, an acyl group, a carbamoyl group, a sulfonyl group, an alkylsulfonyl group, an aryloxycarbonyl group. , a sia7 group, an alkylsulfonyl group, or a trifluoromethyl group, R1 is a hydrogen atom, a fluorine atom, a bromine atom, an alkyl group, an alkoxy group, an aryl group, an acyl group, an acyloxy group, an acylamino group, a carbamoyl group, a sulfamoyl group , an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group or an alkylsulfonyl group, and when Ro is a substituent other than the chlorine atom T, R4 may be a chlorine atom. R5 and R7 are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an acyl group, an acyloxy group, an acylamine 7 group, a carbamoyl group, a sul77 moyl group, an alfkidicarbonyl group, an aryloxycarbonyl group, and a sia7 group. or an alkylsulfonyl group, and R7, R7, VR, and R6 may be bonded to each other to form a ring. ×1− represents an anion, and q represents 1 or 2. General formula (n) In the formula, R represents a lower fulkyl group, an alkoxy group, or a heterocyclic group, and Zl and Z2 each represent a benzothiazole nucleus, a naphthothiazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzoselenazole nucleus, Represents the atomic group necessary to form a naphthoselenazole nucleus, quinoline nucleus or pyridine nucleus, and! , III and 11 each represent 1 or 2, Ro and RIO each represent an alkyl group, X2- represents an anion, and r represents 1 or 2. The silver halide grains according to the present invention have a Miller index (110
) on the outer surface, and at least the surface of the grain consists essentially of silver bromide or silver iodobromide. In addition to the (110) plane, the particle surface has (ioo) planes,
(111) planes etc. may be present, but the ratio of (110 planes) to the total surface area is preferably 2096 or more, particularly preferably 80% or more.
1. Furthermore, the presence of the (iio) plane and its proportion can be determined by a method using an electron microscope or a dye absorption method. In the silver halide 7L agent layer of the present invention, the content of silver halide grains having (110) planes is preferably 30% by weight or more, more preferably 50% by weight or more. In the composition of the silver halide grains according to the present invention, "consisting essentially of silver bromide or silver iodobromide" means silver halide other than silver bromide and silver iodide, to the extent that the effects of the present invention are not impaired. For example, it means that it may contain silver chloride. Specifically, in the case of silver chloride, the ratio is preferably 5 mol% or less, more preferably 1 mol% or less. The proportion of silver iodide in the silver halide grains according to the present invention is preferably from 0 to 40 mol%, more preferably from 0 to 20 mol%, and particularly preferably from 0 to 15 mol%. Even if silver halide grains have a single composition, silver halide grains may contain multiple phases (with different halogen compositions).
For example, it may be a silver halide grain (for example, a core/shell type grain) consisting of a layer). If the silver halide grains do not have a single silver halide composition, the halogen composition inside the grains may be silver chloride, silver chlorobromide, or the like. Furthermore, the halogen composition within each state may be uniform or may vary continuously. One of the preferable forms of the clusters is one in which high iodine nuclei are present inside the grains. In other words, it is a silver halide grain that has a phase (or phases) inside the grain whose normal content is higher than the normal content on the grain surface. There is no particular restriction on the particle size of the silver halide grains according to the present invention, and the present invention is at least effective within the range of preferably 0.1 to 3.0 μIO. In this specification, the grain size of silver halide refers to the length of one side of a cube that is 1γ apart from its main volume. The silver halide grains according to the present invention are usually produced in a form in which they are dispersed in a dispersion medium such as gelatin, that is, in a form called an emulsion, and are also crucified. The particle size distribution of the group of particles at this time may be monodisperse, polydisperse, or a mixture of these, and can be appropriately selected depending on the purpose and the like. In order to produce silver halide grains having (110) planes according to the present invention, Japanese Patent Laid-Open No. 80-222842 or f! The method disclosed in Japanese Patent Application No. 59-158111 can be used. t Sub t-,, Unexamined ++r? G O-222842
In this issue, in a method for producing silver halide photographs 2L in which the surface of the Hiff silver denride grains consists essentially of silver bromide or silver iodobromide, hydrophilic protective colloids and the development of (110) crystal planes are promoted. In an aqueous medium coexisting with compounds that
Silver halide grains having (110) planes are produced by a method for producing a silver halide photographic emulsion, which is characterized by carrying out silver halide grain growth! ! ! ! It has been shown that it can be left behind. (110) Substances that promote the development of crystal planes (hereinafter referred to as
Although a clear chemical classification of crystal control compounds (referred to as crystal control compounds) is not possible at all, specifically, mercaptoazoles are preferred, and mercaptotetrazoles and mercaptothiazoles are particularly preferred. More specifically, compounds represented by the following general formulas (I[[) to [■]] are preferred. In the formula, R1 is a hydrogen atom, an optionally substituted alkyl group (
(total carbon number 15 or less), an optionally substituted aryl group (total carbon number 20 or less), or a heterocyclic group. In the formula, R2 represents a hydrogen atom or an alkyl group (total carbon number 12 or less) which may be substituted with rIl. In the formula, R1 represents an optionally substituted alkyl group (total carbon number of 10 or less) or an optionally substituted amide group (total carbon number of 10 or less). In the formula, R4 is an optionally substituted alkyl group (total carbon number 10 or less) and R4 is an optionally substituted aryl group (total carbon number] 01; J, bottom). In the formula, R5 and Ro represent an optionally substituted alkyl group (total carbon number 10 or less) or an optionally substituted amine group. Crystal control compounds (I[] to [■]) are used before the formation of silver halide grains is completed (including before the completion of Ostwald ripening)
It can be added at any time as long as it is up to. Here, the period of grain formation includes the period from the start of addition of silver ions and halogen ions until the time when new crystal nuclei are substantially no longer generated (nucleation period), and the subsequent period when new crystal nuclei are substantially no longer generated. There is a period during which particles grow without being generated (particle growth period). Preferably, it is added during silver halide grain growth. In particular, it is preferable to add the crystal control compounds (II[) to [■] after the completion of nucleation (nucleation) and before the completion of particle growth in order to limit the production of a large amount of fine particles. Conversely, it is preferable to use the crystal control compounds [III] to [■] during or before nucleation because silver halide grains consisting of fine grains can be prepared. The crystal control compounds (Ill) to [■] may be present in the reaction vessel in advance, or may be added after the start of precipitation. At this time, it may be added directly or as a solution using water, a specific solvent (for example, methanol, ethanol, etc.) as a solvent. Furthermore, the crystal control compounds (I[I) to [■] may be added alone to the reaction vessel, or the silver supply solution (for example,
It may be added to the reaction solution together with a silver nitrate aqueous solution) or a halogen supply solution (for example, a halide aqueous solution). When adding the crystal control compounds [III] to [■], they may be added continuously or intermittently. As the surface area of the silver halide grains increases, the amount of crystal control compound increases (e.g. by increasing the amount of solution added,
It is preferable to increase the concentration (increasing the concentration) in order to effectively control the crystal planes. The (110) silver halide grains of the present invention have
10) Regarding the ratio of planes, the crystal control compound (I
By changing the amounts of [[) to [■]], the ratio can be easily changed. For example, as the amount of the crystal control compound (I [l) to [■] increases, the ratio of the (110) plane increases, and at the beginning of the amount of addition described below, the ratio of the (110) plane reaches a maximum, and further crystallization When the amount of the control compound added exceeds the range described below, the ratio of the (100) plane to the (110) plane increases. The amount of the crystal control compound (I[[) to [■]] varies depending on various conditions such as the type of compound used, emulsion preparation conditions, halogen composition, and grain size, but is 5X10-5 per mole of silver halide. ~5X10-” moles are preferred, l
Xl0-'・~1. X 10-2 mol is more preferred, and 3X10-' to 6 X 10-' mol is particularly preferred. On the other hand, Japanese Patent Application No. 59-158111 describes a method for producing silver bromide or silver iodobromide grains having (110) planes, in which a water-soluble silver salt solution and a water-soluble halide solution are prepared in the presence of a protective colloid. in the step of forming silver halide grains by mixing at least 30% of the total silver halide.
During this period, the pA8 of the emulsion was controlled to a range of 8.0 to 9.5 [■], and during this period, the following general formula [■], (IX), (X) or [ XI
) and a compound having a repeating position represented by the following general formula [n] is included in the emulsion. General formula [■] General formula [: IX)
General formula (X) General formula (XI) General formula [■] I5 +C112-C÷- In the formula, II,..., l'l, 2 and R1, may be the same or different, and each represents a hydrogen atom, a halogen Atom, ami7 group, derivative of ami7 group, alkyl group, derivative of alkyl group, aryl group, derivative of aryl group, cycloalkyl group, derivative of cycloalkyl group, mercapto group, derivative of mercap 1 method or -CONII- R,4(R,
represents a hydrogen atom, an alkyl group, an amine group, a derivative of an alkyl group, a derivative of an amine 7 group, a norodene atom, a cycloalkyl group, or a cycloalkyl derivative. ), and 1<
15 represents a hydrogen atom or an alkyl group, and R11 and R
1□ may be assembled to form a ring (for example, a 5- to 7-shell carbon ring, a heterocycle), and X is a general formula [■], (IX),
A monovalent group obtained by removing one hydrogen atom from the compound represented by [X] or [X1] (for example, R11 to L in the above general formulas [■] to [X■], or one hydrogen atom removed from the 011 moiety) ), and J represents a divalent linking group. The amount of the crystal control compound [■] to (XII) to be added depends on the desired silver halide grain size, the temperature of 7L cutting, p It , p
Although it varies depending on manufacturing conditions such as Ag and silver iodide content,
to-'' to 2X10 per mole of total silver halide produced
-'molar range is preferred. In addition, when the tetrazaindene compound is a compound having a position represented by the general formula [■], the amount added is determined by the number of moles of the tetrazaindene moiety. The crystal control compounds [■] to (X[[) can be added in advance into the protective colloid solution, gradually added as the silver halide grains grow, or in combination. be. In the method for producing silver 10 denide particles according to the present invention,
Seed grains may be used to produce silver halide on their surfaces to grow the grains. The period for controlling Δg ((ii)) above is arbitrary as long as it is within the period during which silver halide is produced, and may be at the beginning, middle, or end of the silver halide production process. Further, although this period is preferably a continuous period, it may be intermittent as long as the effect of the present invention is not impaired. 1) Δg in this period is preferably 8.0 to 9
．． 5, more preferably 8.4 to 9.2. During this period, it is preferable to maintain the pIt of the emulsion within the range of 7 to 10. 1) At? of silver halide outside this period?
is suitably in the range of 4 to 11.5, preferably 6 to 1.
1 range and 1. A suitable range for H is 2 to 12;
Preferably it is in the range of 5-11. In the method for producing silver halide grains according to the present invention, the step of producing silver halide to form silver halide molecules is performed by adding an ammoniacal silver nitrate aqueous solution and a halide aqueous solution by a double jet method in the presence of ammonia. I like doing that. Further, during this grain growth process, it is preferable to add a silver and halide solution so that new crystal nuclei are not generated. The feature of this TI manufacturing method is that it can provide a silver halide emulsion with excellent monodispersity, as described in Japanese Patent Application No. 59-158111. Second, silver halide grains having (110) planes according to the present invention! ! ! Although the outline of the transmission method has been described, the details can be found in Japanese Patent Application Laid-Open No. 60-222842, 1, and T.G. No. 59-1581.
This can be known from the specification of No. 11. The silver halide grains having (110) planes according to the present invention are silver halide grains of type e, i or type I! l! During the ripening process, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt, gold salt or total complex salt, etc. may be allowed to coexist. In order to remove soluble salts from the emulsion after precipitation or physical ripening, a Nudel water washing method in which gelatin is deltized may be used. Alternatively, a precipitation method (70% gelatin method) using gelatin derivatives (eg, acylated gelatin, carbamoylated gelatin, etc.) may be used. The silver halide emulsion may or may not be chemically sensitized. For chemical sensitization, for example, Il, Frleser [D
ie Grundlagen der f'l+
otoHral+I+1scl+enProzesse
u+it 5ilberl+alogcnide
n (8kade+niscbeVerlagsge
sellscbaft, 1988) 675-734
The method described in rc can be used. That is, sulfur sensitization using sulfur-containing compounds (e.g., thiosulfates, thioureas, mercapto compounds, a-genin M) that can react with active gelatin and silver, reducing substances (e.g., stannous reduction sensitization using salts, amines, hydranone derivatives, formaminone sulfinic acid, silane compounds), metal compounds (e.g., total complex salts,
A hammer metal sensitization method using complex salts of metals of group 1 of the periodic table such as Pt, Ir, and Pd can be used alone or in combination. Examples of these include U.S. Pat. No. 1,574,944 and U.S. Pat.
2.278', 947, 2.72!11,6
No. 68, US Pat. No. 3,656,955, etc., and US Pat. No. 2.983,609, US Pat. No. 2,41 regarding reduction sensitization methods.
No. 9,974, No. 4,054. ．． No. 458, etc., and the barium metal sensitization method is described in U.S. Pat. No. 2,399,083, U.S. Pat. Next, the sensitizing dye used in the present invention will be described. In the general formula (1), Y is preferably -N- or 10-, more preferably -N-. The alkyl group represented by R to R includes a straight chain or a branched chain, preferably has 10 or less carbon atoms, and may have a substituent. At least one of R2 and R1 is preferably an alkyl group having a sulfo group or a salt thereof (eg, sulfomethyl, sulfoethyl, sulfopropyl, sulfobutyl, etc. and salts thereof). A preferred example of the alkenyl group represented by R1 or R1 is an awal group. The halogen atoms represented by R5 to R7 include, for example, fluorine atom, chlorine atom, bromine atom, iodine atom, etc., and the alkyl group represented by R4, It5 and R7 is preferably a straight (or branched lower) group having 1 to 5 carbon atoms. It is an alkyl group (for example, methyl, ethyl, propyl, butyl, trifluoromethyl, etc.), and the alkoxy group represented by I't, R5 and R7 and the alkoxycarbonyl group represented by R1 to R7 preferably have 1 carbon number. -5 linear or branched alkoxy groups (e.g. methoxy, ethoxy, etc.), and examples of the 7-aryl group of the aryl group represented by R, R5 and R7 and the aryloxycarbonyl group represented by R4 to R7 include, for example, phenyl. , triple omethylphenyl group) R1 depleted, R1
Examples of the acyl group, acyloxy group, and acylamide 7 group represented by R1 to R1 include an acetyl group and a benzoyl group; examples of the carbamoyl group include an unsubstituted carbamoyl group and a diethylamide 7carbonyl group; and examples of the sulfamoyl group include an unsubstituted carbamoyl group. Examples include a sulf77moyl group, a trimethyl7minosulfonyl group, and a morpholinosulfonyl group. Preferably, R1 is a hydrogen atom, a fluorine atom, a chlorine atom, or a bromine atom, and R6 is a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, a sia/group, a trifluoromethyl group, an aryloxycarbonyl group, an alkylsulfonyl group (especially fluoroalkylsulfonyl group)
Or a halogen atom (when R is a hydrogen atom). Examples of the ring formed by bonding R5 and R7 and R7 and R8 to each other include, for example, a benzene ring. R
8 represents a hydrogen atom when it does not form a ring. Examples of the anion represented by X- include chloride ion,
Examples include bromide ion, iodine ion, perchlorate ion, heptafluoroborate ion, 9) luenesulfonate ion, ethylsulfonate ion, methylsulfonate ion, nitrate ion, and the like. Preferred values of the sensitizing dye represented by the general formula (1) (1-3
> (+-5) ([-5) <1-7) C2H5C2H1 [IL[ILO[II, CH2Cl1,0
C11゜C2H9 ■ 2HS (I-15> 21k C11゜(I -19) Js ([I+2), 503Na (I -20) 2H5 (Cl12), SOJa C21(S (I -23) Surface general formula (II The alkyl group and alkoxy group represented by 1 in ] have 3 or less carbon atoms, preferably an ethyl group, and the heterocyclic group is, for example, a 5-shell or 6-shell ring residue containing a nitrogen atom as a hetero atom ( For example, N,N'-dialkylmalonylurea-5-yl). Zl and Z2 are preferably a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus or a tothiazole nucleus. Rto represents The alkyl group includes a straight chain and a branch, preferably has 10 or less carbon atoms, and may have a substituent. Preferred substituents include, for example, a sulfo group, a carboxy group, and salts thereof. Examples of groups include unsubstituted alkyl groups (e.g., methyl, ethyl, propyl, butyl, etc.), sulfoalkyl groups (e.g., sulfomethyl, sulfoethyl, sulfopropyl, sulfobutyl, etc.) and salts thereof, carboxyalkyl groups (e.g., carboxymethyl, carboxyethyl, etc.). ,
carboxypropyl, carboxybutyl, etc.) and salts thereof. At least one of R3 and R1°
is preferably a sulfoalkyl group or a salt thereof. Further, it is preferable that Il=1, m=2 and n=1. The anion represented by x2- has the same meaning as in X1- above. Preferred representative examples of the sensitizing dye represented by the general formula [■] are shown below. The following margins\' (II-1) (II-2) (II-3) (II-4) (n-5) (II-6) (II-7) (II-8) (II-9) ( fI-10) (If-11) (II-12) ([1-13) (II-14) (II-15) (n-16) (II-17) (I[-18) (U -19 ) (II-20) C2Hs DreC2H9 (II-21) (ff -22) (ll-23) (II-24) (II-25) (II-27) (II-28) (II-29) (ff -30) (n-31) (I[-32) (n-33) (II-34) (It-35) (II-36) (n-37) (II-38) (II-39) ( II-40) DI-41) (n-42) ([[-43) (II-44) The sensitizing dyes represented by the general formula [I] and the general formula (II) are each 3X10 per mole of silver halide. -7
~3×10−3 mol, preferably 3×10−′ to 3×1
0-' mol, particularly preferably lXl0-' to 3X10-
'Added to the silver halide emulsion in molar proportions. The molar ratio of the dye of general formula (II) to the dye of general formula [■] is preferably 1:10 to 100:1, particularly preferably 1:1 to 10:1. The sensitizing dye may be added at any stage, such as at the beginning of chemical ripening (also called m2 ripening) of the silver halide emulsion, during ripening, after the end of ripening, or at an appropriate time prior to emulsion coating. Also, as a method for adding sensitizing dyes to photographic emulsions, there are various methods that have been proposed in the past. If
; 14"+l'r'i1+jij'GIY['
l -A (: Q Q Q 7 Kure 1-e) Total 1
It may also be carried out by dissolving a sensitizing dye such as 4q in a volatile organic solvent, dispersing the solution in a hydrophilic colloid, and adding this dispersion to an emulsion. The sensitizing dyes can also be dissolved individually in the same or different solvents and the solutions can be mixed or added separately before being added to the emulsion. Silver halide milk photography using sensitizing dye? As the solvent for the dye when added to the L agent, water-miscible organic solvents such as methyl alcohol, ethyl alcohol, and acetone are preferably used. The above-mentioned sensitizing dyes can also be used in combination with Ike's sensitizing dyes or supersensitizers. Various hydrophilic colloids including gelatin are used as the binder in the silver halide emulsion in the present invention. Gelatin includes not only gelatin but also derivative gelatin, and derivative gelatin includes a reaction product of gelatin and an acid anhydride, a reaction product of gelatin and incyanate, or a reaction product of gelatin and a compound having an active halogen atom. Reaction products and the like are included. The acid anhydrides used in the reaction with gelatin include, for example, maleic anhydride, 7-talic anhydride, benzoic anhydride, acetic anhydride, isatoic anhydride, succinic anhydride, etc., and the incyanate compounds include: For example phenyl isocyanate, 1)-
Examples include bromophenyl isocyanate, 1)-chlorophenylisocyanate, 1)-tolyl isocyanate, p-nitrophenyl isocyanate, naphthylisocyanate, and the like. Furthermore, examples of compounds having an active halogen atom include benzenesulfonyl chloride, p-methoxybenzenesulfonyl chloride', 1)-7ethoxybenzenesulfonyl chloride, p-1a mobenzenesulfonyl chloride, and p-)luenesulfonyl chloride. Wright, theory - nitrobenzenesulfonyl chloride, transport-sulfobenzoyl dichloride, naphthalene-β-sulfonyl chloride, p-chlorobenzenesulfonylchloride 4-7mi/benzenesulfonyl chloride, 2-carboxy-4-bromobenzenesulfonyl chloride, If
f-carboxybenzenesulfonyl chloride, 2-amino/-5-methylbenzenesulfonyl chloride, 7thalyl chloride, 1]-nitropensoyl chloride,
Benzoyl chloride, ethyl chlorocarbonate, 7
0yl chloride and the like are included. In addition to the above-mentioned derivative gelatin and ordinary photographic gelatin, hydrophilic colloids used for preparing silver halide emulsions include colloidal albumin, agar, gum arabic, dextran, alginic acid, for example, acetyl content 19 Cellulose derivatives such as cellulose acetate hydrolyzed to ~26%, polyacrylamide, imidized polyacrylamide, casein, vinyl alcohol containing fretane carboxylic acid groups or cyanoacetyl groups such as vinyl alcohol-vinyl shea/acetate copolymers. Polymers, polyvinyl alcohol-orivinyl pyrrolidone, hydrolyzed polyvinyl acetate, polymers obtained by polymerizing proteins or saturated acylated proteins with monomers having vinyl groups, polyvinylpyridine, polyvinylamine, polyamino/ethyl methacrylate, polyethyleneimine, etc. You can also use Hardening of the emulsion is carried out according to conventional methods. The hardeners used are conventional photographic hardeners, such as aldehyde compounds such as formaldehyde, glyoxal, and glutaraldehyde, derivative compounds thereof such as their acetals or sodium bisulfite adducts, and methanesulfonic acid esters. compound, epoxy compound, aziridine compound, active halogen compound, maleimide compound, active vinyl compound, carboimide compound, inoxazole compound, N-/tyrol compound, incyanate compound, or chromium compound. Inorganic hardeners such as bread and zirconium sulfate can be mentioned. The silver halide emulsion layer of the present invention contains a coating aid, an antistatic agent,
Various known surfactants may be included for various purposes such as improving slipperiness, emulsifying and dispersing, preventing adhesion, and improving photographic properties (for example, promoting development, increasing contrast, and sensitizing). That is, U.S. Patent Nos. 2,240,472 and 2,8
No. 31,766, No. 3,158,484, No. 3,21
No. 0,191, No. 3,294,540, No. 3,507
．． No. 660, British Patent No. 1, 012,495, No. 1,
022, 878, 1,179,290, 1,198,450, U.S. Patent 2,739,891, 2,823,123, 1,1.79,290, 1 , No. 198,450, No. 2,739.891,
No. 2,823,123, No. 3,068,101, No. 3,415,649, No. 3,666, 478, No. 3
．． 75 [No. 3,828, British Patent No. 1,397,218, British Patent No. 3,113.816, British Patent No. 3,411,413,
No. 3,473,174, No. 3,345,974, No. 3,726,683, No. 3,843.368, Bell Zoichi Patent No. 731, 126, British Patent No. 1,138,51
No. 4, No. 1,159.1325, No. 1,374,78
No. 0, U.S. Patent No. 2,271,623, U.S. Patent No. 2,288,
No. 226, No. 2,944,900, No. 3,235,9
No. 19, No. 3,671,247, No. 3,772,02
No. 1, No. 3,589,906, No. 3,666, 478
No. 3,754.924, West German Open Application (OLS)
No. 1,961,683 and JP-A-50-117414
For example, saponin (steroid type), alkylene oxide: 1 JJ conductor (for example, polyethylene glycol ,
Polyethylene glyfur/polypropylene glycol condensate, polyethylene glycol alkyl or alkylaryl ether1. b) Ethylene glycol esters, polyethylene glycol sorbitan esters,
polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone),
Glycidol derivatives (e.g. alkenyl succinic acid polyglycerides, alkyl 7-ether polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, nonionic surfactants such as urethanes or ethers, Triterpemade saponins, furkyl carboxylates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates,
Alkyl phosphate ester M, N-7 sil- Carboxy group, sulfo group such as N-furkyltaurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc. Anionic surfactants containing acidic groups such as phospho groups, sulfate ester groups, and nistyl phosphate groups, amino acids, ami/alkyl sulfonic acids, ami7 alkyl sulfates or phosphate esters, alkyl betaines, amine imides, amine imides amphoteric surfactants such as alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridium and imidazolium, and cations such as aliphatic or heterocyclic sulfonium or sulfonium salts. Surfactants can be used. In the silver halide emulsion layer of the present invention, as a development accelerator,
In addition to the surfactants mentioned above, OLS 2.
No. 002,871, No. 2,445,611, No. 2,3
It may contain imidazoles, thioethers, selenoethers, etc. described in No. 60.878, British Patent No. 1,352,196, and the like. Further, in order to apply the present invention to a color photosensitive material, the silver halide emulsion layer according to the present invention is used as a red-sensitive silver halide emulsion layer and an a-sensitive silver halide emulsion layer, and cyan and magenta couplers are respectively incorporated. The method and material used for color light-sensitive materials may be used, such as incorporating the coupler, and the coupler is preferably a non-diffusible coupler having a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ion. Also, colored couplers that have a color correction effect, or couplers that release a development inhibitor during development.
(so-called DIR coupler). Additionally, the coupler may be such that the product of the coupling reaction is colorless. In the light-sensitive material of the present invention, a known closed ketomethylene coupler can be used as a yellow color-forming coupler. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. The only example of a yellow coloring coupler that can be used is U.S. Patent No. 2,875,057.
No. 3,265,506, No. 3,408,194, No. 3,551,155, No. 3,127.269,
Accommodation 13. L! Bow, 072 minutes 1 Swamp 9-1'IQIia
Heban Menchi 1t Take 1.547,868, West German Publication (OLS) No. 2,213,461, OLS No. 2,2
No. 19,917, No. 2,261,361, No. 2,41
It is described in No. 4,006, No. 2,263,875, etc. As the magenta coloring coupler, pyrazolone compounds, indacylon compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are particularly advantageous. A specific example of a magenta color-forming coupler that can be used is disclosed in U.S. Pat.
, No. 600,788, No. 2,983,608, No. 3,
No. 062,653, No. 3,127.269, No. 3,3
14.476, 3,419,391, 3,51
No. 9.429, No. 3,558,319, No. 3,582
, No. 322, No. 3,615,506, No. 3,834,
No. 908, No. 3,89L445, West German Patent No. 1.810
, No. 464, West German Publication (OLS) 2,468,6
No. 65, No. 2,417,945, No. 2,418,95
No. 9, No. 2,424,467, Special Publication No. 40-6031
This is what is listed in the issue. As the cyan coloring coupler, phenolic compounds, naphthol compounds, etc. can be used. Specific examples are U.S. Pat. Nos. 2,369,929 and 2,434,27.
No. 2, No. 2,474,293, No. 2,521,908
No. 2,895,826, No. 3,034,892, No. 3,311.476, No. 3,458,315,
No. 3,476.563, No. 3,583,971, No. 3,591,383, No. 3,767.411, OLS No. 2,414,830, No. 2,4
No. 54.329, JP-A-48-59838';'f. Colored couplers include, for example, U.S. Pat.
No. 908, No. 3,034,892, Special Publication No. 1977-20
No. 16, No. 38-22335, No. 42-11304, No. 44-324 (No. 31, Patent Application No. 49-98469, No. 50-118029, West German Application Publication (OLS))
2,418,959 can be used. As DIR couplers, for example, U.S. Pat. Nos. 3,227,554 and 3,617,291
No. 3,701.783, No. 3,790,384, No. 3,632,345, OLS 2
, No. 414,006, No. 2,454,301, No. 2,
Those described in No. 454,329, British Patent No. 953,454, and Japanese Patent Application No. 146,570/1986 can be used. In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor upon development, such as those disclosed in U.S. Pat. No. 3,297,445, U.S. Pat. , 417,914 can be used. Others, JP-A-55-8554
No. 9, No. 57-94752, No. 513-65134, No. 56-135841, No. 54-130716,
No. 56-133734, No. 56-135841, U.S. Patent No. 4,310,618, British Patent No. 2,083,6
No. 40, Research Disclosure - 18360 (1
979), 14850 (1980), 19033
(1980), 19146 (1980), 20
525 (1981), 21728 (1982)
Couplers described in can also be used. Two or more of the above couplers can be contained in the same layer. Further, the same compound may be contained in two or more different layers. To introduce the coupler into the silver halide emulsion layer, known methods such as those described in US Pat. No. 2,322,027 can be used. For example, 7-tar acid alkyl ester (dibutyl 7-thalerate, nooctyl 7-thaletate, etc.),
Phosphate esters (diphenylphos 7!-), ) triphenylphostate, triphrenorphosphate, nooctylbutylphos 7!), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. benzoic acid) octyl), alkylamides (e.g. diethyl laurylamide), or boiling points of about 30°C to 15°C.
After dissolving in an organic solvent at 0°C, such as lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is converted into a hydrophilic colloid. distributed. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used. When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution. These couplers are generally present in amounts ranging from 2 X 10-' moles to 5 X 10-' moles per mole of silver in the silver halide emulsion layer.
mole, preferably 1XIO-2, mole to 5X10-'
molar added. The light-sensitive material of the present invention may contain a hydroquinone derivative, an amino 7-ethyl derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifogging agent, and specific examples thereof are disclosed in U.S. Pat. , 2,336,
No. 327, No. 2,403,721, No. 2,418,6
No. 13, No. 2,675.314, No. 2,701,19
No. 7, No. 2,704,713, No. 2,728.659
No. 2,732,300, No. 2, 735. No. 765, JP-A No. 50-92988, JP-A No. 50-929
No. 89, No. 50-93928, No. 50-110337
No., Japanese Patent Publication No. 50-23813, etc. Antistatic agents include diacetyl cellulose and styrene.
Perfluoroalkylsonorum maleate copolymers, alkali salts of reaction products of styrene-maleic anhydride copolymers and p-7 minobenzenesulfonic acid, and the like are effective. Examples of matting agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers. Furthermore, it is also possible to use colloidal silicon oxide. Further, examples of the latex added to improve the physical properties of the film include copolymers of acrylic esters, vinyl esters, etc., and monomers having ethylene groups. Examples of the gelatin plasticizer include glycerin and glycol compounds, and examples of the thickener include styrene-sodium maleate copolymer, alkyl vinyl ether-malein (fl co-IJ1), etc. Examples of the support include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass paper, cellulose acetate, cellulose nitrate,
Supports include polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate, and polystyrene, and these supports are appropriately selected depending on the intended use of each photosensitive material. These supports are subjected to undercoat processing if necessary. After exposure, the light-sensitive material of the present invention can be developed by a commonly used known method. The black and white developer is an alkaline solution containing developing agents such as hydroxybenzenes, amine/phenols, and aminobenzenes, and may also contain alkali metal salts such as sulfites, carbonates, bisulfites, bromides, and iodides. I can do it. When the light-sensitive material is for color use, color development can be carried out by a commonly used color development method. In the reversal method, the image is first developed with a black-and-white developer, then exposed to white light or treated with a bath containing a fogging agent, and then color developed with an alkaline developer containing a color developing agent. There is no particular limit to the processing method, and any processing power method can be used; for example, typical methods include a method in which color development is followed by bleach-fixing, followed by washing with water and stabilizing treatment if necessary; After color development, bleaching and fixing can be carried out separately, and if necessary, washing with water and stabilizing treatment can be carried out. The photosensitive material according to the present invention can be preferably applied to many uses requiring high sensitivity. For example, black and white general 1. It can be used for various purposes such as X-ray, color, infrared, micro, silver dye bleaching, reversal, and diffusion transfer. When applied to multilayer color light-sensitive materials, the present invention can be applied to various layer configurations well known in the art, including normal layer, reverse layer, and other layer configurations. [Example] The present invention will be specifically described below with reference to Examples. Example 1 Emulsion A An emulsion containing 0.29 mol of octahedral silver bromide grains with an average grain size of 0.68 μm was dispersed in 1000+a1 of distilled water (containing 25% ammonia 30+a12), and then 1-phenyl- Add 75 ml of a 0.1% methanol solution of 5-flucaptotetrazole, and add 100 ml of a 0.47 mol/1 silver nitrate aqueous solution (HL) and a mixed aqueous solution of potassium bromide and potassium iodide (iodide) at 50°C. The potassium ratio was 5 mol %) by a controlled double jet method, by adding 8 g of I) over 40 minutes while controlling the amount to 10.0. Next, after desalting in a conventional manner, gelatin was added and redissolved. As a result of electron microscopic observation, the silver iodobromide grains of emulsion A were (11
It was an almost perfect rhombic dodecahedron consisting of 0) crystal planes (average grain size 1.0 μLL1). Emulsion B (1)-Phenyl-5-mercaptotetrazole 0.1% methanol solution 75 Emulsion B was prepared in the same manner as Emulsion A except that the same amount of methanol was used instead of 75 tol. As a result of electron microscopy, the silver iodobromide grains of emulsion B were (11
1) The crystal planes were a perfect octahedron (average grain size 1.0 μm). Next, sodium periosulfate, chloroauric acid, and ammonium thiocyanate were added to each of the above emulsions A and B, and each was optimized for each emulsion. After sensitization, sensitizing dyes exemplified as sensitizing dyes represented by formulas (1) and (Tl) of the present invention were added according to Table 1 below. Each emulsion was then treated with 4-hydroxy-6-methyl-1,3,3a 7-titrazaindene, 1-phenyl-5-mercapto-tetrazole as a stabilizer, saponin as a coating aid, and 1.2 as a hardener. - addition of 38% of bis(vinylsulfonyl planetary and polyvinylbilidone),
Further, a dispersion of a mixture of cyan coupler, dodecyl late, tricresyl phosphate, ethyl acetate, sodium triisopropylnaphthalene sulfonate and gelatin was added. (Cyan coupler) The emulsion thus prepared was coated on a cellulose triacetate base support and dried to prepare samples 1 to 5. Then each sample was filtered through a green filter with 115
An exposed sample was prepared with a wedge exposure of 0 seconds, and a color negative development process was performed as described below. Processing process (38°C) Processing time Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Stabilization 1
The composition of the processing solution used in each processing step for 30 minutes is as follows. Color developer 4-7 Minnow 3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.8 g Anhydrous sodium sulfite 0.14 g Hydroxylamine 1/2 sulfate 1.98 g Sulfur
Acid 0
．． 74+ng anhydrous potassium carbonate 2
8.85g anhydrous potassium bicarbonate 3,
468 Anhydrous Potassium Sulfite 5.10
FK potassium bromide 1.16
g Sodium chloride 0.14 g Nitrilotriacetic acid trisodium salt (monohydrate) 1.20 g Potassium hydroxide 1.48° Add water and 1! shall be. Bleach solution ethylenediaminetetraacetic acid iron ammonium salt 100.
0g ethylenenoaminethitraacetic acid diammonium salt 10, O
g Ammonium bromide 150.0g Glacial acetic acid 10.0+oN Add water to make 1e, and adjust to 116°0 with ammonium water -1. Fixing solution Ammonium periosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water 11
Adjust to pl+6.0 using acetic acid. Stabilizing liquid formalin (37% aqueous 'tL) 1.5111 Konigunkus (Roku Konishi Photography 'j: Co., Ltd. *) 7. ! 5
Add +n1 water to make 11. 1rLt-Lead paper field I dispute one group x-hsz hakiku! Density was measured through a 7 Nolter to determine red light sensitivity and fog. The sensitivity was determined from the amount of exposure necessary to give an optical density of "Capri+0.1". The sensitometry results are shown in Table 1 below. Note that the sensitivity is expressed relative to the sensitivity of Sample 1 as 100. /〆' As is clear from the margin f51 table below, samples 3 to 5 of the present invention having silver iodobromide grains having a (110) crystal plane sensitized by the combination of sensitization and dyes according to the present invention. , both have higher sensitivity than the comparative samples. Example 2 Emulsion C An emulsion containing 0.29 mol of regular octahedral silver bromide grains with an average grain size of 0.68 μm was dispersed in 10,100 O of distilled water (containing 30 tn (l) of 25% ammonia), and then 1- 7 Enyl-5-flucaptotetrazole 0.1% methanol solution 75 + a l was added and at 50°C 0.47
500τall of a mol/l silver nitrate aqueous solution and a necessary and sufficient mixed aqueous solution of potassium bromide and potassium iodide (the ratio of potassium iodide is 15 mol%) were prepared using a 7-leg purge method. 0.47 mol/l silver nitrate aqueous solution
00+++1 and a necessary and sufficient mixed aqueous solution of potassium bromide and potassium iodide (the ratio of potassium iodide is 2 mol%) using the controlled double jet method for 20 minutes while controlling the temperature to -g10.0. After salting, gelatin was added and redissolved. Emulsion C thus produced was a core/shell emulsion with a high iodine core inside, and as a result of electron microscopic observation, it was found to contain almost perfect rhombic dodecahedral grains consisting of (110) crystal faces. Emulsion average grain size 0.68μIfi octahedral silver bromide grains 0.2
After dispersing the emulsion containing 9 mol in 1000 zf of distilled water (containing 25% ammonia 3011), 75 pl of methanol was added, and at 50°C, 500 t of a 0.47 mol/1 silver nitrate aqueous solution and the necessary and sufficient amount of potassium bromide were dispersed. and a mixed aqueous solution of potassium iodide (the ratio of potassium iodide is 15 mol%) using a 7-leg pull jet method.
0.0, over 30 minutes while controlling the amount of mol %) was added using a controlled double jet in a controlled manner to 1) 8 gIO6O over 20 minutes. Next, gloss gelatin lightly salted was added to dissolve the gelatin again. The emulsion was a core/shell emulsion with a high iodine nucleus inside, and as a result of electron microscopic observation, it was found to contain perfectly regular octahedral grains consisting of (111) crystal faces. Emulsion C and milk shavings were each subjected to chemical ripening in a conventional manner to obtain an emulsion with an average grain size of 1.0 μτn1, a silver content of 0.60 mol/kg, and a gelatin content of 708/kg. 1 kg of this emulsion was heated to 40°C, and 0.030 mol of the following magenta coupler per 1 mol of silver and 0.001 mol of the following DIR compound per 1 mol of silver were dissolved in ethyl acetate and dibutyl 7-thale. Add sodium dodecylbenzenesulfonate and mix with a homogenizer.
It was emulsified and dispersed in a 0% aqueous gelatin solution. This emulsion was added with Meta 7 of each of the sensitizing dyes shown in Table 2.
The solution was added and mixed and stirred. Furthermore, 4-hydroxy-6-methyl-1,3,3a, 7
-20+o1 of a 1.0% by weight aqueous solution of chitrazaindene
was added, 20 b+ 1 of a 1% aqueous solution of 1-hydroxy-3,5-nochlorotriazine sodium salt was added, and 1.
Add 10 ml of 0% by weight aqueous solution and stir for 1! Shita. This completed emulsion was coated on a cellulose triacetate film base so that the coated silver amount was 5 g/+n2, and dried to obtain a sample. This film sample has a color temperature of 540
Using a sensitometer with a 0"K light source and attaching a green filter to the light source, a wedge exposure was carried out. After exposure, the following development process was carried out, bleaching, fixing and drying, and the density of the developed magenta color image was measured. The optical density reference point for determining the sensitivity was Cub 17 + 0.20. The results are shown in the fjS2 table. The sensitivity is expressed as relative sensitivity with the sensitivity of sample 7 as 100. Coupler <Development process> Color development 3 minutes 15 seconds (38℃) Bleaching
Wash with water for 6 minutes and 30 seconds, fix for 3 minutes and 15 seconds.
Rinse with water for 6 minutes and 30 seconds Stable for 3 minutes and 15 seconds
3 minutes and 15 seconds The composition of the treatment liquid used in each step is as follows. Sodium Nitrilotriacetate 1.0g Sodium sulfite 4.0° Sodium carbonate
30.0g sodium bromide
1.4g Hydroxylamine sulfate 2.4g
4-(toethyl-N-73-hydroxyethylamine)
-2-Methylaniline sulfate Add 4.5 g of water to make 11. Bleach solution ammonium bromide 160.0g ammonia (28%) 25. Own/Ethylenenoamine-Tetraacetic acid sodium iron salt 130, Og Glacial acetic acid 14.0ml Add water to make 11. Fixer Tetra Polyphosphoric Acid
2.0g sodium sulfite 4.0g ammonium neosulfate 7096) 175.0ml! Add 4.6g of sodium bisulfite water to make 1r. Add stabilizer formalin 8101 water to make 1r. As is clear from Table 2 below, even in core/shell grains having high iodine nuclei inside the grains, iodine odors having (110) crystal faces were sensitized by the combination of sensitizing dyes according to the present invention. Samples 8 to 11 of the present invention having silver oxide grains have higher sensitivity than the comparative samples. [Effects of the Invention] According to the present invention, without increasing the grain volume of silver halide,
It is possible to obtain higher green to red spectral sensitivity than light-sensitive materials produced by known techniques, and silver savings can be achieved thereby.

Claims (1)

[Scope of Claims] At least the surface of the silver halide grain is substantially composed of silver bromide or silver iodobromide, and the surface of the silver halide grain has a (110) crystal plane, and the surface of the silver halide grain has the following general formula [I ] and at least one sensitizing dye represented by the following general formula [II]. A silver halide photographic light-sensitive material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Y is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -O
- or -S-, and R_9 represents an alkyl group. R
_1, R_2 and R_3 each represent an alkyl group or an alkenyl group, and R_6 is a halogen atom, acyl group, acyloxy group, acylamino group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, alkylsulfonyl group or represents a trifluoromethyl group, R_4 is a hydrogen atom, a fluorine atom, a bromine atom, an alkyl group, an alkoxy group, an aryl group, an acyl group, an acyloxy group, an acylamino group,
It represents a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or an alkylsulfonyl group, and when R_6 is a substituent other than a chlorine atom, R_4 may be a chlorine atom. R_5 and R_7 are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an acyl group, an acyloxy group, an acylamino group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or an alkylsulfonyl group and R_5 and R_7 and R_7 and R_8 may be bonded to each other to form a ring. X_1^- represents an anion, and q represents 1 or 2. ] General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. nuclear,
Represents an atomic group necessary to form a naphthoxazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, quinoline nucleus or pyridine nucleus, l, m and n each represent 1 or 2, and R_9 and R_1_0 each represent an alkyl group. , X_2^- represents an anion, r is 1 or 2
represents. ]