JPH0789202B2 - Silver halide photographic light-sensitive material with improved spectral sensitization sensitivity - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material having a silver halide emulsion layer having improved spectral sensitization sensitivity.

[Prior Art and Background of the Invention]

In recent years, there has been a strong demand for higher sensitivity of silver halide photographic light-sensitive materials.

It is known that in a light-sensitive material using light having a wavelength other than the sensitivity region of silver halide, the sensitivity of silver halide and the effect of spectral sensitization are large.

As a high-sensitivity silver halide emulsion, a silver iodobromide emulsion containing 0 to 10 mol% or less of iodine is well known. As a method for preparing these emulsions, conventionally, a pH method such as an ammonia method, a neutral method, an acid method, a method for controlling pAg conditions, a single jet method, a double jet method, etc. are known as a mixing method. ing.

On the basis of these techniques, precise technical means have been studied and put into practical use for the purpose of achieving higher sensitivity. Regarding silver iodobromide emulsions, emulsions in which not only crystal habit and grain size distribution but also iodine concentration distribution in individual silver halide grains are controlled have been studied. To achieve high sensitivity, improve the quantum efficiency of silver halide, and
Monodisperse emulsions aiming to efficiently achieve high sensitivity while maintaining low fog in chemical ripening are known.
(100) crystal plane disclosed in JP-A-54-48521 and /
Alternatively, a silver iodobromide monodisperse emulsion having a (111) crystal plane is known.

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

On the other hand, regarding the spectral sensitization technique, it is known from many references (PSE 19 207, PSE 18 475, etc.) that the reduction potential of the sensitizing dye is important as a factor controlling the spectral sensitizing ability of the sensitizing dye. ing. However, if the reduction potential is lower than a certain value, whether it is high or low usually does not affect sensitivity. In other words, no matter how the sensitizing dye was selected, the sensitivity limit could not be exceeded.

We have obtained a spectral sensitization that cannot be obtained by conventional techniques by combining a silver halide grain having (nn1) crystal planes (n ≧ 2, n is a natural number) on the outer surface with a sensitizing dye having a specific reduction potential. The inventors of the present invention have found that sensitivity can be obtained, and have completed the present invention.

[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 sensitivity in the spectral sensitization region. Is.

[Structure of Invention]

An object of the present invention is to have a (nn1) crystal plane (n ≧ 2, n is a natural number) on the surface of a silver halide grain, have a reduction potential lower than −1.2 V, and be represented by the following general formula (1). It is achieved by a silver halide photographic light-sensitive material characterized by having a silver halide emulsion layer having silver halide grains spectrally sensitized by a sensitizing dye.

General formula (1) In the general formula (1), Z ₁ and Z ₂ each represent an atomic group necessary for forming a heterocycle, R represents an alkyl group which may be substituted with a sulfo group, and p and q each represent 1 Or represents 2.

Hereinafter, the present invention will be described in detail.

First, the silver halide grains having the (nn1) crystal plane in 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, a ₁ equivalent to 6 vertices b ₁ equivalent to 8 vertices in Figure 1. And bordering the vertex a ₁ in 8 plane, it is in contact with three planes in the vertex b _1. There are also two types of edges. That is, there are 24 sides equivalent to sides a ₁ b ₁ and 12 sides equivalent to a ₁ a ₂ in FIG.

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 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 represents the line of intersection between the plane d and the (nn1) plane. One side, the broken line 2 is the (110) plane, and the dashed line 3 is (1
11) planes, which are (nn1) planes, (110) planes,
The normal vector of each (111) plane is shown by. Therefore, the surface direction is = [11 1 / n] (n ≧ 2, n is a natural number) = [110], and It can be expressed as. Therefore, the faces themselves are (nn1) (11
It is represented by 0) and (111). θ is an angle formed by two (nn1) crystal faces adjacent to each other with the side a ₁ a ₂ as a boundary, and n ≧ 2, n is 110 ° <θ <180 ° due to the limitation of a natural number.

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 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 (Brenting of the Society of Scientific Photography) of an emulsion which was oriented on a substrate and coated was used.・ Japan (Bull
etin of the society of Scientific Photography of Ja
pan) 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 a face, rhomboid, dodecahedron, etc. 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 silver halide grains having a (nn1) crystal plane according to the present invention are not limited in silver halide composition, and they are ordinary halogens such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide and silver chloride. Any of those used in silver halide emulsions can be used.

A preferred embodiment of the present invention is an embodiment in which at least the surface of the silver halide grain is substantially composed of silver bromide or silver iodobromide. Here, "consisting essentially of silver bromide or silver iodobromide" means that the effect of the embodiment is not impaired.
It means that silver bromide and silver halide other than silver bromide, for example, silver chloride may be contained. Specifically, in the case of silver chloride, the ratio is preferably 5 mol% or less, more preferably 1 mol% or less.

In the silver halide composition of the silver halide grains according to the present invention, the ratio of silver iodide is preferably 0 to 40 mol%, more preferably 0 to 20 mol%, particularly preferably 0 to 15 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. When the silver halide grains are not a single composition in the silver halide composition, the above-mentioned grains having at least the surface composed of silver bromide or silver iodobromide have a halogen composition inside the grains such as silver chloride and silver chlorobromide. May be. Further, the halogen composition in each phase may be uniform or may continuously change.

One of the most preferable forms is one having a high iodide phase deep inside the grain. That is, it is a silver halide grain having a phase (or a plurality thereof) 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 according to the application.

A silver halide emulsion containing silver halide grains having a (nn1) plane according to the present invention is a silver halide emulsion prepared by mixing a water-soluble halide solution and a water-soluble silver salt solution in the presence of a protective colloid. (A) A silver halide suspension during a period in which at least 30 mol% of the amount of silver halide produced for forming silver halide grains is produced in a method for producing a silver halide emulsion having a step of forming grains. The pAg of the 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) after formation of the silver halide amount, the silver halide grains are formed and formed. During the heating, the pAg is controlled to 7.0 to 9.5 to obtain a silver halide emulsion.

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 method for producing silver halide grains according to the present invention, any method such as an acidic method, a neutral method or an ammonia method may be used in the step of producing silver halide to form silver halide grains. it can. The method of reacting the soluble silver salt and the soluble halogen salt may be one-side injection method in which one solution is added as the mother liquor, simultaneous mixing method in which both reaction solutions are added to the mother liquor, or a combination thereof. May be used, but as one form of the simultaneous mixing method, a method of keeping pAg constant in the liquid phase in which silver halide is produced,
That is, it is preferable to use the 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 solvent because the grain formation time can be shortened. For example, a commonly known silver halide solvent such as ammonia or 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 to adjust the concentration of the aqueous iodine compound solution to 10 ^-2 mol / l or less and to add it for 10 minutes or more.

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
The range of 1 to 11.5 is suitable, the range of 6 to 11 is preferable, and the range of pH is 2 to 12 is preferable, and the range of 5 is preferable.
The range is 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 the silver halide emulsion containing the silver halide grains according to the present invention is used for controlling the crystal and has the following general formulas (I), (II), ( Compounds represented by III) or (V) and compounds having a repeating unit of the following general formula (V) 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 or heterocyclic ring), and X is a general formula (I), (II), (III).
Alternatively, a monovalent group obtained by removing one hydrogen atom from the compound represented by (IV) (for example, one obtained by removing one hydrogen atom from R _{1 to} R ₃ or the OH moiety in the general formulas (I) to (IV)). ) And J represents a divalent linking group.

In formulas (I) to (V), examples of the alkyl group represented by R _{1 to} R ₄ include a methyl group, an ethyl group, a propyl group, a pentyl group, a hexyl group, an octyl group, an isopropyl group, and sec-butyl. Group, a t-butyl group and the like, and examples of the derivative of the alkyl group include an alkyl group substituted with an aromatic residue (which may be a divalent linking group such as —NHCO—) (eg, benzyl). Group, phenethyl group, benzhydryl group, 1-naphthylmethyl group, 3-phenylbutyl group, benzoylaminoethyl group, etc.), alkyl group substituted with an alkoxy group (for example, methoxymethyl group, 2-methoxyethyl group, 3-ethoxy) Propyl group, 4-methoxybutyl group, etc.), halogen atom, hydroxy group, carboxy group, mercapto group, alkoxycarbonyl group or substituted Is an alkyl group substituted with an unsubstituted amino group (eg, monochloromethyl group, hydroxymethyl group, 3-hydroxybutyl group, carboxyltyl group, 2-carboxyethyl group, 2- (methoxycarboxy) ethyl group, aminomethyl group) , A diethylaminomethyl group, etc.), an alkyl group substituted with a cyclolalkyl group (eg, a cyclopentylmethyl group), a monovalent group obtained by removing one hydrogen atom from the compounds represented by the above general formulas (I) to (IV). Examples thereof include an alkyl group substituted with a group.

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-promophenyl group, p-hydroxyphenyl group, 1-hydroxy-2-naphthyl group, m-methoxyphenyl group, p-ethoxyphenyl group, p-carboxyphenyl group, 0- (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.

Although j is a divalent linking group, it preferably has 1 to 20 total carbon atoms. 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 between the alkylene groups. For example, methylene group, ethylene group, propylene group, -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 −, −CO
NHCH 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 the unit represented by the general formula (V) may be a homopolymer or a copolymer, and examples of the copolymer include acrylamide, methacrylamide, acrylic ester, methacrylic ester and the like.

Next, the general formula (I), (II), (III) or (I
Representative specific examples of the compound represented by V) or the compound having the repeating unit represented by the general formula (V) 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 (V), the number of moles of the tetrazaindene portion is the addition amount.

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

The silver halide grains according to the present invention may have (100) faces, (111) faces and the like in addition to the (nn1) faces, but the ratio of the (nn1) faces to the total surface area is 20 % Or more, and particularly preferably 80% or more.

In the silver halide emulsion layer of the present invention, the amount of silver halide grains having (nn1) faces is preferably 30% by weight or more, more preferably 50% by weight or more.

US Pat. No. 3,501,307 can be referred to for the method of measuring the reduction potential of the sensitizing dye in the present invention. In the present specification, the reduction potential of the sensitizing dye is the potential when the potential of the silver-silver chloride reference electrode is 0.

The sensitizing dye used in the present invention is a compound represented by the general formula (1) and having a reduction potential lower than -1.2V (preferably lower than -1.4V and higher than -2.0V). In the general formula (1), the atom group necessary for forming the heterocycle represented by Z ₁ is specifically an oxazoline nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus (for example, a naphtho [ 2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3
-D] oxazole, 8,9-dihydronaphtho [1,2-d]
Oxazole), thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, naphtho [1,2-
d] thiazole, naphtho [2,1-d] thiazole, naphtho [2,3-d] thiazole, 8,9-dihydronaphtho [1,2
-D] thiazole, selenazoline nucleus, selenazole nucleus,
Benzoselenazole nucleus, naphthoselenazole nucleus, (for example, naphtho [1,2-d] selenazole, naphtho [2,1-
d] selenazole, naphtho [2,3-d] selenazole), imidazole nucleus, benzimidazole nucleus, naphthimidazole nucleus (for example, naphtho [2,3-d] imidazole, naphtho [1,2-d] imidazole), pyridine Represents the atomic group necessary to form the nucleus and quinoline nucleus.

The above nuclei may have one or more various substituents present on the ring.

Preferred examples of such a substituent include a hydroxyl group, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an unsubstituted and substituted alkyl group (eg, methyl, ethyl, propyl, isopropyl, hydroxyethyl, carboxy). Methyl, ethoxycarbonylmethyl, trifluoromethyl, chloroethyl, methoxymethyl etc.), aryl groups (eg phenyl, tolyl, anisyl etc.), aralkyl groups (eg benzyl, phenethyl etc.), alkoxy groups (eg methoxy, ethoxy, butoxy). Etc.), a carboxyl group, an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl,
Butoxycarbonyl etc.), and acylamino groups (eg acetylamino, propionylamino, benzoylamino etc.), methylenedioxy groups, tetramethylene groups, cyano groups, acyl groups (eg acetyl, propionyl, benzoyl etc.), An alkylsulfonyl group (eg, methylsulfonyl, ethylsulfonyl, etc.) can be mentioned.

Specific examples of the group of atoms required to form the heterocycle represented by Z ₂ include a rhodanine nucleus, a 2-thiohydantoin nucleus, a 2-thioselenazolidine-2,4-dione nucleus, and a 2
-Thioxazoline-2,4-dione nucleus, 2-thiobarbituric acid nucleus, 2-isoxazolin-5-one nucleus, 2-
It represents an atomic group necessary for forming an iminothiazolin-4-one nucleus (for example, 2-phenyliminothiazolin-4-one) and the like. In the case of 2-thiohydantoin nucleus and 2-thiobarbituric acid nucleus, the nitrogen atom at the 1-position may be substituted, and a preferable substituent is an alkyl group (for example, methyl, ethyl, propyl, pentyl, decyl, Isoptyl, etc.), alkoxyalkyl group (eg, methoxyethyl, ethoxyethyl, methoxypropyl, etc.), hydroxyalkyl group (hydroxyethyl, 2-hydroxypropyl, 2,3-dihydroxypropyl, etc.), carboxyalkyl group (eg, carboxymethyl) , An alkoxycarbonylalkyl group (eg, ethoxycarbonylmethyl), a hydroxyalkoxyalkyl group (eg, 2- (2-hydroxyethoxy) ethyl), a hydroxyalkylaminocarbonylalkyl group (eg, N
-(2-hydroxyamino) carbonylmethyl) and the like. Rhodanine nucleus, 2-thiohydantoin nucleus, 2-
In the case of a thioselenazolindin-2,4-dione nucleus, a 2-thiooxazolidine-2,4-dione nucleus and a 2-thiobarpituric acid nucleus, the 3-position thereof may be substituted, and the substituent is the same as R. Significant, an alkyl group substituted with a single-membered heterocyclic group (eg, 2-fryflumethyl group), a single-membered heteroaryl group (eg, 2-pyridyl group, 3-pyridyl group, 3-chloro-) 2-pyridyl group, 2
-Thienyl group, 2, -furyl group, etc.) and the like.

Next, specific examples of the sensitizing dye used in the present invention and the reduction potential thereof will be described, but the present invention is not limited thereto.

The sensitizing dye used in the present invention is 6 × 10 ^{−7 to} 6 × 10 ⁻³ mol, preferably 6 × 10 ^{−6 to} 6 × 10 mol per mol of silver halide.
^-4 mol, particularly preferably 2 × 10 ^{-5 to} 6 × 10 ^-4 mol in the silver halide emulsion.

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 sulfonate, alkylnaphthalene sulfonate, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurine, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers Anionic surfactants containing amino groups such as carboxy groups such as polyoxyethylene alkyl phosphates, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, amino acids, aminoalkyl sulfonic acids, amino Amphoteric surfactants such as alkylsulfates or phosphates, alkylbetaines, amineimides and amineoxides, alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocycles such as pyridinium and imidazolium Cationic surfactants such as quaternary ammonium salts and sulfonium or sulfonium salts containing aliphatic or heterocyclic rings 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.

When the present invention is applied to a color light-sensitive material, the silver halide emulsion layer according to the present invention is used as a red-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer, and cyan and magenta couplers are used respectively. It suffices to apply the method and material used for the color light-sensitive material such as inclusion together, and the coupler is preferably a non-diffusible one 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. Further, a colored coupler having a color correcting effect or a coupler releasing a development inhibitor upon development (so-called DIR coupler) may be included. 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 include U.S. Patents 2,875,057 and 3,265,5.
No. 06, No. 3,408,194, No. 3,551,155, No. 3,582,322
No. 3,725,072, No. 3,891,445, West German Patent 1,547,86
No. 8, West German Application Publication (OLS) No. 2,213,461, No. 2,219,917
No. 2,261,361, No. 2,414,006, No. 2,263,875, etc.

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 the DIR coupler include, for example, U.S. Patents 3,227,554, 3,617,291, and 3,701,783.
No. 3, No. 3,790,384, No. 3,632,345, West German application published (OL
S) 2,414,006, 2,454,301, 2,454,329, British Patent 953,454, and those described in Japanese Patent Application No. 50-146570 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 layer, 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 acetates 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 an anti-fogging agent, 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 treatment method, and any treatment 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〕

The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

Example 1 A silver iodobromide core / shell emulsion EMI was prepared using the following 6 kinds of solutions. As the seed emulsion, a silver iodobromide emulsion having an average grain size of 0.25 μm, a grain size distribution variation coefficient of 11% and a silver iodide content of 4 mol% was used.

(Solution A-1) Ocein gelatin 18.9 g Distilled water 3700 ml Polyisopropyleneoxy-succinic acid ester sodium salt 10% aqueous ethanol solution 10 ml 4-Hydroxy-6-methyl-1,3,3a, 7-tetraazaindene 420 mg 28 % Ammonia water 235 ml Emulsion 0.0552 mol equivalent (Solution B-1) Ocein gelatin 143.7 g KBr 143.7 g KI 27.89 g 4-Hydroxy-6-methyl-tetraazaindene 42 mg Distilled water is added to 400 ml.

(Solution B-2) Ocein gelatin 8 g KBr 316.7 g KI 13.94 g 4-hydroxy-6-1,3,3a7-tetraazaindene 84 mg Distilled water to make 800 ml.

(Solution C-1) AgNO ₃ 590.5g 28% Ammonia water 481ml Distilled water to make 993ml.

(Solution D-1) 50% KBr aqueous solution pAg adjustment required amount (Solution E-1) 56% acetic acid aqueous solution pH adjustment required amount At 50 ° C, the mixing stirrer disclosed in JP-A-57-92523 and 57-92524. To (Solution A-1) to (Solution C-
1) and (Solution B-1) were added by the simultaneous mixing method for a minimum time without the generation of small particles on the way. PA during simultaneous mixing
g is 8.6, and the addition rate of pH and (Solution C-1) is
Control was performed as shown in 3. The pAg and pH were controlled by changing the flow rates of (Solution D-1) and (Solution E-1) with a roller tube pump having a variable flow rate.

Average grain size of silver halide grains (side length of cubic body with the same volume)
When the calculated value reached 0.65 μm, (Solution B-1) was switched to (Solution B-2) and the addition was continued. (Solution B
-1) and (Solution B-2) have an iodide ion concentration of 12 mol% and 3% with respect to the total halide ion concentration, respectively.
Has been adjusted as

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 is washed by a conventional method, and ossein gelatin is used.
Disperse in an aqueous solution containing 63.3 g, and then add distilled water to a total volume of 150
Adjust to 0 ml, and further add (solution D-1) and (solution E-
1) was used to adjust pAg 8.5 and pH 5.8 at 40 ° C.

As a result of electron microscope observation, it was found that EM1 was a monodisperse emulsion and the variation coefficient of the grain size distribution was 12%. EM1 is a core / shell type silver iodobromide emulsion having a high iodine shell inside the grain.

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

Separately, a comparative emulsion EM2 was prepared by the following method.

The production method was such that the pAg was continuously changed from 9 to 10 and the amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene added was changed with the growth of particles. It is the same as EM1 except that it was done.

Like EM1, EM2 is composed of core / shell type silver iodobromide grains having a high-iodity shell inside, and the grains have a coefficient of variation of particle size distribution of 13% and are almost completely composed of (111) faces. It is a regular octahedron.

Next, sodium thiosulfate, chloroauric acid and ammonium thiocyanate were added to each of the emulsions of EM1 and EM2 described below, and each was subjected to optimum chemical sensitization, followed by the sensitizing dyes exemplified as the sensitizing dye of the present invention and a comparison. Sensitizing dyes were added according to Table-4 below.

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 further the following cyan coupler, dodecyl gallate, tricresyl phosphate, ethyl acetate, sodium triisopropylnaphthalenesulfonate and A dispersion of a mixture of gelatin was added.

(Cyan coupler) The emulsions thus prepared were coated on a cellulose triacetate base support and dried to prepare Samples 1 to 12. Next, each of the above-mentioned samples was exposed to a wedge of 1/50 second through a red filter ratten 26 to prepare an exposed sample, and a color negative development process was carried out as follows.

<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 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline sulfate 4.8g Anhydrous sodium sulfite 0.14g Hydroxylamine 1/2 sulfate 1.98g Sulfuric acid 0.74mg Anhydrous potassium carbonate 28.85g Anhydrous potassium hydrogen carbonate 3.46g Anhydrous potassium sulfite 5.10g Potassium bromide 1.16g Sodium chloride 0.14g Nitrilotriacetic acid-3 sodium salt (monohydrate) 1.20g Potassium hydroxide 1.48g Add water to make 1.

Bleaching solution Ethylenediaminetetraacetic acid iron ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water to adjust the pH to 6.0 with ammonia water.

Fixing solution Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.6 g Sodium metasulfite 2.3 g Add water to make 1 and adjust to pH 6.0 with acetic acid.

Stabilizer Formalin (37% aqueous solution) 1.5 ml Conidax (Konishi Rokusha Kogyo Co., Ltd.) 7.5 ml Add 1 to add water.

The obtained dye image was subjected to density measurement through a red filter to determine red light sensitivity and fogging. 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. Note that the sensitivity was expressed relative to the sensitivity of Sample 1 being 100.

From Table 4, it can be seen that the color light-sensitive material using the combination of the silver halide grains of the present invention and the sensitizing dye has remarkably higher red sensitivity than the comparative sample.

Example 2 A silver iodobromide core / shell emulsion EM3 was prepared using the following 5 kinds of solutions. The seed emulsion has an average grain size of 0.25 μm,
A silver iodobromide emulsion having a grain distribution variation coefficient of 11% and a silver iodide content of 4 mol% was used.

(Solution A-2) (Solution B-3) (Solution B-4) (Solution B-5) (Solution C-2) (Solution D-2) 50% KBr aqueous solution pAg adjustment required amount (Solution E-2) 56% acetic acid aqueous solution pH adjustment required amount At 50 ° C, mixing and stirring described in JP-A-57-92523 and 57-92524. (Solution A-2) to (Solution C-
2) and (Solution B-3) were added by the simultaneous mixing method for a minimum time without generation of small particles 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)
Is calculated to reach 0.65 μm, (solution B-3) is switched to (solution B-4), and the average particle size is calculated to be 0.80.
When the solution reaches μm, (solution B-4) is replaced with (solution B-5)
I switched to. (Solution B-3), (B-4), (B-
In 5), the iodide ion concentration is adjusted to 15 mol%, 5 mol% and 0.3 mol% with respect to the total halide ion concentration.

For EM3, 1 minute after the addition of (Solution C-2) was completed, (Solution E-
The pH was adjusted to 6.0 according to 2).

Next, deionized water was washed by a conventional method, and ossein gelatin 63.3
After dispersing in an aqueous solution containing g, add distilled water to bring the total volume to 1500 ml.
And (Solution D-2) and (Solution E-2) were further adjusted to pAg8.5 and pH 5.8 at 40 ° C.

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

The EM3 silver iodobromide grains have the form shown in Fig. 1,
The outer surface was a dodecahedron grain composed of all (331) faces, and the ridge line c was clearly observed.

Separately, the pAg was continuously changed from 9 to 10 depending on the particle shape, and 4-hydroxy-6-methyl-1,3,3 was added.
EM4 was prepared in the same manner as EM3 except that the amount of a, 7-tetrazaindene was changed.

Then, after desalting by a conventional method, gelatin was added and redissolved.

Like EM3, EM4 is composed of core / shell type silver iodobromide grains having a high iodine shell inside, and the grains are nearly perfect octahedrons composed of (111) faces.

EM3 and EM4 were each chemically ripened by a conventional method to obtain an emulsion having a silver content of 0.60 mol / kg. 1 kg of this emulsion was heated to 40 ° C., each sensitizing dye in methanol solution shown in Table 6 was added, and mixed and stirred.

Furthermore, 4-hydroxy-6-methyl-1,2,3,3a, 7
-Add 20 ml of a 1.0% by weight aqueous solution of tetrazaindene,
The following magenta coupler was dissolved in ethyl acetate and dibutyl phthalate in an amount of 0.030 mol per 1 mol of silver and 0.001 mol of the following DIR compound in 1 mol of silver, sodium dodecylbenzenesulfonate was added, and the mixture was mixed with a homogenizer at 10%. This was added and used after being emulsified and dispersed in the gelatin aqueous solution. To this emulsion was added 20 ml of a 1% by weight aqueous solution of 1-hydroxy-3,5-dichlorotriazine sodium salt, and then 1. of dodecylbenzenesulfonic acid sodium salt.
10 ml of 0 wt% aqueous solution was added and stirred. This finished emulsion was coated on a cellulose triacetate film base so that the coated silver amount was 5 g / m ² , and dried to obtain a sample.
This film sample was subjected to optical wedge exposure by using a sensitometer having a light source with a color temperature of 5400 ° K and attaching a green filter ratten 58 to the light source. After exposure, the following development processing is performed, bleaching,
The density of the magenta color image developed by fixing and drying was measured. The reference point of the optical density for which the sensitivity was determined was the fog +0.20 point.

The results are shown in Table-6. Note that the sensitivity of Sample 14 is 100
Is shown by relative sensitivity.

<Development treatment> Color development 3 minutes 15 seconds (38 ° C) Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Fixation 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stability 3 minutes 15 seconds Treatment used for each step The liquid composition is as follows.

Color developer Sodium nitrilotriacetate 1.0 g Sodium sulfite 4.0 g Sodium carbonate 30.0 g Sodium bromide 1.4 g Hydroxylamine sulfate 2.4 g 4- (N-ethyl-N-β-hydroxyethylamine) -2-methylaniline sulfate 4.5 g Add water to make 1.

Bleaching solution Ammonium bromide 160.0 g Ammonia (28%) 25.0 ml Ethylenediamine-sodium tetraacetate iron salt 130.0 g Glacial acetic acid 14.0 ml Add water to make 1.

Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0ml Sodium bisulfite 4.6g Add water to make 1.

Stabilizer Formalin 8 ml Add water to make 1.

As is clear from Table-6, the color photographic material sample prepared by the combination of the silver halide of the present invention and the sensitizing dye has significantly higher green sensitivity than the comparative sample.

Example 3 According to the formulation shown below, the silver bromide content was 25 mol%, and the average particle size was
A 0.3 μm emulsion EM5 according to the invention was prepared. As the seed emulsion, a silver bromide monodisperse emulsion having an average grain size of 0.12 μm was used.

(Solution A-3) Ocein gelatin 57.5g Distilled water 6900ml Polyisopropylene-polyethyleneoxy disuccinate sodium salt 10% ethanol aqueous solution 6.5ml 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaine Den 151 ml Acetic acid 56% Aqueous solution 28 ml NH ₄ OH 1.76 mol Seed emulsion 0.452 mol Equivalent (Solution B-6) Ocein gelatin 48 g KBr 128.5 g NaCl 357.7 g Polyisopropylene-polyethyleneoxy disuccinate sodium salt 10% Ethanol aqueous solution 4.8 ml 4-hydroxy-6methyl-1,3,3a, 7-tetrazaindene 1060 mg Distilled water to 2400 ml.

(Solution C-3) to 2400ml with AgNO ₃ 1223g of distilled water 672ml NH ₄ OH 15.12 moles of distilled water.

(Solution D-3) KBr 0.317 g NaCl 116.8 g Make up to 2000 ml with distilled water.

(Solution E-3) A 65% acetic acid solution in 2000 ml at 40 ° C while stirring with a mixing stirrer described in JP-B-58-58288 and 58-58289 (Solution A-
(Solution B-6) and (Solution C-3) were added to 3) by the duffle jet method. The addition rate increased linearly with addition time as shown in Table 7. During addition of each solution, use (Solution D-3) to adjust the pAg of the mixed solution to 8.8.
It was controlled to (EAg value + 52 mV) and the pH of the mixed solution was controlled to decrease with time as shown in Table 7 using (Solution E-3). The addition of (Solution B-6), (Solution C-3), (Solution D-3), and (Solution E-3) used a variable flow rate roller tube metering pump.

Two minutes after the addition of (Solution B-6) and (Solution C-3) was completed, the pH was adjusted to 6.0 with (Solution E-3). Next, the emulsion was washed with water and desalted by the following operations. 913 ml of 5% aqueous solution of Demol N (Kao Atlas) as a precipitant
Then, 691 ml of a 20% aqueous solution of magnesium sulfate was added to the emulsion to agglomerate it, and the emulsion was settled and allowed to settle. The supernatant was decanted, and 15375 ml of distilled water was added to disperse the emulsion again. After adding 541 ml of 20% magnesium sulfate aqueous solution and aggregating and reprecipitating the emulsion again, the supernatant is decanted and an aqueous solution of ossein gelatin is added.
Add 1000 ml (including 80 g of ossein gelatin), 20 at 40 ℃
After stirring and dispersing for a minute, the shipping cost was adjusted to 5000 ml with distilled water.

Furthermore, using (Solution D-3), the pAg at 40 ° C was 7.5.
Adjusted to.

As a result of observation with an electron microscope, EM5 has an average particle size of 0.3 μm,
The emulsion was a monodisperse emulsion consisting of almost perfect 24-sided grains having a variation coefficient of 12% in grain size distribution.

Next, in the above-mentioned method for producing EM5, from (Solution A-3) and (Solution B-6) to 4-hydroxy-6-methyl-1,
A comparative emulsion EM6 was prepared in the same manner as EM5 except that 3,3a, 7-tetrazaindene was removed.

As a result of observation with an electron microscope, EM6 has an average particle size of 0.3 μm,
It was a monodisperse emulsion consisting of almost perfect cubic grains with a variation coefficient of 12% in the grain size distribution.

The above emulsions EM5 and EM6 were subjected to gold-sulfur sensitization, 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer, and sensitizing dyes were added as shown in Table-8. Added and spectrally sensitized. Next, 700 mg of the compound represented by the following structural formula (A) per 1 mol of AgX, 400 mg of sodium p-dodecylbenzenesulfonate, 2 g of styrene-maleic acid copolymer polymer and styrene-butyl acrylate-acrylic acid copolymer latex (average particle size) Diameter
0.25 μm) 15g is added, Ag amount 3.5g / m ² , gelatin amount 2.00
It was coated on the base so as to be g / m ² . At that time as spreading agent so that gelatin amount 1.0 g / m ² 1-decyl-2-
Sodium (3-isopentyl) succinate-2-sulfonate 30 mg / m ² and formalin 25 mg / m ² as a hardening agent
A protective layer containing m ² was applied simultaneously in multiple layers.

The above sample was exposed with a tungsten light source using an optical wedge, and the following development processing was performed using an automatic processor GR-27 (manufactured by Konishi Rokusha Kogyo Co., Ltd.).

<Development processing> Development 28 ℃ 30 seconds Fixing 28 ℃ 20 seconds Water washing 20 minutes at room temperature Developer formulation (Composition A) Pure water (ion exchanged water) 150ml Ethylenediaminetetraacetic acid disodium salt 2g Diethylene glycol 50g Sodium sulfite (55% W / V Aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-Methylbenzotriazole 200 mg 1-Phenyl-5-mercaptotetrazole 30 mg Potassium hydroxide Amount to make the pH of the used solution 10.4 Potassium bromide 4.5 g (Composition B) Pure water (ion exchange water ) 3 ml Diethylene glycol 50 mg Ethylenediaminetetraacetic acid disodium salt 25 mg Acetic acid (90% aqueous solution) 0.3 ml 5-Nitroindazole 110 ml 1-Phenyl-3-pyrazolidone 500 mg Dissolve the above composition A and composition B in water 500 ml in this order when using the developer. 1 was used after finishing.

Fixer formulation (Composition A) Ammonium thiosulfate (72.5% aqueous solution) 240ml Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid 6g Sodium citrate dihydrate 2g Acetic acid (90% W / W aqueous solution) 13.6ml (Composition B) ) Pure water (ion-exchanged water) 17 ml Sulfuric acid (50% W / W aqueous solution) 4.7 g Aluminum sulfate (Al ₂ O ₃ equivalent content is 8.1% W / W aqueous solution) 26.5 g When using the fixer, add the above to 500 ml water. Composition A and composition B were melted in this order, and finished to 1 before use. The pH of this fixer is about 4.
Was 3.

The transmission density of the obtained sample was measured with a densitometer PDM-65 (manufactured by Konishi Rokusha Kogyo Co., Ltd.) to determine fog and sensitivity (reciprocal of exposure amount required to give fog + 1.0 density). The results are shown in Table-8.

From Table-8, the sample in which the silver halide grains according to the present invention and the sensitizing dye are combined has a higher spectral sensitization sensitivity for the same silver halide grain size in the silver chlorobromide emulsion as compared with the comparative sample. I understand.

〔The invention's effect〕

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

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroshi Otani 1 Sakura-cho, Hino-shi, Tokyo Konishi Roku Photo Co., Ltd. Kayoko Yasuda (56) References JP-A-61-83531 (JP, A) Kaisho 62-196646 (JP, A)

Claims (1)

[Claims] 1. A sensitization represented by the following general formula (1) having a (nn1) crystal plane (n ≧ 2, n is a natural number) on the surface of a silver halide grain and having a reduction potential lower than −1.2V. A silver halide photographic light-sensitive material having a silver halide emulsion layer having silver halide grains spectrally sensitized by a dye. General formula (1) [In the formula, Z ₁ and Z ₂ each represent an atomic group necessary for forming a heterocycle, R represents an alkyl group which may be substituted with a sulfo group, and p and q each represent 1 or 2. Represent. ]