JPH07113740B2 - Silver halide photographic light-sensitive material - Google Patents

Description

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

[Conventional technology]

In recent years, the demand for silver halide emulsions for photography has become more and more stringent, and higher and higher standards are demanded for photographic performance such as high sensitivity, excellent graininess, high sharpness, low fog density and sufficiently high optical density. Has been done.

In response to these requirements, a silver iodobromide emulsion containing 0 to 10 mol% of iodine is well known as a high-sensitivity emulsion. And, as a method for preparing these emulsions, conventionally, pH conditions such as ammonia method, neutral method and acidic method, pAg
As a method for controlling the conditions and a mixing method, a single jet method, a double jet method and the like are known.

On the basis of these known techniques, technical means have been studied and put into practical use with a high degree of precision for the purpose of achieving higher sensitivity, improved graininess, high sharpness and low fog.

Regarding the silver iodobromide emulsion which is one of the objects of the present invention, an emulsion in which not only the crystal habit and the grain size distribution but also the iodine concentration distribution in each silver halide grain is controlled has been studied.

In order to achieve photographic performance such as high sensitivity, excellent graininess, high sharpness, low fog density and sufficiently high covering power as described above, the quantum efficiency of silver halide is improved and chemical ripening is performed. In JP-A-54-48521, a monodisperse emulsion aimed at efficiently achieving high sensitivity while maintaining low fog is known and disclosed in JP-A-54-48521 (10).
A silver iodobromide monodisperse emulsion having a 0) crystal face and / or a (111) crystal face is known.

Further, JP-A-60-222842 discloses that a silver iodobromide emulsion having a (110) crystal plane can achieve a low fog.

Techniques relating to the spectral sensitization necessary for applying such a silver halide emulsion to a light-sensitive material are also described in the above-mentioned respective documents, and in addition to these documents, the spectrally sensitized high-sensitivity silver halide. Numerous techniques have been disclosed for emulsions.

However, there is a demand for technological development capable of further increasing the sensitivity than these known techniques.

[Object of the Invention]

An object of the present invention is to provide a high-sensitivity silver halide photographic light-sensitive material, and also to provide a silver halide photographic light-sensitive material having a silver halide emulsion layer with improved edge spectral sensitivity. is there.

[Structure of Invention]

The object of the present invention is a silver halide grain having a (nn1) crystal plane (n ≧ 2, n is a natural number) on the surface of the silver halide grain, which is represented by the following general formula [I]. A silver halide emulsion layer having silver halide grains which are spectrally sensitized by combining at least one sensitizing dye and at least one sensitizing dye represented by the following general formula [II] or [III] And a silver halide photographic light-sensitive material.

General formula [I] General formula (II) General formula (III) In the above general formula [I], R ₁ and R ₂ each represent an alkyl group, an alkoxyalkyl group, a hydroxyalkyl group, a sulfoalkyl group, or a carboxyalkyl group, and R ₃ represents a hydrogen atom, a halogen atom, a lower alkyl group, Represents an aryl group or a lower alkoxy group,
Z ₁ , Z ₂ , Z ₃ and Z ₄ are each a halogen atom, a hydroxyl group, an alkoxy group, an amino group, an alkylamino group,
It represents an acylamino group, an acyloxy group, an alkoxycarbonyl group, an alkoxycarbonylamino group, an aryl group, an alkyl group or a cyano group. Z ₁ and Z ₂ and Z ₃ and Z ₄
May be connected to each other to form a ring.

See also X₁ Represents an anion. m represents 1 or 2
And the dye represented by the general formula [I] forms an intramolecular salt.
M represents 1. n, n ', l and l'are
Represents 0 or 1, respectively.

In the above general formula [II], Y ₁ is —S— or And R ₉ represents an alkyl group. R ₄ and R ₅ each represent an alkyl group, an alkoxyalkyl group, a hydroxyalkyl group, a sulfoalkyl group, or a carboxyalkyl group, and R ₆ represents a lower alkyl group when Y ₁ is —S—. Then represents a hydrogen atom.

Z ₅ and Z ₆ are a halogen atom, a hydroxyl group,
It represents an alkoxy group, an amino group, an acylamino group, an acyloxy group, an alkoxycarbonyl group, an alkoxycarbonylamino group, an aryl group, an alkyl group or a cyano group. Z ₅ and Z ₆ may combine with each other to form a ring.

When Y ₁ is —S—, Z ₇ and Z ₈ are each a halogen atom, a hydroxyl group, an alkoxy group, an amino group, an acylamino group, an acyloxy group, an alkoxycarbonyl group,
It represents an alkoxycarbonylamino group, an aryl group, an alkyl group or a cyano group, and Z ₇ and Z ₈ may be linked to each other to form a ring.

Y ₁ is In the case of, Z ₇ and Z ₈ are both a methyl group, both are chlorine atoms, and one of them is a benzene ring condensed with the benzene ring of the benzimidazole ring in the formula (II) (substituted by an alkyl group) And the other is a hydrogen atom, one of which is a benzene ring condensed at the e-position or the g-position of the benzimidazole ring in the formula [II], the other is a hydrogen atom, and one of them is a 5-methoxy group and the other is [II]. In the formula, it represents a benzene ring fused to the g-position of the benzimidazole ring, or an alkyl group or an aryl group, respectively.

X₂ Represents an anion, and p represents 1 or 2.
r, r ′, s and s ′ each represent 0 or 1.

In the above general formula [III], Y ₂ is —S— or R ₇ , R ₈ and R ₁₁ each represent an alkyl group, an alkoxyalkyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group, and Z ₉ and Z ₁₀ are both methyl groups and both are chlorine groups. Atoms, one of which is a benzene ring (substituted by an alkyl group) fused to the benzene ring of the benzimidazole ring in the formula [III], the other is a hydrogen atom, and one of these is a benzimidazole in the formula [III] A benzene ring fused to the e- or g-position of the ring, the other being a hydrogen atom, one of which is a 5-methoxy group and the other is a benzene ring fused to the g-position of the benzimidazole ring in the formula [III], or an alkyl Represents a group or an aryl group.

When Y ₂ is —S—, Z ₁₁ and Z ₁₂ are each a halogen atom, a hydroxyl group, an alkoxy group, an amino group, an acylamino group, an acyloxy group, an alkoxycarbonyl group, an alkoxycarbonylamino group, an aryl group, an alkyl group or It represents a cyano group, and Z ₁₁ and Z ₁₂ may combine with each other to form a ring.

Y ₂ is In the case of, Z ₁₁ and Z ₁₂ are both a methyl group, both are chlorine atoms, and one of these is a benzene ring condensed with the benzene ring of the benzimidazole ring in the formula [III] (substituted by an alkyl group) And the other is a hydrogen atom, and one of these is [II
I] In the formula, the benzene ring condensed at the e-position or the g-position of the benzimidazole ring is a hydrogen atom, and one of them is 5
-A methoxy group represents a benzene ring fused to the g-position of the benzimidazole ring in the formula [III], or an alkyl group or an aryl group, respectively.

X₃ Represents an anion, and q represents 1 or 2.
u, u ', v and v'represent 0 or 1, respectively.

Hereinafter, the present invention will be described in detail.

First, the (nn1) crystal plane of the outer surface of the silver halide grain of the present invention will be described.

FIG. 1 is a diagram showing the morphology of the entire silver halide microcrystal when the outer surface is constituted only by (nn1) crystal faces. FIG. 2 is a side view seen from the direction of the straight line b ₁ b ₂ . (Nn
1) There are 24 equivalent crystal faces expressed as crystal faces. For this reason, all outer surfaces are crystals with (nn1) crystal faces in the shape of a dodecahedron, and each outer surface is an obtuse triangle. There are two types of vertices,
That is, there are 6 vertices equivalent to a ₁ and 8 vertices equivalent to b ₁ in FIG. At apex a ₁ , 8 planes are in contact with each other,
At the vertex b ₁ , the three planes are in contact with each other. There are also two types of edges. That is, 24 equivalent to side a ₁ b ₁ in FIG.
There are 12 edges equivalent to a and a ₁ a ₂ .

Fig. 12 shows an electron micrograph of nearly perfect tetrahedral silver halide grains whose outer surface is composed of (nn1) planes.

Next, the relationship between the (nn1) plane, the (111) plane, and the (110) plane will be described with reference to sectional views. Including the straight line b ₁ b ₂ of the tetrahedron of FIG.
A cross-sectional view in a plane perpendicular to the triangle a ₁ a ₂ b ₁ and the triangle a ₁ a ₂ b ₂ is shown by a solid line 1 in FIG.

That is, in FIG. 3, the solid line 1 is the plane d and (nn1)
It represents the line of intersection with the surface. One side, broken line 2 is (110)
The plane and the alternate long and short dash line 3 represent the (111) plane, and (n
The normal vectors of the (n1) plane, the (110) plane, and the (111) plane are indicated by and. Therefore the direction of the surface is = [110] and can be expressed as = [111]. Therefore the faces themselves are (nn1), (110) and (111) respectively.
Is represented. Two (nn is θ adjacent boundary edges a ₁ a ₂
1) The angle formed by the crystal planes, and n ≧ 2, n is 110 ° <θ <180 ° due to the limitation of natural numbers.

From the above, it is clear that the (nn1) crystal plane according to the present invention is a crystal plane which is completely different from the (111) crystal plane and the (110) crystal plane which are conventionally known in silver halide microcrystals. . Also, it does not require any particular explanation that it is different from the (100) crystal plane.

The (nn1) crystal plane in the present invention is synonymous with the crystal plane which we previously described as “quasi (110) plane” in Japanese Patent Application No. 59-206765.

The silver halide grains according to the present invention do not need to have all the outer surfaces composed of (nn1) planes, ie (111)
The plane, (100) plane, or (110) plane may exist. Examples of these are shown in FIGS. (11
A mixture of 1) planes and (100) planes creates a 30-faced structure (see 4.5.
(Fig. 6) It takes the form of a 38-sided body (Fig. 7.8.9) or a 32-sided face (Fig. 10.11).

In order to identify the crystal planes of fine silver halide grains, powder method X-ray diffraction (Britin of the Society of Scientific Photographics) of the emulsion which was oriented on the substrate and coated was used.・ Japan (Bullet
in of the Society of Scientific Photography of Jap
an) Volume 13, page 5) is often used.

However, regarding the (nn1) plane according to the present invention, even if all the outer surfaces are dodecahedron particles composed of the (nn1) plane, the ratio of the area of one surface to the particle volume is 8
Remarkably small compared to the face piece and rhomboid dodecahedron. For this reason, it is difficult to align the (nn1) plane on the substrate. In addition, since the (nn1) plane is of higher order, its diffraction strength is also small. For the above reasons, powder method X was used to identify the (nn1) plane.
Since line diffraction cannot be used, at present, it is necessary to identify the Miller index of a surface by obtaining the ratio of the lengths of two kinds of sides from the electron micrograph and the angle between the two surfaces. Absent. According to this, it was found that the (nn1) plane according to the present invention exists in a wide range of the value of n.

The silver halide grain according to the present invention is a crystal having a (nn1) plane on its outer surface, and may be a normal crystal or a twin crystal (including a multiple twin crystal). The particles have the following crystal form.
Those falling under at least one of the terms are included.

The ratio of the surface area of the (nn1) plane to the total surface area is at least 30%.

If the boundary between two crystal planes is unclear (for example, the boundary has a rounded shape) when obtaining this ratio, the intersection line between these two planes is obtained as the boundary.

It belongs to the range of crystal forms shown in the electron micrographs of FIG. 12 and Japanese Patent Application No. 59-206765, FIGS. 10 to 13.

 It belongs to the range of crystal morphology shown in FIGS. 1 to 11 described later.

The ratio of silver iodide in the silver halide grains according to the present invention is preferably 0 to 40 mol%, more preferably 0 to 20 mol%, particularly preferably 0 to 15 mol%. The ratio of silver chloride is preferably 0 to 99 mol%. The silver chloride ratio is preferably 0 to 99 mol%.

The silver halide grain according to the present invention is a silver halide grain having a uniform silver halide composition, but it is composed of a plurality of phases (eg layers) having different halogen compositions (eg core / shell type grains). ) May be sufficient.

The halogen composition in each phase may be uniform or may change continuously.

One of the most preferable forms is one having a high iodine phase inside the grains. That is, it is a silver halide grain having a phase (which may be a plurality of layers) having a higher iodine content than the grain surface.

The grain size of the silver halide grains according to the present invention is not particularly limited, and the present invention is effective at least in the range of 0.1 to 3.0 μm. In the present specification, the grain size of silver halide refers to the length of one side of the cube which is equal to the volume.

The silver halide grains according to the present invention are usually produced and used in a form dispersed in a dispersion medium such as gelatin, that is, a form called an emulsion. 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 application etc., but the coefficient of variation of the particle size distribution is The effect of the present invention is more remarkable in a monodisperse emulsion of 20% or less.

This coefficient of variation is Is a measure of monodispersity.

As described above, the silver halide grain according to the present invention may include a surface other than the (nn1) plane, for example, a (111) plane, a (100) plane, etc.
1) As described above, the ratio of the surface area is at least 30% or more, preferably 50% or more, and more preferably 70% or more.

Further, the silver halide emulsion according to the present invention has the above (nn
1) It is desirable that the silver halide grains having faces are contained in an amount of 30% by weight or more, more preferably 50% by weight or more.

A silver halide emulsion containing silver halide grains having a (nn1) plane according to the present invention is halogenated by mixing a water-soluble silver halide solution and a water-soluble silver salt solution in the presence of a protective colloid. In a method for producing a silver halide emulsion having a step of forming silver grains, (a) a silver halide suspension is produced during a period in which at least 30 mol% of the amount of silver halide produced for forming silver halide grains is produced. The pAg of the turbid mother liquor is controlled to 7.0 to 9.8, and (b) the tetrazaindene compound is allowed to coexist in the mother liquor during the period, and (c) the silver halide grains are conditioned after the production of the amount of silver halide It is obtained by a method for producing a silver halide emulsion in which pAg is controlled to 7.0 to 9.5 during formation.

The term "during the formation of the silver halide grains" means that the grain constitution is finally determined experimentally from the practical point of view by adjusting the physical properties of grains such as intra-crystalline dislocation, dissolution thermal equilibrium, and crystal surface state. It is a period.

In this manufacturing method, any method such as an acidic method, a neutral method or an ammonia method can be used in the step of forming silver halide to form silver halide grains.
The method for reacting the soluble silver salt with the soluble halogen salt may be a one-sided mixing method in which one solution is added as the mother liquor, a simultaneous mixing method in which both reaction solutions are added to the mother liquor, or a combination thereof. May be used, but at the same time, pA in the liquid phase where silver halide is produced is one form of the mixing method.
It is preferable to use a method of keeping g constant, that is, a so-called controlled double jet method.

According to this method, a silver halide emulsion (monodisperse emulsion) having a regular crystal form and a substantially uniform grain size can be obtained. Further, it is preferable to use a silver halide emulsion because grain formation can be performed in a single hour.

For example, generally known silver halide emulsions such as ammonia and thioether can be used.

In addition, in order to make the particle size uniform, British Patent 1,535,01
No. 6, JP-B-48-36890 and JP-A-52-16364, a method of changing the addition rate of an aqueous solution of silver nitrate or an alkali halide according to the grain growth rate, and US Pat.
It is preferable to use the method of changing the concentration of the aqueous solution as described in 4,242,445 and JP-A-55-158124 to grow quickly in a range not exceeding the critical saturation.

These methods are preferably used also when forming grains having a plurality of layers having different silver halide compositions, because each silver halide grain is uniformly coated without regenerating nuclei.

When providing layers having different silver halide compositions, a halogen substitution method can also be used.

The halogen substitution method can be carried out, for example, by adding an aqueous solution mainly containing an iodine compound (preferably potassium iodide), preferably an aqueous solution having a concentration of 10% or less. For details, see US Patents 2,592,250 and 4,074.
It can be carried out by the method described in 5,020, JP-A-55-127549 and the like. At this time, in order to reduce the difference in iodine distribution between grains in the high silver iodide containing layer, it is desirable that the concentration of the aqueous iodine compound solution be 10 ⁻² mol / l or less and the addition be performed over 10 minutes.

When a layer having a different silver halide composition is provided, a desalting step may be performed according to a conventional method, if necessary, on the way,
The layers may be continuously formed without performing the desalting step.

In the method for producing silver halide grains of the present invention, one of the most preferable modes is a method of adding an aqueous ammoniacal silver nitrate solution and an aqueous halide solution by a controlled double jet method in the presence of ammonia.

In the method for producing silver halide grains according to the present invention, seed grains may be used, and silver halide may be produced on the surface thereof to grow the grains.

PAg during the period when the amount of silver halide produced reaches 30 mol%.
Can be controlled within the period during which silver halide is produced, and may be at the beginning, midway or end of the silver halide producing step. Further, this period is preferably a continuous period, but may be intermittent as long as the effect of the present invention is not impaired. PAg in this period is 7.0 ~ 9.8, preferably 7.3 ~ 9.5, more preferably 7.6.
~ 9.2. During this period, the pH of the emulsion is preferably kept in the range of 7-10. The pAg of silver halide outside this period and the period for forming and forming the silver halide grains is 4
A range of -11.5 is suitable, preferably a range of 6-11, and a pH of 2-12, preferably 5-11.

The silver halide grains according to the present invention may be doped with various metal salts or metal complex salts at the time of silver halide precipitation formation, at the time of grain growth or after the growth is finished. For example, metal salts or complex salts of gold, platinum, palladium, iridium, rhodium, bismuth, cadmium, copper and the like and combinations thereof can be applied.

The silver halide grains according to the present invention may be used as they are, or may be prepared by blending two or more kinds having different average grain sizes at any time after grain formation to obtain a predetermined gradation. May be offered. In addition, it can be used as a mixture with silver halide grains other than those of the present invention.

The tetrazaindene compound used in the production of a silver halide emulsion containing silver halide grains according to the present invention is used for crystal control and has the following general formula [I
Compounds represented by V], [V], [VI] or [VII] and compounds having a repeating unit of the following general formula [VIII] are preferred.

Wherein R ₁ , R ₂ and R ₃ may be the same or different,
Hydrogen atom, halogen atom, amino group, amino group derivative, alkyl group, alkyl group derivative, aryl group,
Aryl group derivative, cycloalkyl group, cycloalkyl group derivative, mercapto group, mercapto group derivative or -CONH-R ₄ (R ₄ is a hydrogen atom, alkyl group, amino group, alkyl group derivative, amino group derivative , Halogen atom, cycloalkyl group, derivative of cycloalkyl group,
It represents an aryl group or a derivative of an aryl group. ), R ₅ represents a hydrogen atom or an alkyl group, and R ₁ and R ₂
May combine with each other to form a ring (for example, a 5- to 7-membered carbocyclic ring, heterocyclic ring), and X is a compound represented by the general formula [IV], [V], [VI] or [VII]. A monovalent group excluding one hydrogen atom (for example, the above general formulas [IV] to [VII]
R _{1 to} R ₃ or an OH moiety in which one hydrogen atom is removed), and J represents a divalent linking group.

In the general formulas [IV] to [VIII], examples of the alkyl group represented by R _{1 to} R ₄ include a methyl group, an ethyl group,
Examples thereof include a propyl group, a pentyl group, a hexyl group, an octyl group, an isopropyl group, a sec-butyl group, a t-butyl group, and the like. Examples of the alkyl group derivative are substituted with an aromatic residue (divalent linking A group such as -NHCO- or the like) alkyl group (e.g., benzyl group, phenethyl group, benzhydryl group, 1-naphthylmethyl group, 3-phenylbutyl group, benzoylaminoethyl group, etc.), alkoxy group Alkyl group (eg, methoxymethyl group, 2-methoxyethyl group, 3-ethoxypropyl group, 4-methoxybutyl group, etc.), halogen atom, hydroxy group, carboxy group, mercapto group, alkoxycarbonyl group or substituted or unsubstituted Alkyl groups substituted with amino groups (eg monochloromethyl group, hydroxymethyl group, 3-hydro) Xybutyl group, carboxyltyl group, 2-carboxyethyl group, 2- (methoxycarbonyl) ethyl group, aminomethyl group, diethylaminomethyl group, etc.), cycloalkyl group-substituted alkyl group (for example, cyclopentylmethyl group, etc.), The above general formula (I
Examples thereof include an alkyl group substituted with a monovalent group obtained by removing one hydrogen atom from the compounds represented by V] to [VII].

Examples of the aryl group represented by R _{1 to} R ₄ include phenyl group and 1-naphthyl group, and examples of the derivative of the aryl group include p-tolyl group, m-ethylphenyl group, m-cumenyl group, Mesityl group, 2,3-xylyl group,
p-chlorophenyl group, o-bromophenyl group, p-hydroxyphenyl group, 1-hydroxy-2-naphthyl group, m-methoxyphenyl group, p-ethoxyphenyl group, p-carboxyphenyl group, o- (methoxycarbonyl) Examples thereof include a phenyl group, m- (ethoxycarbonyl) phenyl group and 4-carboxy-1-naphthyl group.

Examples of the cycloalkyl group represented by R _{1 to} R ₄ include a cycloheptyl group, a cyclopentyl group, a cyclohexyl group, and the like, and as the cycloalkyl group derivative,
Examples thereof include a methylcyclohexyl group and the like. R ₁ ~ R ₄
Examples of the halogen atom represented by are fluorine, chlorine, bromine, iodine and the like, and examples of the derivative of the amino group represented by R _{1 to} R ₄ are butylamino group, diethylamino group and anilino group. Examples of the mercapto group derivative represented by R _{1 to} R ₃ include a methylthio group, an ethylthio group, and a phenylthio group.

The alkyl group represented by R ₅ preferably has 1 to 6 carbon atoms.
And examples thereof include a methyl group and an ethyl group.

R ₅ is particularly preferably a hydrogen atom or a methyl group.

J is a divalent linking group, and preferably has a total carbon number of 1 to 20. Among such linking groups, the following formula (J-
Those represented by I) or (J-II) are preferable.

In the formula, Y is -O- or (Here, R ₆ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Z is an alkylene group (preferably having up to 10 carbon atoms. An amide bond, an ester bond, or an ether bond may be interposed in the alkylene group. For example, a methylene group, an ethylene group, a propylene group, or -CH ₂ OCH ₂ −, −CH _{2
CONHCH 2 -, - CH 2 CH} 2 COOCH 2 -, - CH 2 CH 2 OCOCH 2 -, - C
H ₂ NHCOCH ₂ — etc.) —O-alkylene group, —CONH-alkylene group, —COO-alkylene group, —OCO-alkylene group or —NHCO-alkylene group (these alkylene groups preferably have up to 10 carbon atoms. ) Or an arylene group (preferably having 6 to 12 carbon atoms, such as a p-phenylene group).

Particularly preferable divalent linking groups as J include the following.

-CONHCH _2- . −CONHCH ₂ CH ₂ −, −CONHCH ₂ OCOCH ₂ −, −
_{CONHCH 2 CH 2 CH 2 OCOCH 2} -, - COOCH 2 -, - COOCH 2 CH 2 -,
−COOCH ₂ CH ₂ OCOCH ₂ , −COOCH ₂ CH ₂ CH ₂ OCOCH ₂ −, The compound having a unit represented by the general formula [VIII] may be a homopolymer or a copolymer, and examples of the copolymer include acrylamide, methacrylamide, acrylic ester, methacrylic ester and the like.

Next, the above general formula [IV], [V], [VI] or [VI]
Typical specific examples of the compound represented by I] or the compound having the repeating unit represented by the general formula [VIII] are shown below.

The addition amount of the tetrazaindene compound used for producing the silver halide grains of the present invention is a desired silver halide grain size,
It depends on the production conditions such as the temperature of emulsion, pH, pAg, and silver iodide content, but it is 10 ^-5 per mol of total silver halide produced.
It is preferably in the range of 2 × 10 ^-1 mol.

When the tetrazaindene compound is a compound having a unit represented by the general formula [VIII], the amount added is the number of moles of the tetrazaindene portion.

The more preferable addition amount is as shown in Table 1 with respect to the particle size. The addition amount with respect to the particle size other than the particle size listed in Table 1 can be obtained by extrapolation or interpolation by making the addition amount inversely proportional to the particle size.

Further, the more preferable addition amount is as shown in Table 2 with respect to pAg and silver iodide content in the case of silver iodobromide.

The tetraazaindene compound may be added to the protective colloid solution in advance, added gradually as the silver halide grains grow, or added together.

The emulsion containing silver halide grains of the present invention may be subjected to the Nudel water washing method in which gelatin is gelled in order to remove soluble salts from the emulsion after precipitation formation or after physical ripening. A precipitation method (flocculation method) using a surfactant, an anionic polymer (such as polystyrene sulfonic acid), or a gelatin derivative (such as acylated gelatin or carbamoylated gelatin) may be used.

The silver halide emulsion containing silver halide grains according to the present invention may or may not be chemically sensitized. For chemical sensitization, for example, H. Frieser edited by Die Grund lagen der Photograp
hischen Prozesse mit Silberhalogeniden (Akademisch
e Verlagsgesellsch aft. 1968) pages 675-734 can be used.

That is, a sulfur-sensitizing method using a sulfur-containing compound capable of reacting with active gelatin or silver (eg, thiosulfate, thioureas, mercapto compounds, rhodanines), a reducing substance (eg, first tin salt, Reduction sensitization using amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds), noble metal compounds (eg, gold complex salts, complex salts of metals of Group VIII of the periodic table such as Pt, Ir, Pd) The noble metal sensitizing method to be used can be used alone or in combination.

These examples are described in US Pat.
No. 574,944, No. 2,410,689, No. 2,278,947, No.
No. 2,728,668, No. 3,656,955, etc., for reduction sensitization methods, U.S. Patent Nos. 2,983,609, 2,419,974, 4,05
US Patent No. 2,399,0 for precious metal sensitization method such as 4,458
No. 83, No. 2,448,060, British Patent No. 618,061 and the like.

Next, the sensitizing dye used in the present invention will be described.

The sensitizing dyes according to the present invention are represented by the general formulas [I] and [I
Examples of the halogen atom represented by Z ₁ , Z ₂ , Z ₃ and Z ₄ in the above general formula [I] include chlorine, bromine, iodine and fluorine. And the alkoxy group is, for example, methoxy,
There are various groups such as ethoxy, and as the alkylamino group,
For example, each group such as aminomethylamino, dimethylamino, diethylamino and the like can be mentioned. Examples of the acylamino group include each group such as acetamide and propionamide, and examples of the acyloxy group include each group such as acetoxy and propionoxy. Examples of the alkoxycarbonyl group include groups such as ethoxycarbonyl and methoxycarbonyl, examples of the alkoxycarbonylamino group include groups such as ethoxycarbonylamino and propoxycarbonylamino, and examples of the aryl group include phenyl and tolyl. And the like, and the alkyl group is preferably a lower alkyl group such as methyl, ethyl or propyl.

In the general formula [I], Z ₁ and Z ₂ and / or Z ₃ and Z ₄ are respectively linked to form a ring, and as a result, a naphthoxoxal ring, for example, a naphtho [2,3-d] oxazole ring,
A naphtho [1,2-d] oxazole ring, a [2,1-d] oxazole ring or the like is formed in the molecule of the compound represented by the general formula [I], or Z ₂ and Z ₄ are at the 5-position. It is preferably a substituted phenyl group, more preferably a phenyl group in which Z ₂ and Z ₄ are substituted at the 5-position.

In the general formula [I], examples of the alkyl group represented by R ₁ and R ₂ include groups such as methyl, ethyl and butyl, and examples of the alkoxyalkyl group include 2-
There are groups such as methoxyethyl, examples of the hydroxyalkyl group include groups such as 2-hydroxyethyl, examples of the sulfoalkyl group include groups such as sulfoethyl and sulfobutyl, and examples of the carboxyalkyl group include:
For example, there are groups such as carboxypropyl, which may be the same or different from each other.

See also X₁ Examples of anions represented by
Substance, bromide, iodide, thiocyanate, sulfate,
Methyl sulphate, ethyl sulphate, park lore
And anions such as p-toluene sulfonate.

In the general formula [II], the groups represented by R ₄ and R ₅ are the same as those described above in R ₁ and R ₂ , and examples of the lower alkyl group represented by R ₆ include methyl and ethyl. Examples include groups such as propyl, each group represented by Z ₅ and Z ₆ , and Z ₇ when Y ₁ is —S—.
And the groups represented by Z ₈ are the same as described above for Z ₁ to Z ₄ .

Y ₁ is In the case of Z ₇ or Z ₈ represents an alkyl group of the “benzene ring fused to the benzene ring of the benzimidazole ring in the formula (II)” includes, for example, each group such as methyl, ethyl, propyl, The group preferably includes lower alkyl groups such as methyl, ethyl and propyl, and the aryl group includes groups such as phenyl and tolyl.

X₂ The anion represented by ₁In case of
The same thing can be illustrated.

In the general formula [III], R₇, R₈And R₁₁Represented by
Each group represented by R₁And R₂Similar to that described in
Can be applied, Z₉And Z_TenAnd Y₂But Z for₁₁And Z₁₂Is Y₁But Z when₇And Z₈As in, and Y₂Is -S-
Z for₁₁And Z₁₂Each group represented by₁No
Z_FourAs in, and X ₃Anion represented by
As the above X₁ The same thing as the case of can be illustrated.

The typical examples of the sensitizing dyes represented by the above general formulas [I], [II] and [III] are shown below, but the present invention is not limited thereto.

Exemplary compounds of general formula [I] Exemplary compound of general formula [II] Exemplary compound of general formula [III] The sensitizing dye represented by the general formula [I] and the sensitizing dye represented by the general formula [II] or [III] are 3 × 10 ^{−7 to} 3 × 10 ⁻³ mol per mol of silver halide, respectively.
Preferably 3 × 10 ^{-6 to} 3 × 10 ^-4 mol, particularly preferably 1
It is added to the silver halide emulsion in a ratio of ^10-5 to ^310-4 mol.

The formula [II] or [II] for the dye of the formula [I]
The use ratio of the dye of [I] is preferably 1:10 to 100: 1, and particularly preferably 1: 1 to 10: 1 in terms of molar ratio.

The sensitizing dye may be added at any time such as the start of chemical ripening (also called second ripening) of the silver halide emulsion, the progress of ripening, the end of ripening, or an appropriate timing prior to emulsion coating.

As a method of adding a sensitizing dye to a photographic emulsion, various methods conventionally proposed can be applied. For example, as described in US Pat. No. 3,469,987, the sensitizing dye may be dissolved in a volatile organic solvent, the solution may be dispersed in a hydrophilic colloid, and the dispersion may be added to an emulsion. Also, the sensitizing dyes may be individually dissolved in the same or different solvents, and these solutions may be mixed or added separately before being added to the emulsion.

As the dye solvent when the sensitizing dye is added to the silver halide photographic emulsion, a water-miscible organic solvent such as methyl alcohol, ethyl alcohol or acetone is preferably used.

The sensitizing dye may be used in combination with other sensitizing dyes or supersensitizers.

As the binder of the silver halide emulsion in the present invention, various hydrophilic colloids such as gelatin are used.
Gelatin includes not only gelatin but also derivative gelatin. Derivative gelatin includes a reaction product of gelatin and an acid anhydride, a reaction product of gelatin and an isocyanate, or a reaction of gelatin and a compound having an active halogen atom. Products and the like are included. Examples of the acid anhydride used for the reaction with gelatin include maleic anhydride, phthalic anhydride, benzoic anhydride, acetic anhydride, isatoic anhydride, succinic anhydride, and the like, and the isocyanate compound includes, for example, phenyl. Examples thereof include isocyanate, p-promophenyl isocyanate, p-chlorophenyl isocyanate, p-tolyl isocyanate, p-nitrophenyl isocyanate, and naphthyl isocyanate.

Further, examples of the compound having an active halogen atom include benzenesulfonyl chloride, p-methoxybenzenesulfonyl chloride, p-phenoxybenzenesulfonyl chloride, p-promobenzenesulfonyl chloride, p-toluenesulfonyl chloride, m-nitrobenzenesulfonyl chloride, m- Sulfobenzoyl dichloride, naphthalene-β-sulfonyl chloride, p-chlorobenzenesulfonyl chloride, 3-nitro-4-aminobenzenesulfonyl chloride, 2-
Carboxy-4-bromobenzenesulfonyl chloride, m-carboxybenzenesulfonyl chloride, 2
-Amino-5-methylbenzenesulfonyl chloride,
It includes phthalyl chloride, p-nitrobenzoyl chloride, benzoyl chloride, ethyl chlorocarbonate, furoyl chloride and the like.

Further, as a hydrophilic colloid for preparing a silver halide emulsion, in addition to the above-mentioned derivative gelatin and usual photographic gelatin, colloidal albumin, agar, gum arabic, dextran, alginic acid, for example, acetyl content 19 as necessary. ~ 26% hydrolyzed cellulose derivatives such as cellulose acetate, polyacrylamide, imidized polyacrylamide, casein, vinyl alcohol polymers containing urethane carboxylic acid groups or cyanoacetyl groups, such as vinyl alcohol-vinyl cyanoacetate copolymers, Polyvinyl alcohol-
It is also possible to use polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, a polymer obtained by polymerizing a protein or a saturated acylated protein with a monomer having a vinyl group, polyvinyl pyridine, polyvinyl amine, polyaminoethyl methacrylate, polyethylene imine and the like.

Hardening treatment of the emulsion is carried out according to a conventional method. The hardener used is a conventional photographic hardener, for example, aldehyde compounds such as formaldehyde, glyoxal, and glutaraldehyde, and their derivative compounds such as acetal or sodium bisulfite adduct, methanesulfonic acid ester compounds. Compounds, epoxy compounds, aziridine compounds, active halogen compounds, maleimide compounds, active vinyl compounds, carbodiimide compounds, isoxazole compounds, N-methylol compounds, isocyanate compounds, or chrome meiban, An inorganic hardener such as zirconium sulfate can be used.

The silver halide emulsion layer of the present invention comprises 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, development acceleration, hardening, and sensitization).

That is, U.S. Patent Nos. 2,240,472, 2,831,766, and
3,158,484, 3,210,191, 3,294,540, 3,50
7,660, British Patents 1,012,495, 1,022,878, 1,1
79,290, 1,198,450, U.S. Patents 2,739,891, 2,
823,123, 1,179,290, 1,198,450, 2,739,8
No. 91, No. 2,823,123, No. 3,068,101, No. 3,415,649
No. 3,666,478, No. 3,756,828, British Patent No. 1,397,21
No. 8, No. 3,113,816, No. 3,411,413, No. 3,473,174,
3,345,974, 3,726,683, 3,843,368, Belgian Patent 731,126, British Patent 1,138,514, 1,159,82
5, No. 1,374,780, U.S. Patent No. 2,271,623, No. 2,288,2
No. 26, No. 2,944,900, No. 3,235,919, No. 3,671,247
No., No. 3,772,021, No. 3,589,906, No. 3,666,478,
No. 3,754,924, West German Application Publication (OLS) 1,961,683 and Japanese Patent Laid-Open Nos. 50-117414, 50-59025, and Japanese Patent Publication No. 40-378.
No. 40-379, No. 43-13822, for example, saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl or alkylaryl ethers, polyethylene glycol). Esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (eg alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, Alkyl esters of sugars, nonionic surfactants such as urethanes or ethers, triterpenoid saponins, Alkyl carboxylate, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, Carboxy groups such as polyoxyethylene alkyl phosphates, sulfo groups, phospho groups, sulfuric acid ester groups, anionic surfactants containing acidic groups such as phosphoric acid ester groups, amino acids,
Amphoteric surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkylbetaines, amineimides, amine oxides, alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, imidazolium Cationic surfactants such as heterocyclic quaternary ammonium salts such as and aliphatic or heterocyclic containing sulfonium or sulfonium salts can be used.

In the silver halide emulsion layer of the present invention, as a development accelerator,
In addition to the above surfactants, West German application publication (OLS) 2.002,871
, 2,445,611, 2,360,878, British Patent 1,352,19
It may contain imidazoles, thioethers, selenoethers, etc. described in No. 6 and the like.

In order to apply the present invention to a color light-sensitive material, the silver halide emulsion layer according to the present invention is used as a green-sensitive silver halide emulsion layer, and a magenta coupler is used in combination to be used in a color light-sensitive material. The method and materials may be applied, and the coupler is preferably a non-diffusible type having a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent with respect to silver ion. It may also include a colored coupler having color-correcting curing or a coupler that releases a development inhibitor upon development (so-called DIR coupler). Further, the coupler may be a coupler in which the product of the coupling reaction is colorless.

In the light-sensitive material of the present invention, a known closed ketomethylene type coupler can be used as a yellow color forming coupler. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous.

Specific examples of yellow color forming couplers that can be used are described in US Pat.
No. 7, No. 3,265,506, No. 3,408,194, No. 3,551,155,
No. 3,582,322, No. 3,725,072, No. 3,891,445, West German patent 1,547,868, West German application publication (OLS) 2,213,461,
2,219,917, 2,261,361, 2,414,006, 2,2
It is described in No. 63,875.

As the magenta color coupler, a pyrazolone compound, an indazolone compound, a cyanoacetyl compound or the like can be used, and a pyrazolone compound is particularly advantageous.
Specific examples of magenta color couplers that can be used are described in US Pat.
600,788, 2,983,608, 3,062,653, 3,127,2
No. 69, No. 3,314,476, No. 3,419,391, No. 3,519,429
No., No. 3,558,319, No. 3,582,322, No. 3,615,506,
No. 3,834,908, No. 3,891,445, West German patent 1,810,464
No. 2, West German Application Publication (OLS) No. 2,468,665, No. 2,417,945
No. 2,418,959, No. 2,424,467, and Japanese Patent Publication No. 40-6031.

As the cyan color coupler, a phenol compound, a naphthol compound or the like can be used. Specific examples thereof are U.S. Patents 2,369,929, 2,434,272, and 2,474,293.
Issue, Issue 2,521,908, Issue 2,895,826, Issue 3,034,892,
3,311,476, 3,458,315, 3,476,563, 3,5
83,971, 3,591,383, 3,767,411, West German Application Publication (OLS) 2,414,830, 2,454,329, JP-A-48-5983
It is described in No. 8.

Examples of colored couplers include U.S. Pat.
No. 0, No. 2,521,908, No. 3,034,892, Japanese Patent Publication No. 44-2016
No. 38-22335, No. 42-11304, No. 44-32461, Japanese Patent Application No. 49-98469, No. 50-118029, West German Application Publication (OLS) 2,
Those described in No. 418,959 can be used.

Examples of DIR couplers include U.S. Pat.
3,617,291, 3,701,783, 3,790,384, 3,63
2,345, West German Application Publication (OLS) 2,414,006, 2,454,3
01, 2,454,329, British Patent 953,454, Japanese Patent Application No. 50-1
The one described in No. 46570 can be used.

In addition to the DIR coupler, a compound which releases a development inhibitor upon development may be contained in the light-sensitive material. For example, U.S. Patent Nos. 3,297,445 and 3,379,529, West German application publication (OL
S) Those described in No. 2,417,914 can be used. In addition, JP-A-55-85549, JP-A-57-94752, JP-A-56-65134, and JP-A-56-1
35841, 54-130716, 56-133734, 56-135841
US Patent 4,310,618, UK Patent 2,083,640, Research Disclosure 18360 (1979), 14850 (19
80 years), 19033 (1980), 19146 (1980), 20525 (1
The couplers described in 981) and 21728 (1982) can also be used.

Two or more of the above couplers can be contained in the same layer.
The same compound may be contained in two or more different layers.

To introduce the coupler into the silver halide emulsion, known methods such as the method described in US Pat. No. 2,322,027 are used. For example, alkyl phthalate (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid ester (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid ester (eg tributyl acetylcitrate), benzoic acid ester (Eg, octyl benzoate), alkylamides (eg, diethyllaurylamide), etc., or organic solvents having a boiling point of about 30 ° C. to 150 ° C.,
For example, lower alkyl acetate such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol,
After being dissolved in methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The high boiling point organic solvent and the 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 added in an amount of 2 × 10 ^{−3 to} 5 × 10 ⁻¹ mol, preferably 1 × 10 ^{−2 to} 5 × 10 ⁻⁴ mol, per mol of silver in the silver halide emulsion layer.

The light-sensitive material of the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant, and specific examples thereof are U.S. Patents 2,360,290, 2,336,327, and 2, 40
3,721, 2,418,613, 2,675,314, 2,701,197
No., No. 2,704,713, No. 2,728,659, No. 2,732,300,
2,735,765, JP-A-50-92988, 50-92989, 5
No. 0-93928, No. 50-110337, and Japanese Patent Publication No. 50-23813.

Diacetyl cellulose, styrene-
Perfluoroalkyl sodium maleate copolymers, alkali salts of the reaction products of styrene-maleic anhydride copolymers and p-aminobenzenesulfonic acid are effective. Examples of the matting agent include polymethylmethacrylate, polystyrene and alkali-soluble polymers. It is also possible to use colloidal silicon oxide. Examples of the latex added to improve the physical properties of the film include copolymers of acrylic acid ester, vinyl ester and the like with other monomers having an ethylene group. Examples of the gelatin plasticizer include glycerin and glycol compounds, and examples of the thickener include styrene-sodium maleate copolymer and alkyl vinyl ether-maleic acid copolymer.

As the support of the photosensitive material of the present invention, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass paper, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate,
There are polystyrene and the like, and these supports are appropriately selected according to the intended use of each light-sensitive material.

These supports are subjected to a subbing process, if necessary.

The light-sensitive material of the present invention can be developed after exposure by a known method usually used.

The black-and-white developer is an alkaline solution containing developing agents such as hydroxybenzenes, aminophenols and aminobenzenes, and may further contain alkali metal sulfites, carbonates, bisulfites, bromides and iodides. it can. When the light-sensitive material is for color, color development can be performed by a commonly used color development method. In the reversal method, first, development is carried out with a black-and-white negative developing solution, then white exposure is carried out or processing is carried out in a bath containing a fogging agent, and then color development is carried out with an alkaline developing solution containing a color developing agent. There is no particular limitation on the processing method, and any processing method can be applied,
For example, as a typical example thereof, after color development, a bleach-fixing treatment is further performed, followed by washing with water if necessary, a method of performing a stabilizing treatment, or after color development, bleaching and fixing are separately performed and further washed with water, if necessary, A method of performing stable processing can be applied.

The light-sensitive material according to the present invention can be preferably applied to many uses requiring high sensitivity. For example, general black and white, X ray, color, infrared, micro, silver dye bleaching method,
It can be used for various purposes such as inversion and diffusion transfer method.

When it is applied to a multilayer color light-sensitive material, it can be applied to various layer structures well known in the art, that is, any layer structure such as a forward layer and a reverse layer.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.

Example 1 Emulsion EM1 of a dodecahedron composed of (nn1) crystal faces by the following method
And a cubic grain emulsion EM2 consisting of (100) crystal faces were prepared.

(EM1) A silver iodobromide emulsion EM1 was prepared using the following 5 kinds of solutions. As the seed emulsion, a monodisperse silver iodobromide emulsion containing 4 mol% of silver iodide having an average grain size of 0.25 μm and a variation coefficient of grain distribution of 11% was used.

(Solution A-1) (Solution B-1) (Solution C-1) (Solution D-1) Required amount of pAg adjustment with 50% KBr aqueous solution (Solution E-1) Required amount of 56% acetic acid aqueous solution pH adjustment Mixing and stirring shown at JP-A-57-92523 and 57-92524 at 40 ° C. (Solution A-1) to (Solution C-
1) and (Solution B-1) were added by the simultaneous mixing method so as to require a minimum time during which no small particles were generated on the way. During simultaneous mixing
The pAg was 8.6, and the pH and addition rate of (Solution C-1) were controlled as shown in Table 3. The pAg and pH are controlled by a roller tube pump with variable flow rate (solution D-1).
This was performed while changing the flow rates of (Solution E-1) and (Solution B-1).

One minute after the addition of (Solution C-1) was completed, the pH was adjusted to 6.0 with (Solution E-1).

Next, deionized water was washed by a conventional method, and ossein gelatin 56.3
After dispersing in an aqueous solution containing g, add distilled water to bring the total volume to 1500 ml.
Then, (solution D-1) and (solution E-1) were used to prepare pAg8.5 and pH 5.8 at 40 ° C.

As a result of electron microscope observation, it was found that EM1 was a monodisperse emulsion having an average grain size of 1.0 μm and a highly monodisperse emulsion having a variation coefficient of grain size distribution of 11%.

The silver iodobromide grains of EM1 have the morphology shown in Fig. 1,
The outer surface was a dodecahedral grain composed entirely of (331) faces.

(EM2) In the manufacturing method of EM1, (solution A-1) and (solution B-
Comparative emulsion EM2 was prepared in the same manner as EM1 except that 1) was not added with 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene.

As a result of electron microscopic observation, EM2 was a monodisperse emulsion consisting of almost perfect cubic silver iodobromide grains having an average grain size of 1.0 μm, a variation coefficient of grain size distribution of 11%, and an average silver iodide content of 4 mol%. It was

For the above EM1 and EM2, the above general formulas [I] and [II]
Alternatively, the sensitizing dye represented by [III] was used as shown in Table 4 and added at 60 ° C.

Furthermore, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, sodium thiosulfate, chloroauric acid and ammonium thiocyanate were added, and chemical ripening and spectral sensitization were performed under optimum conditions. did.

Next, as stabilizers for each emulsion, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 1-phenyl-5-
Mercapto-tetrazole, saponin as coating aid,
And 3 g of polyvinylpyrrolidone and an appropriate amount of 1,2-bis (vinylsulfonyl) ethane as a hardener, respectively, and the following magenta coupler, dodecyl gallate, tricresyl phosphate, ethyl acetate, sodium triisopropylnaphthalenesulfonate and A dispersion of a mixture of gelatin was added.

(Magenta coupler) The emulsion thus prepared was coated on a cellulose triacetate base support and dried to prepare a sample. Then, each sample was exposed to a wedge for 1/50 second through a yellow filter, and then subjected to color negative development processing as described below.

<Development processing> Processing process (38 ℃) Processing time Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Each treatment The composition of the treatment liquid used in the process is as follows.

Color developer composition: Bleach solution composition: Fixer composition: Stabilizer composition: The resulting dye images were each subjected to density measurement through a green filter to determine sensitivity and fog. The sensitivity was obtained from the exposure amount required to give an optical density of "fog + 0.1". The results of sensitometry are shown in Table 4 below.
Shown in. Note that the sensitivity was expressed relative to the sensitivity of Sample No. 1 as 100.

From Table 4, the sensitizing dye represented by the general formula [I] and the sensitizing dye represented by the general formula [II] or [III] are used in combination to spectrally sensitize the (331) crystal plane of the present invention. The sample having silver halide grains clearly shows an increase in the sensitivity of the color sensitized portion as compared with the comparative material.

Example 2 (EM3) A silver iodobromide core / shell emulsion EM3 was prepared using the following five kinds of solutions. The seed emulsion has an average grain size of 0.25 μm,
A silver iodobromide emulsion having a variation coefficient of grain size distribution of 11% and a silver iodide content of 4 mol% was used.

(Solution A-2) (Solution B-2) (Solution B-3) (Solution B-4) (Solution C-2) (Solution D-2) Required amount for adjusting pAg with 50% KBr aqueous solution (Solution E-2) Required amount for adjusting pH for 56% acetic acid aqueous solution At 50 ° C, mixing and stirring shown in JP-A-57-92523 and 57-92524 (Solution A-2) to (Solution C-
2) and (Solution B-2) were added by the simultaneous mixing method so as to require the minimum time during which no small particles were generated on the way. During simultaneous mixing
The pAg was 8.6, and the pH and addition rate of (solution C-2) were controlled as shown in Table-5.

The pAg and pH were controlled by changing the flow rates of (Solution D-2) and (Solution E-2) with a roller tube pump having a variable flow rate.

Average grain size of silver halide grains (side length of cube of the same volume)
When the calculated value reached 0.65 μm, (Solution B-2) was switched to (Solution B-3), and the average particle size was calculated to be 0.80.
When the solution reaches μm, (solution B-3) is replaced with (solution B-4)
I switched to. (Solution B-2), (B-3), (B-
In 4), the iodide ion concentration is adjusted to 15 mol%, 5 mol% and 0.3 mol% with respect to the total halide ion concentration.

One minute after the addition of (Solution C-2) was completed, the pH was adjusted to 6.0 with (Solution E-2).

Next, deionized water was washed by a conventional method, and ossein gelatin 63.8
After dispersing in an aqueous solution containing g, add distilled water to bring the total volume to 1500 ml.
To (Solution D-2) and (E-2)
It was adjusted to pAg 8.5 and pH 5.8 at 40 ° C.

As a result of electron microscope observation, it was found that EM3 was a monodisperse emulsion having an average grain size of 1.0 μm and the variation coefficient of grain size distribution was 13%. EM3 is a core / shell type silver iodobromide emulsion having a high silver iodide content phase inside the grain size.

The EM4 silver iodobromide grains have the form shown in Fig. 1,
The outer surface was a dodecahedral grain composed entirely of (331) faces.

(EM4) (Solution A-2), (Solution B-
2), (Solution B-3) and (Solution B-4) were compared with EM3 except that 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene was not added. Emulsion E
Manufactured M4.

As a result of electron microscopic observation, EM4 is a monodisperse emulsion consisting of almost perfect cubic silver iodobromide grains having an average grain size of 1.0 μm, a variation coefficient of grain size distribution of 15%, and a high silver iodide content phase inside the grains. Met.

Each emulsion prepared as described above was subjected to optimum chemical sensitization (using a gold salt and a sulfur sensitizer), and then a sensitizing dye represented by the general formula of the present invention was added according to Table 6 below.

These emulsions were coated and dried in the same manner as in Example 1, exposed to light in the same manner as in Example 1, and developed to measure the sensitivity and change in fogging. The obtained results are shown in Table-6.

The sensitivity is expressed as a relative sensitivity with the sensitivity of Sample No. 25 being 100.

As is clear from Table 6, even in core / shell grains having a high iodine phase inside the grain, silver iodobromide having a (nn1) crystal plane sensitized by the combination of the sensitizing dyes according to the present invention. The sample of the present invention having particles is more sensitive than the comparative sample.

〔The invention's effect〕

The present invention improves the green sensitivity of silver halide photographic light-sensitive materials.

[Brief description of drawings]

1, 2, and 3 are schematic explanatory views of the (nn1) plane according to the present invention. FIGS. 4 to 11 are schematic explanatory views when another type of surface is mixed in the (331) surface. FIG. 12 is an electron micrograph of silver halide grains having a (331) plane. 1 …… (nn1) plane 2 …… (110) plane 3 …… (111) plane 4 …… (100) plane a and b …… vertices c …… Two (nn1) planes that overlap the (110) plane Ridge line formed by intersection lines

Front Page Continuation (72) Inventor Tomomi Yoshizawa 1 Sakura-cho, Hino-shi, Tokyo Konishi Roku Photo Co., Ltd. Inspector Kayoko Yasuda (56) Reference JP 61-83531 (JP, A) JP Sho 62-205338 (JP, A) JP-A-62-208043 (JP, A)

Claims (1)

[Claims] 1. A (nn1) crystal plane (n ≧ 2, n is a natural number)
It is a silver halide grain having the following general
At least one sensitizing dye represented by the formula [I] and one of the following
Less sensitizing dye represented by general formula [II] or [III]
Silver halide spectrally sensitized in combination with
Characterized by having a silver halide emulsion layer having grains
A silver halide photographic light-sensitive material. General formula [I]General formula (II)General formula (III)[In the above general formula [I], R₁And R₂Are each
Alkyl group, alkoxyalkyl group, hydroxyalkyl
Group, sulfoalkyl group or carboxyalkyl group
I, R₃Is a hydrogen atom, a halogen atom, a lower alkyl group,
Represents an aryl group or a lower alkoxy group, Z₁,
Z₂, Z₃And Z_FourAre halogen atom and hydroxyl respectively
Group, alkoxy group, amino group, alkylamino group, acyl group
Luamino group, acyloxy group, alkoxycarbonyl
Group, alkoxycarbonylamino group, aryl group, ar
It represents a kill group or a cyano group. Z₁And Z₂And Z₃And Z
_FourMay be connected to each other to form a ring. See also X₁ Represents an anion. m represents 1 or 2
And the dye represented by the general formula [I] forms an intramolecular salt.
M represents 1. n, n ', l and l'are
Represents 0 or 1, respectively. ] In the above general formula [II], Y₁Is -S- orRepresents R₉Represents an alkyl group. R_FourAnd R_FiveIs it
Alkyl group, alkoxyalkyl group, hydroxy group
Alkyl group, sulfoalkyl group, or carboxyalkyl group
R group₆Is Y₁Is -S-, a lower alkyl group
Represents,Then represents a hydrogen atom. Z_FiveAnd Z₆Are halogen atom, hydroxyl group,
Alkoxy group, amino group, acylamino group, acyloxy group
Si group, alkoxycarbonyl group, alkoxycarbonyl
Represents an amino group, aryl group, alkyl group or cyano group
Forget Z_FiveAnd Z₆May combine with each other to form a ring. Y₁Is -S-, Z₇And Z₈Is the halogen source
Child, hydroxyl group, alkoxy group, amino group, acyl
Amino group, acyloxy group, alkoxycarbonyl group,
Alkoxycarbonylamino group, aryl group, alkyl
Represents a group or a cyano group, Z₇And Z₈Are connected to each other
May be formed. Y₁But , Then Z₇And Z₈Are both methyl groups and both are chlorine sources.
Child, one of which is a benzimidazole ring in the formula [II]
Benzene ring fused to benzene ring (substitute with alkyl group
The other is a hydrogen atom, and one of these is the formula [II]
Condensed at the e or g position of the benzimidazole ring in
The other is a benzene ring and the other is a hydrogen atom, and one of these is 5-meth
Xy group, the other being the g position of the benzimidazole ring in the formula [II]
A benzene ring fused to, or an alkyl group or
Represents an aryl group. X₂ Represents an anion, and p is 1
Or represents 2. r, r ′, s and s ′ are respectively
Represents 0 or 1. ] In the above general formula [III], Y₂Is -S- orRepresents R₇, R₈And R₁₁Are alkyl groups and
Lucoxyalkyl group, hydroxyalkyl group, sulphoa
Represents a alkyl group or a carboxyalkyl group, Z₉Oh
And Z_TenAre both methyl groups, both are chlorine atoms,
Is one of the benzimidazole benzes in the formula [III]
Benzene ring fused to a ring (substituted with an alkyl group
The other is a hydrogen atom, and one of these is a hydrogen atom in the formula [III].
Benzo condensed at the e-position or the g-position of the benzimidazole ring
The other is a hydrogen atom in the zen ring, and one of these is a 5-methoxy group.
And others are condensed to the g position of the benzimidazole ring in the formula [III].
Combined benzene ring, or an alkyl group or ant, respectively
Represents a group. Z₁₁And Z₁₂Is Y₂Is -S-, each is halogen.
Atom, hydroxyl group, alkoxy group, amino group, reed
Luamino group, acyloxy group, alkoxycarbonyl
Group, alkoxycarbonylamino group, aryl group, ar
Represents a kill group or a cyano group, Z₁₁And Z₁₂Are connected to each other
To form a ring. Y₂But , Then Z₁₁And Z₁₂Both are methyl groups, both are chlorine
An atom, one of which is a benzimidazole in the formula [III]
Benzene ring fused to the benzene ring of
Substituted) and the other is a hydrogen atom, one of which is [II
I] in the e-position or g-position of the benzimidazole ring in the formula
The other is a condensed benzene ring with a hydrogen atom, one of which is 5
-Methoxy group and the others are benzimidazoles in the formula [III]
Benzene ring fused to ring g or alkyl group
Alternatively, it represents an aryl group. X₃ Represents an anion, and q represents 1 or 2.
u, u ′, v and v ′ each represent 0 or 1.
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