JPH03135548A - Silver halide sensitive material containing calyx-attached silver halide crystal grain - Google Patents

Abstract

PURPOSE:To enhance spectral sensitivity to red by incorporating silver halide crystal grains having ridge line calyces attached and color sensitized by a combination of 2 kinds of sensitizing dyes. CONSTITUTION:The regular octahedron can be bisected by the 3 planes which contains the 4 ridge lines of the total 12 ridge lines, and each of the 3 planes is rectangular to each other. The ridge line calyx slips of each of the silver halide octahedron crystals protrude along these bisecting planes AB, BC, and CA and are attached to the main crystal. The silver halide photosensitive material contains these crystals as well as the crystal particles sensitized by the sensitizing dyes each represented by formulae I and II in which R1 is H, alkyl, or the like; each of R2 and R3 is alkyl; each of V1-V8 is H, alkyl, halogen, or the like; (X1)l1 is counter ions for balancing electric charge, and l is an integer of >=0; and each of R5 and R6 is alkyl; each of Y1 and Y2 is S or Se; and R4, W1-W8, and (X2)l2 are same as R1, V1-V8, and (X1)l1, thus permitting high red sensitivity to be obtained in the case of spectrally sensitizing the photosensitive material in the red wavelength region.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to silver halide crystal grains having a unique shape, and further relates to a silver halide photosensitive material in which the grains exhibit an effect on photographic performance.

[Background of the Invention] In recent years, demands on silver halide emulsions for photography have become increasingly strict, and photographic performance such as high sensitivity, excellent graininess, high sharpness, low fog density, and sufficiently high optical density has become increasingly important. High standards are required.

In order to meet these demands, silver iodobromide emulsions containing 10 mol % or less of silver iodide are well known as high-sensitivity emulsions. Conventionally, known methods for BM Ning these emulsions include methods that control pH conditions and PAg conditions such as ammonia method, neutral method, and acidic method, and mixing methods such as single jet method and double jet method. It is being

Based on these known techniques, technical means have been elaborately studied and put into practical use for the purpose of achieving high sensitivity, improved graininess, high sharpness, and low fog. In particular, research has been carried out on silver bromide and silver iodobromide emulsions in which not only the crystal phase and grain size distribution but also the concentration distribution of silver iodide within each silver halide grain is controlled.

The most traditional way to achieve the above-mentioned photographic performance such as high sensitivity, excellent graininess, high sharpness, low fog density and sufficiently high covering power is to improve the quantum efficiency of silver halide. That's true. For this purpose, knowledge of solid state physics is actively incorporated. According to research that theoretically calculated this quantum efficiency, narrowing the particle size distribution to create a monodisperse emulsion is effective in improving the quantum efficiency. It is inferred that monodisperse emulsions are advantageous in order to efficiently achieve high sensitivity while maintaining low fog in a process called chemical sensitization.

For engineering monodisperse emulsion preparation, JP-A No. 54-4852
After strict control of PAg and pH as described in No. 1, control of the supply rate of the theoretically hydrated silver ions and halide ions to the reaction system and sufficient stirring conditions are required. Ru. The silver halide emulsions produced under these conditions have cubic, octahedral, or tetradecahedral shapes with various proportions of (100) and (111) planes, so-called Consists of normal crystal grains. It is known that such normal crystal particles can increase sensitivity.

Furthermore, as silver halide grains capable of obtaining high sensitivity, silver iodobromide grains having excellent photographic properties and having (110) planes are disclosed in Japanese Patent Application Laid-Open Nos. 61-35440 and 60-222842, respectively. In addition, in Japanese Patent Publication No. 55-42737, there is a rhombus with (110) face as a product with less fog.
Photographic emulsions containing dihedral silver chlorobromide grains are disclosed.

On the other hand, JP-A No. 61-83531 discloses silver bromide and silver iodobromide grains having crystal planes having a ridge line in the center of the (110) plane, and it has been shown that this allows for even higher sensitivity. has been done. This crystal plane is considered to be a very high-order crystal plane, and its characteristics are described in Japanese Patent Application Laid-Open No. 61-83
It is stated in No. 531.

The crystal plane is expressed as (nnl), and examples such as the (331) plane are shown.

Other aspects are described in JP-A Nos. 62-124551, 62-124550, and 62-123447.

On the other hand, silver iodobromide emulsions comprising polydisperse twin crystal grains have been known as silver halide emulsions suitable for high-speed photographic films.

Moreover, silver iodobromide emulsions containing oblate twin grains are disclosed in Japanese Patent Application Laid-open No. 58-113927 and others.

Although these twin-related techniques contribute to high sensitivity, they tend to be irregular in shape and size, making it difficult to precisely control photographic characteristics, and causing problems in reproducibility.

On the other hand, in the field of chemical sensitization treatment, chemical sensitization reactions for normal crystals have a large crystal phase preservation property, and for example, in normal methods, there are many sulfur sensitizing nuclei on the (111) plane compared to the (100) plane. As a result, latent image formation becomes dispersive and inefficient, and therefore, it is known that sensitization efficiency is poor.Therefore, it is difficult to put silver halide grains having the above-mentioned (111) plane into practical use. have been considered disadvantageous or difficult.

For example, Japanese Patent Application Laid-open No. 50-63914 and German patent application (
OLS) No. 2,419,798 discloses that after sulfur-sensitizing a monodisperse silver halide grain emulsion of cubic grains with a silver bromide content molar ratio of 80% or more, a hydroxytetrazaindene compound is added. It is stated that the sensitivity increases, and this publication states that for crystal shapes other than cubic, for example, octahedral grains substantially surrounded by (111) planes, the sensitivity may actually decrease or even increase. It is also noted that the extent of the damage is slight.

As mentioned above, research from the viewpoint of crystal morphology is progressing at an impressive rate toward improving the photographic properties of silver halide photosensitive materials, but with the exception of minute concave portions of twins or concave portions of fusion, all of them are There is no research on crystals that are outwardly convex and have clearly large concave portions on the crystal plane.

However, the lines or points of intersection of the surfaces forming the concave portions are thought to exhibit specificity in the concentration of effects in chemical sensitization, exposure, and development, and development from crystals having concave surfaces is expected.

Further, crystal particles having such a concave surface are considered to have unique properties regarding adsorption of a sensitizing dye during spectral sensitization and phenomena during electron transfer.

Regarding silver halide photographic materials in recent years, many techniques have been developed to spectral sensitize silver halide emulsions so that they can be appropriately sensitized to blue, green, and red light, and this method is known as spectral sensitization. It is being The objectives of such spectral sensitization are that the spectral sensitization wavelength range is appropriate, that it is not reactive with various additives, that it does not deteriorate photographic properties, and that it has excellent storage stability. Alternatively, it must not only satisfy various conditions such as not causing color staining after development processing, but first of all, it must not be able to achieve high spectral sensitivity.

Among the above-mentioned spectral sensitization methods, an effective spectral sensitization technique is essential to achieve high sensitivity in the visible light region. As a means for spectral sensitization, it is widely known that a dye such as cyanine or melonidianine is used alone, and that a plurality of dyes are used in combination to superchemically sensitize any wavelength range. Regarding sensitization in the red light region using dyes in this way, for example, U.S. Patent No. 3,338,7
No. 14, No. 4,326,023, Special Publication No. 48-25
No. 653, No. 5854378, JP-A-59-1.14
The combination of these dyes has little interaction with photographic additives and has been evaluated as a technology that provides high sensitivity and low fog density.

However, even if the above-mentioned existing techniques are applied directly to conventional silver halide grains containing normal crystals and twin crystals, a significant increase in color sensitization sensitivity will not necessarily be observed. In conventional silver halide emulsions containing sensitizing dyes, as the amount of sensitizing dyes added increases, the inherent sensitivity of the emulsion decreases, and a method to solve this fundamental problem of sensitization during adsorption of sensitizing dyes has been desired. .

[Problem that the invention seeks to solve]

Silver halide crystal grains that most effectively concentrate the effects of chemical sensitization, spectral sensitization, exposure or development mentioned above include:
One example is a crystal in which the concentration site is the intersection line or point of intersection of the crystal planes forming the concave surface, but this requires precise and novel control of the specific crystal structure. is preferably a normal crystal without any lattice defects or other singular points that would be a substantial hindrance.

However, in systems in which normal crystals with a predetermined crystal phase, especially monodisperse silver halide grains, are freely suspended, the crystal grains grow surrounded by almost isotropic planes, and there are usually no peculiarities such as crystal habit. Otherwise, there are few opportunities to exhibit anisotropy.

On the other hand, under conventional conditions that exhibit anisotropy such as twin crystals, it is difficult to precisely control grains, control chemical sensitization associated therewith, and ultimately control photographic properties.

Furthermore, conventional silver halide emulsions containing normal crystals and twin crystals suffer from desensitization due to adsorption of sensitizing dyes, and therefore, silver halide emulsions with less desensitization and high spectral sensitivity have been desired.

[Purpose of the invention]

It is an object of the present invention to provide silver halide crystal grains that exhibit concentration of effects on sensitization, exposure, or development and have high red light sensitivity when spectral sensitized to the red light range; The object of the present invention is to provide a novel silver halide photosensitive material having an emulsion layer containing the sensitized silver halide crystal grains.

[Structure of the invention]

The above-mentioned objects of the present invention are achieved by a photographic light-sensitive material containing the following silver halide crystal grains. That is,
Silver halide grains in photographic emulsions, which are parallel to three planes formed by four edges on the same plane of a regular octahedron assumed in its normal crystal, and interlock with each other at right angles. It is a silver halide crystal grain with calyx fragments attached with crystal fragments extending out (hereinafter, such crystal grains are also referred to as the crystal grains with calyx fragments J of the present invention), and also has the general formula (13) described in detail later. A silver halide sensitizer containing silver halide crystal grains with calyx fragments sensitized with a small number of sensitizing dyes represented by one type of sensitizing dye and at least one type of sensitizing dye represented by the following general formula (II). This is achieved through the use of materials.

Next, the present invention will be explained in detail.

In general, the crystal planes of silver halide crystal grains contained in silver halide emulsions have a certain density depending on the dense density, lattice energy, surface energy, or growth conditions of the silver ions and halide ions arranged on the plane. Crystal planes with specific Miller indices are dominantly expressed and give the crystal a specific crystal phase.

Furthermore, when there is a difference in the grain size scale in the growth conditions surrounding each crystal grain, the sizes of the planes differ even though they have the same Miller index, resulting in a crystal habit in each grain.

On the other hand, the plane that becomes the final crystal plane that gives the crystal a crystal phase is the plane that has the minimum growth rate in the normal direction to the cough plane (A, Jo
hnsen, 1910)", by selecting the growth conditions, even silver halide crystals belonging to the cubic system can be given a crystal form having a predetermined crystal phase.

For example, in order to give cubic silver halide a hexahedral (cubic) crystal phase, the growth rate on cubic planes, that is, the deposition of silver ions and halide ions, is slower than on other Miller index crystal planes. should be given.

Furthermore, when changing the crystal phase from an octahedral silver halide crystal grain surrounded by (111) planes to a hexahedral (cubic) host grain, growth conditions are provided to suppress the growth of cubic (100) planes. As silver is further precipitated, a cuboctahedron, that is, a tetradecahedron with six vertices of the octahedron removed, appears in the middle, and the (111) face gradually degenerates until a crystal with only cubic faces appears. In other cases, cubic crystal grains enlarge as silver halide is added.

Finally, cubic crystal particles can be used as host particles to form octahedral crystal particles.

Similarly, for example, trioctahedral crystal grains can also be derived from cubic crystal grains as host grains. In other words, if silver halide precipitation is continued by selecting growth conditions in which growth in the normal direction of trioctahedral crystal planes is slower than planes of other Miller indices, trioctahedral crystal planes will first be recognized, and then Eventually, the host grains are occupied by trioctahedral crystal faces.

Desired crystal particles can also be obtained with other crystal grains having tetrahexahedral, rhomboid icosahedral, and hexahedral crystal faces by selecting growth conditions that suppress the growth of the faces that provide the respective crystal phases.

The growth conditions for the silver halide grains having various crystal phases are as follows:
Deposition of silver halide on crystal surfaces is influenced by a wide variety of factors such as silver halide composition, density of ions arranged on crystal planes, temperature, lattice or surface energy, adsorbate, silver halide solvent, etc. A growth modifier is added as a factor to retard the process.

Many compounds are already known as growth regulators, and for photographic silver halide, there are photographic dyes such as cyanine dyes that have adsorption properties on the surface, stabilizers such as azaindene and imidazole, and fog suppressants. Some of these are known to be useful. (The above-mentioned disclosed patent publication, Japanese Patent Application No. 62-15
No. 9280, etc.).

However, at present, there is a lack of theory that relates the various factors that influence crystal growth as described above and the crystal form produced, and in particular, there is no theoretical support for the unexplored technical field of producing concave surfaces in crystal grains as in the present invention. Therefore, we have no choice but to search for a method to realize the intended crystal form through trial and error.

In the present invention, conditions for preparing crystal particles include, for example, PAg,
By trial and error regarding the temperature or silver halide addition rate and fluctuation of conditions, for example, the production and/or growth of silver halide crystal grains was controlled at pAg 7 to 11.5 and pH 5.8 to 11.
．． 5, and at the time of growth when the crystal shape is octahedral or tetradecahedral, add 1 to 300 mg/8 g of cyanine dye.
By adding 1 mol of AgX at once and continuing AgX growth, the ridges are parallel to each other along the three planes (referred to as ridge planes) formed by the ridge lines of the octahedron, and the three ridge planes are at right angles to each other. Silver crystal grains having eight quadrants each having concave portions with the preceding crystal plane as the bottom surface are obtained.

As the particle growth process, a means for creating core/shell type particles is used, and the crystal part with calyx is also considered to be a deformed shell part.

In the present invention, the specificity of the particles can be further amplified by appropriately doping a metal complex salt during the generation and/or growth of crystal particles.

Further, when the normal crystal particles are used in a photosensitive material, it is preferable to make them monodisperse using a known method.

A schematic diagram of the calyx-clipped crystal grain having a concave surface of the present invention is shown in FIG. 1, and electron micrographs are shown in FIGS. 2 to 4.

In FIG. 1, an octahedral crystal is taken as an example of a host normal crystal, and (a-b), (b-c), and (c-a) are the ridge planes formed by axes a, b, and C. The figure shows only one quadrant of the three ridges.

(AB), (BC) and (CA) are parallel to the ridge plane,
They are crystals of sepals that interlock with each other at right angles and protrude. FIG. 2 is an electron micrograph of a crystal with calyx fragments seen from an angle similar to the schematic diagram in FIG. 1. FIG. 3 shows the crystal viewed from the axes a, b or c direction. Figure 4 shows a group of crystals with sepals in the process of growth.

This means that growth inhibitory factors do not act in the direction of sepal growth, but the disc-like growth in this direction in a homogeneous suspension system is probably due to the growth of twins. .

The silver halide emulsion used in the light-sensitive material of the present invention includes those used in ordinary silver halide emulsions such as silver bromide, silver iodobromide, silver chlorobromide, and silver chloride. However, silver bromide and silver iodobromide are particularly preferred.

The silver halide grains used in the silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown continuously or may be grown stepwise while creating seed particles. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Further, while taking into account the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding them while controlling the pH and pAg in the mixing pot. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained.

During the growth of silver halide grains, a known silver halide solvent such as ammonia, 1,000-onythyl, thiourea, etc. can be present.

Silver halide grains contain at least one selected from cadmium salts, zinc salts, lead salts, thallium salts, iridium salts, rhodium salts, iron salts, and complex salts thereof during the process of forming and/or growing the grains. These metal elements can be added inside the particles and/or on the surface of the particles by adding metal ions, and by placing them in an appropriate reducing atmosphere, reduction sensitization can be carried out inside the particles and/or on the surface of the particles. Can give a nucleus.

In the silver halide emulsion used in the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, Research Discology p (Res.
EARCH DISCLOSUREhereinafter abbreviated as RD07
This can be carried out based on the method described in No. 643, Item (3).

The calyx-clipped crystal particles of the present invention contain at least one kind of spectral sensitizing dye represented by the following general formula [■] and the following general formula (I[
) Color sensitization is performed in combination with at least one sensitizing dye represented by:

General formula [I] General formula (n) In the present invention, "color sensitization in combination" refers to general formula [
This shows that it is not necessary to use the compound represented by formula (I) and the compound represented by general formula (II) at the same time, and it is sufficient that sensitization is achieved by both, regardless of the timing of addition, etc. .

-i Formula CI), R is a hydrogen atom, an alkyl group,
represents an aryl group or a heterocyclic group, R2 and R3 each represent an alkyl group, V2゜Va , Va ,
Va, Vb, Vt and V are each a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, an aryl group,
Represents a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a hydroxy group, a cyano group, an amino group, an acylamino group, a sulfonylamino group, an acyloxy group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an acyl group, or a heterocyclic group. Further, the present invention provides V,
and V,, Vt and V,, V, and V,, V, and v6゜■6 and ■? It also includes cases where + and/or V, and V are linked to each other to form a ring. Moreover, ■, ~V, and ■, ~■ may simultaneously form a ring.

(XI)! + represents a charge-balanced counterion, and 11 represents the value necessary to neutralize charges of 0 or more.

-i In formula (II), R1 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, R7 and R6 each represent an alkyl group, Yl and Yi each represent a sulfur atom or a selenium atom, W+, W2, W!
, W4, Ws, Wb, Wt and W are each a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, an aryl group, a carboxyl group, an alkoxycarbonyl group,
Represents an aryloxycarbonyl group, a hydroxy group, a cyano group, an amino group, an acylamino group, a sulfonylamino group, an acyloxy group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an acyl group, or a heterocyclic group.

Further, the present invention provides W, and W2. W2 and W! , Wx and W4゜W, and W, , W, and W? , and/or W7 and W.

This also includes cases where these are linked to each other to form a ring.

()h) 1g represents a charge-balanced counterion, and 2□ represents the value necessary to neutralize charges of 0 or more.

The present invention will be further explained below. First, general formula (I) will be explained.

R1 in the formula is preferably an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a benzyl group, and a phenethyl group. preferable. Examples of the aryl group represented by R include phenyl group and p-tolyl group.

Examples of the heterocyclic group include aromatic heterocyclic groups such as thienyl and furyl, or the general formula (I
ll) Low.

Q in the general formula [I[1] is, for example, a pyrazolone derivative, an isoxacilone derivative, an oxacilone derivative, 2
,4. i triketohexahydropyrimidine derivative, 2-
Thio-2,4,6-)liketohexahydrobyrimidine derivatives, rhodanine derivatives, 2,4-thiazolidinedione derivatives, 2-thio-2゜4-oxazolidinedione derivatives, thianafuthynone derivatives, hydantoin derivatives, indanedione derivatives, Represents a group of nonmetallic atoms necessary to form a 5- or 6-membered heterocyclic nucleus selected from oxindole derivatives, etc.

The sensitizing dye represented by the general formula [■] is of the inner salt type. That is, the sensitizing dye is one in which a quaternary nitrogen as a cation forms a salt with any anion present in the molecule. In the present invention, one of R2 and R□ can form an inner salt, for example, an alkyl group substituted with an acidic group (2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-sulfobutyl group, sulfopropyl group, P-sulfobenzyl group, 2-carboxyethyl group, carboxymethyl group, 3-carboxypropyl group, p-carboxybenzyl group, etc.) to form an inner salt, and R2 and R3 , the other is an alkyl group (methyl group, ethyl group, butyl group, etc.) without a substituent, or a hydroxyalkyl group (2-hydroxyethyl group, 4-hydroxybutyl group, etc.), an acetoxyalkyl group (2-hydroxyethyl group, 4-hydroxybutyl group, etc.) -acetoxyethyl group, 3-acetoxypropyl group, etc.), alkoxyalkyl group (2-methoxyethyl group, 2-ethoxyethyl group, etc.), carbamoylalkyl group (carbamoylmethyl group, carbamoylethyl group, etc.), aralkyl group (benzyl group, phenylethyl group, etc.)
, a sulfamoyl alkyl group (such as a sulfamoylethyl group), etc.

Vl+ VZ+ ”3+ V4+ V of general formula (1)
Details of the groups or atoms represented by S+ V6+■ and ■8 are as follows.

The charge-balancing counter ions represented by
The type is arbitrary. When the charge within the molecule is neutralized by an ion present in another group within the molecule, such as R1 or R3, 1=0. X is an anion when it neutralizes the charge of the nitrogen atom as a cation and/or the cation present in other groups in the molecule, but if an anion exists in another group in the molecule, In some cases, cations are taken for overall neutralization.

First, the alkyl group preferably has 1 to 6 carbon atoms, and may be linear, branched, or cyclic, and may be saturated or unsaturated. Furthermore, it may have a substituent, and specific examples of the alkyl group include a methyl group, an ethyl group, a 1so-propyl group, a cyclohexyl group, an allyl group,
Examples include trifluoromethyl group, hydroxyethyl group, acetoxymethyl group, carboxymethyl group, and ethoxycarbonylmethyl group.

Next, the alkoxy group preferably has 1 to 6 carbon atoms, and may have a substituent (specific examples of the alkoxy group include methoxy group, 1so-propoxy group, chloroethoxy group, etc.). can be mentioned.

Examples of the aryl group include phenyl group, naphthyl group,
Examples of the alkoxycarbonyl group include an ethoxycarbonyl group and a butoxycarbonyl group, and examples of the aryloxycarbonyl group include a phenoxycarbonyl group.

Examples of the amino group include an amino group, an alkylamino group, an arylamino group, a di-substituted amino group, and specific examples include a methylamino group, a diethylamino group, an anilino group, and the like.

Examples of the acylamino group include an acetamido group and a benzamide group.

Examples of the sulfonylamino group include an alkylsulfonylamino group and an arylsulfonylamino group, and specific examples include a methanesulfonamide group and a benzenesulfonamide group.

Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.

Examples of the carbamoyl group include a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, a di-substituted carbamoyl group, and specific examples include a methylcarbamoyl group and a phenylcarbamoyl group.

Examples of the sulfamoyl group include sulfamoyl group,
Examples include an alkylsulfamoyl group, an arylsulfamoyl group, a di-substituted sulfamoyl group, and specifically,
Examples include ethylsulfamoyl group, dimethylsulfamoyl group, and phenylsulfamoyl group.

Examples of sulfonyl groups include alkylsulfonyl groups,
Examples include an arylsulfonyl group, a heterocyclic sulfonyl group, and specific examples include a methanesulfonyl group, a cyclohexanesulfonyl group, a benzenesulfonyl group, a p-toluenesulfonyl group, a pyridinesulfonyl group, a 1-piperidinesulfonyl group, and an N-morpholino group. Examples include sulfonyl groups.

Examples of the acyl group include acetyl group, benzoyl group,
Examples include 1-piperidinocarbonyl group and N-morpholinocarbonyl group.

Examples of the heterocyclic group include a benzoxacylyl group, a benzothiazolyl group, a piperidino group, a morpholino group, a succinimide group, a furyl group, and a thienyl group.

However, ■1 and Vz, Vz and Vs, Vz and V4. V.

and v & + v, and V? + and/or ■, and ■8 can each form a ring, but the rings that can be formed include:
Examples of the ring formed by the above-mentioned (1) to V together with the substituted benzene ring include a naphthalene ring, a quinoline ring, a benzothiophene ring, an isobenzofuran ring, an indole ring, a chroman ring, and a tetrahydroquinoline ring. Preferably it is a naphthalene ring. These rings also have substituents such as alkyl groups, halogen atoms, aryl groups, carboxy groups, alkoxycarbonyl groups, alkoxy groups, hydroxy groups, cyano groups, amino groups, acylamino groups, sulfonylamino groups, acyloxy groups, and carbamoyl groups. Each group such as a group, a sulfamoyl group, a sulfonyl group, an acyl group, and a heterocyclic group may be substituted.

Next, the above general formula (I[) will be further explained.

In the cough formula, R4 is preferably an alkyl group, an aryl group,
or a heterocyclic group, and specific examples of these groups include:
The same groups as those mentioned in the explanation of R2 above can be mentioned.

R3 and R8 each represent an alkyl group, and also include an alkyl group normally used in cyanine dyes. in particular,
For example, in addition to alkyl groups without substituents (methyl group, ethyl group, butyl group, etc.), hydroxyalkyl groups (2-hydroxyethyl group, 4-hydroxybutyl group, etc.), acetoxyalkyl groups (2-acetoxyethyl group, etc.) , 3-acetoxypropyl group, etc.), alkoxyalkyl group (2-methoxyethyl group, 2-ethoxyethyl group, etc.), carboxyalkyl group (2-carboxyethyl group, 3-carpoxypropyl group, P-carboxybenzyl group) etc.), carbamoylalkyl groups (carbamoylmethyl group, carbamoylethyl group, etc.), sulfoalkyl groups (2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-
sulfobutyl group, 2-hydroxy-3-sulfopropyl group, p-sulfobenzyl group, etc.), aralkyl group (benzyl group, phenylethyl group, etc.), and sulfamoylalkyl group (sulfamoylethyl group, etc.).

W,, Wz, W3. Wa, Ws, Wb, W? Specific examples of the group represented by and w8 include the same groups as those listed in the explanation of (1) to Va above, and examples of the halogen atom include fluorine, chlorine, bromine, and iodine atoms. be able to.

Also, W, and W z , W z and W s , W x
and Wa, Ws トW, , W, and Wl, and/or w7
The explanation and specific examples of the ring that can be formed by and W are also the same as the explanations and specific examples of (1) to (8) above.

Regarding the charge-balanced counter ion represented by X2 and its number 2□, in general formula (1),

It is similar to

In the present invention, color sensitization is carried out using a combination of at least one dye represented by general formula (I) and at least one dye represented by general formula (II). Among the dyes Wl to W4 and W.

or W, is a group of pigments in which neither of them forms a ring (If
-a), if at least one of W, -W, and W, ~W forms a ring, the group of dyes is (n-b),
At least one dye represented by general formula [I], at least one dye represented by general formula (II-a), and at least one dye represented by general formula (11-b). It is more preferable to carry out color sensitization in combination in order to achieve the object of the present invention. .

Typical examples of sensitizing dyes used in the present invention are listed below, but the sensitizing dyes used in the present invention are not limited thereto.

First, typical examples of the compound represented by the general formula [I] are shown below, but the dye that can be used in the present invention is not limited to these compounds.

In addition, general formulas (II-a) and (II-b) shown below
The same applies to

<Specific examples of compounds represented by general formula [I]> zHs (CL)sS(h” ■ 3 -4 -5 -13 l-16 ■ 0 ■-17 ■ 21 ■ 8 ■ 22 ■ = 19 ■ 23 Specific examples of compounds represented by general formula [■ a]> (II-5) (■ 6) (II-7) (■ 8) H3 (■ 24) (■ 25) (II-26) (■ 34) -NH (■ 28) (■ 29) (■ 30) (■ 31) (It-35) Specific examples of compounds represented by the general formula [■ b]> (U-36) ([-38) ( 53) The sensitizing dyes represented by the general formula (I), -kuri [■a], and the general formula (II-b) used in the present invention are, for example, F, M
, Palmer, "The Cyanine Soybean and Related Compounds" (Interscience Publishers, 2nd York, 1964):
Compounds that can be easily synthesized and are not described in the literature should be synthesized by a method similar to the synthesis method.Also, as a method for adding the above-mentioned sensitizing dyes to photographic emulsions, there are no conventional methods proposed. Various methods described above can be applied. For example, as described in U.S. Pat. No. 3,469.987, a sensitizing dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and this dispersion is added to an emulsion. You can. Furthermore, the sensitizing dyes according to the invention can be individually dissolved in the same or different solvents and the solutions can be mixed or added separately before being added to the emulsion.

As the solvent for the dye when the sensitizing dye is added to the silver halide emulsion, water-miscible organic solvents such as methyl alcohol, ethyl alcohol, and acetone are preferably used.

When the sensitizing dye is added to the silver halide emulsion, the preferred amount is 1×10-s mol to 2.5×10-”
mol, more preferably from 2X10-' mole to IXl,0-" mole per mole of silver halide.

The preferable usage ratio of the sensitizing dye according to the present invention is that the ratio of the above general formula CI) to the general formula (II) is 1 to 9.
It ranges from 9 to 1 vs.

In the photosensitive material of the present invention, silver halide grains having regular crystal shapes such as cubes, octahedrons, and tetradecahedrons, as well as those having regular crystal shapes such as spherical and plate shapes, in addition to the calyx-clipped crystal grains of the present invention, are used. It is also possible to use a substance with an irregular crystal shape.

The grain size of silver halide grains is 0.05 to 3μ
m1 is preferably 0.1 to 3.0 μm.

The silver halide grains used in combination may have any grain size distribution. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or a monodisperse emulsion with a narrow grain size distribution may be used. Monodispersity as used herein means that the standard deviation of the particle size distribution divided by the average particle size is 0.20 or less.

Monodisperse emulsions may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

In the present invention, various commonly used chemical sensitization treatments can be performed. Chalcogen sensitizers used in chemical sensitization include sulfur sensitizers, selenium sensitizers, and tellurium sensitizers, and sulfur sensitizers and selenium sensitizers are preferred for use in photography. As the sulfur sensitizer, known ones can be used. For example, thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine,
Examples include p-toluenethiosulfonate and rhodanine. Others, U.S. Patent No. 1,574,944, U.S. Patent No. 2,
No. 410.689, No. 2,278,947, No. 2,7
No. 28,668, No. 3,501,313, No. 3,65
No. 6.955, OLS 1, 422
．． No. 869, JP-A-56-24937, JP-A No. 55-45
Sulfur sensitizers described in No. 016 and the like can also be used. The amount of sulfur sensitizer added may be sufficient to effectively increase the sensitivity of the emulsion. This appropriate amount depends on pH, temperature,
It varies over a considerable range depending on various conditions such as the size of silver halide grains, but as a rough guide, it is preferably about 10-7 mol to about 10-' mol per mol of silver halide.

Examples of selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenoamides, selenocarboxylic acids and esters, selenobosphates, diethylselenide, diethylselenide, etc. Selenides and the like can be used, and specific examples thereof can be found in US Patent No. 1. ．． 57
No. 4,944, No. 1,602,592, No. 1,623
．． No. 499.

As with the sulfur sensitizer, the amount added varies over a wide range, but as a guide, approximately 10
It is preferably about -7 mol to 10-1 mol.

In the present invention, various gold compounds are used as the gold sensitizer, and the valence of gold may be +1 or +3. Typical examples include chloroauric acids, potassium chloroaurate,
Auric Trichloride, Potassium Auric Thiocyanate, Potassium Iodoaurate, Tetracyano Auric Acid, Ammonium Auric Thiocyanate,
Examples include pyridyltrichlorogold.

The amount of gold sensitizer added varies depending on various conditions, but as a guide, it is about 10-7 mol to 1 mol per mol of halogenated metal.
A range of up to 0-' mol is preferred.

The gold sensitizer may be added at the same time as the sulfur or selenium sensitizer, or during or after the sulfur or selenium sensitization step.

I)Ag of the emulsion subjected to sulfur sensitization, selenium sensitization, and gold sensitization in the present invention is 5.0 to 10.0, and pH is 5.
A range of 0 to 9.0 is preferred.

The chemical sensitization method in the present invention can also be combined with a sensitization method using other noble metals, such as metal salts such as platinum, palladium, iridium, and rhodium, or complex salts thereof.

Furthermore, complexes such as Rh5Pcl, Ir, and Pt are effective as compounds that release gold ions from gold-gelatinate and promote adsorption of gold ions to silver halide grains.

A specific compound is (NI+4)2 [P tc
14], (NH4) 2 [P tCI! ,4],K1
[TrBr61, (NH4)! [RhCl &
] 12HzO, etc., but particularly preferred is ammonium tetrachloropalladate (II) (NH
4) zPtCf 4. The amount added is preferably 10 to 100 times the stoichiometric ratio (mole ratio) to the gold sensitizer.

The timing of addition may be at the start of, during, or after the chemical sensitization process, but preferably during the chemical sensitization process, and particularly preferably at the same time as or before or after the addition of the gold sensitizer. It is.

In the present invention, reduction sensitization can also be used in combination. The reducing agent is not particularly limited, but includes known stannous chloride, urea dioxide, hydrazine derivatives, polyamines, and the like.

Although reduction sensitization is performed during the growth of silver halide grains, it is preferably performed after completion of chalcogen sensitization, gold sensitization, and noble metal sensitization.

Furthermore, in the chemical sensitization treatment, a compound having a nitrogen-containing heterocycle, particularly preferably an azaindene ring, may be coexisting.

The amount of the nitrogen-containing heterocyclic compound added varies over a wide range depending on the emulsion grain size, composition, chemical sensitization conditions, etc., but preferably forms a monomolecular layer to 10 molecular layers on the silver halide grain surface. It is best to add the amount to the extent that The amount added can also be adjusted by controlling the adsorption equilibrium state by changing the pH and/or temperature during sensitization. Alternatively, two or more of the above compounds may be added to the emulsion in such a way that the total amount falls within the above range.

The compound can be added to the emulsion by dissolving it in a suitable solvent (for example, water or aqueous alkaline solution) that does not have a harmful effect on the photographic emulsion, and then adding it as a solution. The timing of addition is preferably before or at the same time as adding a sulfur sensitizer or a selenium sensitizer for chemical sensitization. The gold sensitizer may be added during or at the end of sulfur or selenium sensitization.

Further, the silver halide grains can be optically sensitized to a desired wavelength range using a sensitizing dye.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

A coupler is used in the emulsion layer of a light-sensitive material for color photography. Furthermore, by coupling with colored couplers that have a color correction effect, competitive couplers, and oxidized forms of developing agents, development accelerators, bleaching accelerators, developing agents, silver halide solvents, toning agents, and hardening agents can be produced. , fogging agent, antifogging agent,
Compounds that release photographically useful fragments such as chemical sensitizers, spectral sensitizers and desensitizers can be used.

The photosensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer, an antiirradiation layer, and the like. These layers and/or the emulsion layer may contain dyes that are washed out of the light-sensitive material or bleached during the development process.

Photosensitive materials include formalin scavengers, optical brighteners,
A capping agent, a lubricant, an image stabilizer, a surfactant, a color antifoggant, a development accelerator, a development retardant, and a bleach accelerator can be added. As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

When a dye image is obtained using the light-sensitive material of the present invention, commonly known color photographic processing can be performed after exposure.

〔Example〕

EXAMPLES Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Prior to the examples, comparative emulsions will be shown first.

Comparative Example 1 Comparative emulsion EM1 was prepared using the seven types of solutions shown below.

(Solution A) Ossein gelatin 8 g Average molecular weight 1700 - 10% ethanol solution of pronone (NOF) 20m228
% ammonia water 104-56% acetic acid aqueous solution 62-seed emulsion (0.27μ
m, tetradecahedral silver iodobromide.

Agi content 2.0 mol%) Halogenated XI O, 139 mole equivalent amount 6771 ml Distilled water (Solution B) ossein gelatin Br Make up to 3383cc with distilled water.

(Solution C) A　g　O! 28% ammonia water Make it 3299- with distilled water.

67.6g 845.4g 1177g 960 50% KBr aqueous solution p, Ag adjustment required amount (solution E) 50% acetic acid aqueous solution pH adjustment required amount 40°C
In, JP-A-57-92523, JP-A No. 57-925
Solutions B and C were added to solution A by simultaneous mixing method for 73.7 minutes using a mixing stirrer shown in No. 24.

PAg, pH, and addition rate of solutions B and C during simultaneous mixing were controlled as shown in Table 1. PAg and pH were controlled by changing the flow rates of the solution and solution E using a variable flow rate roller tube pump. Two minutes after the addition of Solution C was completed, the pH was adjusted to 6.0 by adding a solution.

Next, it was washed with demineralized water using a conventional method and dispersed in an aqueous solution containing ossein gelatin.

Electron microscopy revealed that this emulsion had an average grain size of 1, Oa
The emulsion was found to be a highly octahedral dispersion emulsion with a coefficient of variation of particle size distribution of 12%.

Table Example 1 Emulsion EM-2 containing calyx-cleared crystal grains of the present invention was prepared in the same manner as Comparative Example 1 except that the following two types of sensitizing dye aqueous solutions were added 43.2 minutes after the start of addition. .

0.2% methanol aqueous solution of sensitizing dye (I) 736 0.2% methanol aqueous solution of sensitizing material (n) 864m
1 Sensitizing dye (1) Sensitizing dye (n) The sensitizing dye adsorbed to this silver halide emulsion EM-2 is desorbed by the following method to produce a silver halide emulsion EM with calyx-cleared grains that has not been spectrally sensitized. -3 was created.

That is, extraction treatment with a solvent was performed to remove the sensitizing dye. Methanol was added to the above-prepared silver halide emulsion EM-2 on which the sensitizing dye had been adsorbed under acidic conditions, and the sensitizing dye was imaged.

The emulsion was then allowed to settle and the supernatant liquid was discarded. This process was repeated three times to create emulsion EM-3, which only had intrinsic anger.

Example 2 Next, an example of a silver halide color light-sensitive material using the emulsion according to the present invention will be shown.

Here, a case will be described in which the present invention is applied to a sample consisting of an emulsion layer containing a coupler.

In this example, a cyan coloring coupler was used.

Specifically, in this example, a coupler represented by the following formula (A) was used as the cyan coloring coupler.

As the high boiling point solvent for dissolving the coupler of formula (A), tricresyl phosphinyl 1-(TCP) was employed.

The coupler was used after being dispersed in oil protection according to a conventional method.

Next, the silver iodobromide emulsion (
EM-1 and EM-3) were optimally chemically sensitized using an unstable sulfur compound and a gold salt according to a conventional method. Also,
At the time of chemical sensitization, the sensitizing dye shown in Table 2 (indicated by the specific example No. in the above-mentioned example) was added to carry out color sensitization to red sensitivity.

Silver iodobromide emulsion 1.8 subjected to the above chemical sensitization and color sensitization
A high-speed red-sensitive emulsion layer was prepared containing 1.9 g of gelatin and 0.06 g of TCP (licresyl phosphate) dispersion in which 0.20 g of cyan coupler was dissolved.

Each sample was wedge exposed using red light according to a conventional method and subjected to sensitometric evaluation.

Each exposed sample was processed in the next processing step.

Processing steps: Color development 3 minutes 15 seconds bleaching 6 minutes 30 seconds washing with water
Fixed for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
Stabilization for 3 minutes and 15 seconds Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is shown below.

<Color developer> 4-Amino-3-methyl-N-(β-hydroxyethyl)-aniline 6Nr311 salt 4.75 g Anhydrous sodium sulfite 4.25 g Hydroxylamine Each sulfate Anhydrous potassium carbonate Sodium bromide Nitrilotriacetic acid 3 Add sodium salt potassium hydroxide water to make 12.

<Bleach solution> Iron ethylenediaminetetraacetate ammonium salt Ethylenediaminetetraacetic acid 2 ammonium salt ammonium bromide glacial acetic acid Add water and 1! year, Adjust the pH to 6.0.

Fixer> Ammonium thiosulfate Anhydrous ammonium sulfite Sodium metasulfite 10.0 g 150.0 g 10.0 d Using aqueous ammonia 2.0 g 37.5 g 1.3 g (monohydrate) 2.5 g 1.0 g 100.0 g 175.0 g 8.6 g 2.3 g Add water to make 12, and adjust to pH 6.0 using acetic acid.

<Stabilizing liquid> Formalin (37% solution> 1.5 d
Konidax (manufactured by Konica ■) 7.5, d
Add water to make 11.

The developed sample was subjected to sensitometry using red light.

Fog: The larger the minimum optical density C value of the so-called characteristic curve obtained by sensitometry, the higher the capri is, which is unfavorable).

Sensitivity: Reciprocal of the exposure amount (anti-value) that gives an optical density of 1J + 0.1 on the characteristic curve (In the table of the results of the example, the sensitivity during normal exposure (1150 seconds exposure) of sample Nα1 is 100 (The higher the value, the faster the sensitivity, which is preferable.)

Actual [1m degree...value obtained by subtracting the lowest concentration from the highest concentration on the characteristic curve. (In Table 2, the actual concentration of sample NcL1 is 1
It is expressed as a relative value of 00. The larger the value, the faster the development speed, which is preferable. ) As is clear from the results in Table 2, the emulsion of the present invention was found to have low fog, high sensitivity, high real density, and development activity.

Example 3 Preparation of a multilayer color photosensitive material (referred to as a multilayer sample): The same chemically sensitized and color sensitized iodine used in the preparation of the single color sensitive coating sample in Example 2 above was used. A color photosensitive material consisting of nine layers having three types of photosensitive layers: a blue photosensitive layer, a green photosensitive layer, and a red photosensitive layer was prepared using a silver bromide emulsion in the following manner. The emulsions of EM-1 and EM-3, which have undergone chemical sensitization and color sensitization, have a red-sensitive high-sensitivity layer (layer 2).
Changes were made only in For the other photosensitive layers, the same emulsion was used in each sample.

It consists of an undercoated cellulose triacetate film and has an antihalation layer (0.40 g of black colloid).
and 3.0 g of gelatin. ) A sample was prepared by coating each of the following layers in order on a transparent support. In all of the following Examples, the amounts added to the light-sensitive materials are shown per 1 nf, and are shown in terms of silver halide emulsion and colloidal silver.

Layer 1...1.4g low-sensitivity red-sensitive emulsion layer color-sensitized to red sensitivity! l (containing 7 mol% silver iodide) emulsion and 1.2
g of gelatin and 0.8 g of 1-hydroxy-4-(
β-methoxyethylaminocarbonylmethoxy)-N-
(δ-(2,4-di-t-amylphenoxy)butyl)
-2-naphthamide [hereinafter referred to as C-1]. ], 0.0
75 g of 1-hydroxy-4-(4-(1-hydroxy-δ-acetamido-3,6-disulfo-2-naphthylazo)phenoxy)-N-(δ-(2,4-diL-
amylphenoxy)butyl-2-naphthamide disodium [hereinafter referred to as colored cyan coupler (CC-1). ] and 0.015 g of 1-hydroxy-2-
[δ-(2,4-di-monoamylphenoxy)butyl]naphthamide, 0.07 g of 4-occudecylsuccinimide-2-(1-phenyl-5-tetrazolylthio)
-1-indanone [hereinafter referred to as DIR compound (D-1). ] A low-speed red-sensitive emulsion layer containing 0.65 g of tricresyl phosphate (TCP) dispersion dissolved therein.

Layer 2: 1.3 g of highly sensitive red-sensitive silver iodobromide emulsion (EM
-1, EM-3), 1.2 g of gelatin and 0.2
0.23 in which 1 g of cyan coupler (C-1) and 0.02 g of colored cyan coupler (CC-1) were dissolved.
A highly sensitive red-sensitive emulsion layer containing a TCP dispersion of g.

Layer 3: 0.07 g of 2.5-di monooctylhydroquinone [hereinafter referred to as antifouling agent (HQ-1).

] was dissolved in 0.04 g of dibutyl phthalate [hereinafter referred to as DBP]. ] Interlayer containing dispersion and 0.8 g of gelatin.

Layer 4: 0.80 g of low-sensitivity silver iodobromide (containing 6 mol% silver iodide) emulsion sensitized to green sensitivity, 2.2 g of gelatin, and 0.8 g of 1-(2 ,4°6-dolychlorphenyl)3-(3-(2°4-di-t-amylphenoxyacetamide)benzamide]-5-pyrazolone and 0.15 g of 1- chlorophenyl)-4-(1-naphthylazo)-3-(2-chloro-5-octasecenylsuccinimideanilino)-5
-Pyrazolone [hereinafter referred to as colored magenta coupler (CM)
-1). ] and 0.95 g of TCP dispersion in which 0.016 g of DIR compound (D-1) was dissolved.

Layer 5...1.8g chemically sensitized and color sensitized to green sensitivity
High-sensitivity green-sensitive silver iodobromide emulsion, 1.9 g of gelatin, 0.20 g of pyrazolotriazole coupler represented by M-1, and 0.049 g of colored magenta coupler (CM-1) were dissolved. A high-speed green-sensitive emulsion layer containing 0.06 g of DNP dispersion.

Layer 6: Yellow filter layer containing 0.15 g yellow colloidal silver, 0.11 g DBP dispersion in which 0.2 g antifouling agent (HQ-1) was dissolved and 1.5 g gelatin.

Layer 7: 0.2 g of low-sensitivity silver iodobromide (containing 4 mol% silver iodide) emulsion sensitized to blue sensitivity, 1.9 g of gelatin, and 1.5 g of α-pivaloyl-α- (1-benzyl-2-phenyl-3゜5-dioxoimidazolidine-
4-yl)-2'-chloro-5'-[α-dodecyloxycarbonyl)ethoxycarbonyl]acedoanilide [hereinafter referred to as Y-1. ] 0.6g of TC dissolved in
A low-speed red-sensitive emulsion layer containing a P dispersion.

Layer 8...1.0g chemically sensitized and color sensitized to blue sensitivity
A highly sensitive blue-sensitive emulsion layer containing the above-mentioned highly sensitive blue-sensitive silver iodobromide emulsion, 0.65 g of TCP dispersion in which 1.5 g of gelatin and 1.30 g of yellow coupler (Y-1) were dissolved. The type and amount of sensitizing dye and the type of emulsion are as follows:
See Table-3.

Layer 9: Protective layer containing 2.3 g of gelatin.

M-1 Measurement of multilayer sensitivity: The multilayer color photosensitive material thus prepared was exposed to white wedge light according to a conventional method, processed in the above processing steps, and red light sensitivity was obtained by sensitometry (the definition of sensitivity is (Same as for the single medorochromatic coating sample above).

As seen in Table 3, the samples of the present invention have low fog and high sensitivity. Furthermore, the actual density is high and the development activity is high. As described above, it was found that the effects of the present invention can be obtained even with a sample having a multilayer structure, as in Example 2.

[Brief explanation of the drawing]

FIG. 1 shows a schematic diagram of a silver halide crystal according to the present invention and a second diagram.
Figures 3 and 4 are electron micrographs of silver halide crystals according to the present invention.

Claims (1)

[Scope of Claims] 1. Silver halide crystal grains of a photographic emulsion, each of which has four particles lying on the same plane of a regular octahedron assumed in its normal crystal.
It is a silver halide crystal grain with a calyx piece, which is parallel to the three planes formed by the two ridges, and is attached with crystal pieces that protrude by interlocking with each other at right angles, and has the following general formula [I
Silver halide which has been color sensitized by combining at least one kind selected from the inner salt type sensitizing dyes represented by ] and at least one kind of sensitizing dye represented by the following general formula [II] A silver halide photographic material characterized by containing crystal grains. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the general formula [I], R_1 is a hydrogen atom, an alkyl group, an aryl group, or a heterocycle represents a group, R_2 and R_
3 each represents an alkyl group, V_1, V_2, V_
3, V_4, V_5, V_6, V_7 and V_8 are each hydrogen atom, alkyl group, alkoxy group, aryl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, hydroxy group, cyano group, amino group, acylamino group, sulfonyl It represents an amino group, an acyloxy group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an acyl group, or a heterocyclic group, and V_1 and V
_2, V_2 and V_3, V_3 and V_4, V_5 and V_
6. It also includes cases where V_6 and V_7 and/or V_7 and V_8 are connected to each other to form a ring. Also, V_1
~V_4 and V_5 to V_8 may form a ring at the same time. In addition, (X_1)_l_1 represents a charge balancer ion,
l_1 represents a value necessary to neutralize charges of 0 or more. In general formula [II], R_4 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R_5 and R_6
each represents an alkyl group, Y_1 and Y_2 each represent a sulfur atom or a selenium atom, W_1, W_2
, W_3, W_4, W_5, W_6, W_7 and W_8
are hydrogen atom, alkyl group, halogen atom, alkoxy group, aryl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, hydroxy group, cyano group, amino group, acylamino group, sulfonylamino group, acyloxy group, carbamoyl group, respectively. , represents a sulfamoyl group, a sulfonyl group, an acyl group, or a heterocyclic group, and W_1 and W_2, W_2 and W_3, W_3 and W_4, W_5 and W_6, W_6 and W_7, and/or W_7 and W_8 are connected to each other to form a ring. This also includes cases where it is formed. (X_2)_l_2 represents a charge balancer ion, and l_2 represents a value necessary to neutralize charges of 0 or more.