JPH0644136B2 - (110) surface silver halide photographic light-sensitive material which also uses a sensitizing dye - Google Patents

Description

Detailed Description of the Invention

(Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material, and more specifically, it regulates the crystal planes of silver halide grains contained in the emulsion layer of the light-sensitive material and the sensitizing dye adsorbed on the crystal surface. The present invention relates to a silver halide photographic light-sensitive material.

[Prior art]

 Higher than the photographic characteristics of silver halide emulsions for photography in recent years.
Sensitivity, excellent graininess, high sharpness, low fog density, high
Very high standards such as the highest concentration were required.
It was The improvement of these characteristics is due to the silver halide contained in the emulsion.
It results in how to increase the sensitivity of particles to light. Immediately
If you can arrange the particles with high sensitivity, you will feel the required sensitivity.
Miniaturizing silver halide grains to obtain optical materials
It is possible to improve the image quality, fog, etc.
As is well known. Conventionally, the request for higher sensitivity is mainly odorous.
It was for a negative photosensitive material using a silver halide emulsion.
However, recently, the color palette which has been regarded as good because of its relatively low sensitivity
For photographic materials using silver chlorobromide emulsions for supermarkets, etc.
There is a strong demand for higher sensitivity to improve work efficiency.
, Silver halide grains having various silver halide compositions
Status of continuous development of high sensitivity technology applicable to
Is. In response to these requirements, iodobromide is used as a high-sensitivity emulsion.
Emulsion containing less than 15 mol% of silver iodide, which is silver, is well known.
There is. Conventional methods for preparing these emulsions are
PH conditions such as ammonia method, neutral method, acidic method, pAg condition
Control method, single jet method as a mixing method,
The double jet method and the like are known. Based on these well-known techniques, higher sensitivity and fine grain
More precise technology to achieve high performance, high sharpness and low fog
Means have been developed and in the iodobromide emulsion, crystal habit and particle size distribution
Of course, the silver iodide content in individual silver halide grains
Emulsions whose concentration distribution is controlled have been studied. Most orthodox to achieve high photographic performance as mentioned above
Another method is to increase the quantum efficiency of silver halide grains.
However, the quantum efficiency is theoretically calculated and the effect of particle size distribution is considered.
The research done, for example, on the progress of photography in 1980 Tokyo Shin
Proceedings of Podium "Interactions Bitouy"
Light and Materials for Fotog
Raffic Applications “See page 91
It According to this research, a monodisperse emulsion with a narrow particle size distribution
Use is effective for improving quantum efficiency
Is suggested. Furthermore, chemical enhancement performed after grain formation
In the process of feeling
We believe monodisperse emulsions are advantageous for achieving sensitivity.
To be To industrially produce a monodisperse emulsion, JP-A-55-48521
Strict pAg and pH control as described in
And the theoretically determined silver and halogen ions
Control of the feed rate to the reaction system and sufficient agitation are required.
It Silver halide grains produced under these conditions are
It has a rectangular, octahedral or 14-sided shape
It is known that it is made up of normal crystals and can be made highly sensitive.
Has been. In addition, it is special as a silver halide grain that can obtain higher sensitivity.
In Japanese Patent Application No. 59-158111, iodobromide having (110) planes is disclosed.
Silver particles are disclosed, and in Japanese Examined Patent Publication No. 55-42737,
Rhombic dodecahedron with (110) plane as less fog
Photographic emulsions containing silver chlorobromide grains are disclosed. In addition, in JP-A-60-222842, there is less fog.
The surface is a (110) crystal plane made of silver iodobromide.
Silver halide grains are disclosed. As described above, the relationship between the crystal plane of silver halide grains and photographic characteristics is
There is a very deep contact, and as an adsorption surface for the sensitizing dye.
It seems that there is a decisive influence, and the relationship hidden between them is updated.
A more detailed study will show more excellent characteristics.
There is potential for silver halide emulsions to be developed. On the other hand, there are many conventional sensitizing dyes used for spectral sensitization.
Have been improved, and oxygen, sulfur, selenium, and other oxygen groups have been studied.
A sensitizing dye containing an element and nitrogen in the same ring is a silver halide.
It has been widely used in the field of photography. JP-A-60-78444
And as described in JP-A-60-78445.
Substitution of tellurium for offspring gives maximum bathochromic effect
Shift can be generated, and good sensitization is given. However
However, both nitrogen atoms in the dye mother nucleus have alkyl groups.
When introduced, is susceptible to interaction with additives,
There are drawbacks such as limited use conditions and color contamination. Well
In addition, the sulfoalkyl group is attached to both nitrogen atoms of the dye nucleus.
Introducing a group or alkyl group is difficult to dissolve,
Special solvent such as lumamide or fluorinated alcohol
Medium must be used and the amount of solvent for dissolution
Therefore, it is not suitable for recent high speed coating. In addition, both nitro groups in the dye mother nucleus have sulfo groups introduced respectively.
Adds water-solubility when added, and improves removal after processing
On the other hand, the effect of
Decrease sensitivity during storage and keep in high temperature and high humidity conditions.
If there is, decrease in sensitivity, increase in fog,
The diffusion phenomenon appears. In addition, sensitivity changes in emulsion coating solutions
The shortcoming of bringing about a change was found. Therefore, improvement of these defects has been desired. Furthermore, in image quality improvement thin film and silver saving from the viewpoint of resource saving
Halo consisting of (110) and (111) faces of silver halide crystals.
The maximum concentration of silver genide grains including the adsorption of sensitizing dyes is
Not enough. (Object of the invention) The object of the present invention is to provide crystals which are convenient for chemical and optical sensitization.
Containing silver halide grains with a face
High density and low coating amount of silver with high sensitivity and high illumination
And providing a silver halide photographic light-sensitive material. Still another object is silver halide milk as a raw material of the light-sensitive material.
In the provision of agents. (Structure of the Invention) The above-described object of the present invention is such that the surface of the silver halide grain is substantially
Is a (110) crystal plane composed of silver bromide or silver iodobromide.
The sensitization of silver genide grains represented by the following general formula (I) or (II)
At least one of the dyes and at least one of the sensitizing dyes represented by the following general formula (III)
Containing an emulsion spectrally sensitized by the combined use of
Halo characterized by having at least one silver emulsion layer
It is achieved by a silver photographic light-sensitive material. General formula (I)Where R₁To form an alkyl group or holopolar
Represents the atomic group of. R_Two, R_ThreeRepresents an alkyl group. R
_Four, R₅, R₆, R₇Are hydrogen atom and halogen respectively
Atom, alkoxy, alkyl, alkoxycarbonyl,
Represents an aryl, carbamoyl, and hydroxy group. X
⁻ ₁Represents an anion, and q represents 1 or 2. R_Four, R₅, R₆, R₇May be the same or different. ] General formula (II)Where R ′₁Forms an alkyl group or holopolar
Represents an atomic group for. R '_Two, R '_ThreeRepresents an alkyl group
You R₈And R₉Or R₉And R₁₀Is R₁₀And R₁₁Is
Each is bonded to form a condensed ring. R₁₂，
R_Thirteen, R₁₄, R₁₅Are hydrogen atom and halogen
Atom, and also alkoxy, alkyl, alkoxycarbo
Represents each group of nyl and arylcarbamoyl. Also R₁₂When
R_ThirteenOr R_ThirteenAnd R₁₄Or R₁₄And R₁₅Is that
They may combine with each other to form a condensed ring. X_Two ⁻Is anio
And r represents 1 or 2. R₈, R₉, R₁₀，
R₁₁, R₁₂, R_Thirteen, R₁₄, R₁₅Are the same but different
May be. General formula (III)In the formula, X is -0- or -NR_{twenty two}-, Y are -S-, -0- or
Is -NR_{twenty three}Represents- (where R₂₂And R₂₃Is alkyl
Is the base). R ″₁Represents an alkyl group and hydrogen H. R ″_Two, R ″_ThreeRepresents an alkyl group. R when X is -0-
₁₆, R₁₇, R₁₈Is a hydrogen atom, a halogen atom,
Alkoxy, alkyl, alkoxycarbonyl, ally
Lucarbamoyl, hydroxy, carboxy, acylami
No, acyloxy or aryloxycarbonyl groups
Represents Also R₁₆And R₁₇Or R₁₇And R₁₈Is united
To form a condensed ring. When Y is -S- or -0-, R₁₉, R₂₀, R₂₁Is
Each atom of hydrogen and halogen, alkoxy, alkyl,
Alkoxycarbonylaryl, carbamoyl, hydro
Xy, carboxy, acylamino, acyloxy, or
Represents each group of aryloxycarbonyl. Also R₁₉And R
₂₀Or R₂₀And R₂₁Are bonded to form a condensed ring
good. X is -NR_{twenty two}-When R₁₆, R₁₇Is a chlorine atom, R₁₈
Is a hydrogen atom, and Y is -NR_{twenty three}-When R₁₉, R₂₀Is
Chlorine atom R₂₁Represents a hydrogen atom. X_Three ⁻Is an anion
And s represents 1 or 2. R₁₆, R₁₇, R₁₈, R₁₉, R₂₀, R₂₁Is the same
It may be the same or different. Next, the present invention will be described in detail. The silver halide grains according to the present invention have a Miller index (110).
Defined crystal planes consisting essentially of silver bromide and silver iodobromide
It is a particle having. In addition to (110) plane, (100) plane, (111) plane, etc. are present on the surface of particles.
It may exist, but the (110) plane of the total surface area
The ratio is preferably 20% or more, and 80% or more
Is particularly preferable. For the existence and proportion of the (110) plane, see the electron microscope.
It can be known by a method using or a dye adsorption method. The silver halide emulsion of the present invention contains a halo having a (110) plane.
More preferably, the silver genide grains are 30 wt% or more,
It is more preferably 50 wt% or more. In the overall composition of the silver halide grains according to the present invention
Is substantially silver bromide or silver iodobromide, that is, the present invention.
Other than silver bromide and silver iodide, as long as the effect of
The grains may contain silver halide, for example silver chloride.
It is preferable that silver chloride is not present on the surface of the child. Specifically, in the case of silver chloride in the overall composition, the ratio is
5 mol% or less is desirable, and 1 mol% or less
More desirable. The ratio of silver iodide in the silver halide grains relating to the present invention is preferably
It is preferably 0 to 40 mol%, more preferably 0 to 20 mol%.
The range of 0 to 15 mol% is particularly preferable. The silver halide grains according to the present invention have a silver halide composition of
Multiple different layers or phases, such as core and
Core / shell type silver halide grains consisting of several shell layers
May be Silver halide composition inside multi-phase grains
May contain silver chloride, silver bromide and the like. See again
Even if the silver halide composition is uniform in each phase, it continuously transfers to the other phase.
It may change. The preferred form of the silver halide according to the present invention is the inside of the grain.
It has a high silver iodide content. That is, the particle surface
Shells with higher silver iodide content than silver iodide content
Or may have a core inside the particle
Silver halide grains. The grain size of the silver halide grain according to the present invention is not particularly limited.
The present invention is at least 0.1 to 3.0 μm.
Is also effective. In the present specification, silver halide
Particle size is expressed by the length of one side of the cube equal to its volume
Be done. The silver halide grain according to the present invention is usually a dispersion of gelatin or the like.
Made in a form dispersed in a medium, that is, a form called an emulsion
Created and used again. Particle size of the group of particles at this time
The distribution can be monodisperse or polydisperse, or a mixture of these.
Distribution, and can be selected appropriately according to the application etc.
Wear. As in the present invention, the grain surface has a (110) crystal plane substantially
Contains silver halide grains composed of silver bromide or silver iodobromide.
By using the silver halide photographic emulsion which has
Conventional silver bromide emulsion without (110) crystal plane or silver iodobromide
As various photographic emulsions that could not be obtained with emulsions
You can now get the benefits of. For example, silver bromide having a (110) face and / or a (100) face
Fog can be suppressed compared to emulsions or silver iodobromide emulsions
it can. Has (111) face and / or (100) face but does not include (110) face
Higher sensitivity than silver bromide emulsion or silver iodobromide emulsion
be able to. Silver halide milk having (111) plane and / or (100) plane
It has a completely different spectral sensitizing ability from the agent. For example spectral increase
The spectral sensitivity spectrum when feeling can be made rectangular. did
Therefore, the color reproducibility is remarkably improved, and the color mixture is prevented.
Can be improved. Since the spectral sensitivity spectrum is rectangular, it can be
Therefore, LED (light emitting diode) whose wavelength is easily shifted
Stable exposure can be performed even when exposure is performed using. Production of silver halide grains having (110) plane according to the present invention
To achieve this, Japanese Patent Application Laid-Open No. 60-222842 or Japanese Patent Application No. 59-158111
Can be used. That is, in JP-A-60-222842, silver halide grains
A halogen whose surface consists essentially of silver bromide or silver iodobromide.
In the method for producing a silver halide photographic emulsion, a hydrophilic protective colloid is used.
Coexist with a compound that promotes the development of the (110) crystal plane.
Of silver halide grains in an aqueous medium.
Depending on the manufacturing method of the silver halide photographic emulsion,
It has been shown that silver halide grains with (0) faces can be produced.
Has been. Substances that promote the development of the (110) crystal plane (hereinafter referred to as the crystal control compound
A clear chemical classification of
Specifically, mercaptoazoles are preferable, and mercaptoazoles are particularly preferable.
Captotetrazoles and mercaptothiadiazoles
preferable. More specifically, compounds represented by the following general formulas (1) to (V)
Compounds are preferred. (I)Where R₁Is a hydrogen atom, an optionally substituted alkyl group
(Total carbon number 15 or less), optionally substituted aryl group (total
Represents a heterocyclic group having 20 or less carbon atoms). (II)Where R_TwoIs a hydrogen atom or an optionally substituted alkyl
Represents a group (total carbon number of 12 or less). (III)Where R_ThreeIs an optionally substituted alkyl group (total
C10 or less) or optionally substituted amino group (total carbon
Represents a prime number 10 or less). (IV)Where R_FourIs an optionally substituted alkyl group (total
C10 or less) or optionally substituted aryl group (total
It has 10 or less carbon atoms). (V)Where R₅, R₆Is an optionally substituted alkyl group (total
Represents an optionally substituted amino group having 10 or less carbon atoms)
You The crystal control compounds (I) to (V) are capable of forming silver halide grains.
Before completion (including before completion of Ostwald ripening)
If so, it may be added at any time. Where the particle formation
Start adding silver and halogen ions during the period
From among the generated precipitated embryos.
Crystal nucleus generation period (nucleation period) and subsequent new
Particles grow without substantially generating new crystal nuclei
There is a period (period of grain growth). It is preferably added during the growth of silver halide grains. Special
In addition, after completion of nucleation (nucleation) and before completion of particle growth,
Addition of crystal control compounds (I) to (V) produces a large amount of fine particles.
It is preferable in limiting the growth. On the contrary, if nucleation occurs
Or earlier, when using the crystal control compound (I) ~ (V),
Preferable in that silver halide grains composed of fine grains can be prepared.
Good The crystal control compounds (I) to (V) already exist in the reaction vessel.
It may be left in place, or added after the start of precipitation.
Good. At this time, it may be added directly, or it may be dissolved in water or an organic solvent.
A solvent such as a medium (eg, methanol, ethanol, etc.)
You may add as a solution consisting of. Also, the crystal control compounds (I) to (V) should be added individually to the reaction vessel.
Alternatively, a silver supply solution (for example, silver nitrate aqueous solution) may be used.
Liquid) or halogen supply solution (eg halide solution)
It may be added together with the reaction vessel. Crystal control compound (I)
When adding ~ (V), even if added continuously,
May be added in a positive manner. Increased surface area of silver halide grains
The amount of the crystal control compound of the present invention is increased accordingly (eg,
For example, increase the amount of solution added or increase the concentration.
In order to effectively control the crystal plane.
preferable. The (110) plane of the silver halide grain having the (110) plane of the present invention
Regarding the proportion, the addition of the crystal control compounds (I) to (V)
You can easily change the proportion by changing the amount.
You can For example, the amount of the crystal control compound (I) to (V) added
The ratio of (110) plane increases with the increase of
In the region, the ratio of (110) plane becomes maximum,
If the amount of the compound added exceeds the range described below (1
The ratio of (00) plane to (110) plane increases. The addition amount of the crystal control compounds (I) to (V) depends on the compound used.
Type, emulsion preparation conditions, halogen composition, grain size, etc.
5 × per mol of silver halide, depending on various conditions
Ten^-Five~ 5 x 10^-2Mol is preferred, 1 × 10^-Four~ 1 x 10^-2Mo
Is more preferable, especially 3 × 10^-Four~ 6 x 10^-3Mol is good
Good On the other hand, Japanese Patent Application No. 59-158111 discloses that silver bromide having a (110) surface.
Alternatively, as a method for producing silver iodobromide grains, a protective colloid
Water-soluble silver salt solution and water-soluble halide solution in the presence of
In the process of mixing silver halide to form silver halide grains
The period during which at least 30 mol% of total silver halide is produced
Control the pAg of the emulsion between 8.0 and 9.5, and
In the meantime, as a crystal control compound, a compound represented by the general formula (VI), (VII), (VIII) or
Or a compound represented by (IX) and a compound represented by the general formula (X)
At least selected from compounds having repeating units
Is characterized in that one compound is contained in the above emulsion.
How to do is shown. General formula (VI)General formula (VII)General formula (VIII)General formula (IX)General formula (X)Where R₁₁, R₁₂And R_ThirteenAre the same but different
May be present, hydrogen atom, halogen atom, amino group,
Amino group derivative, alkyl group, alkyl group derivative,
Aryl groups, derivatives of aryl groups, cycloalkyl groups,
Cycloalkyl group derivative, mercapto group, mercapto
Group derivative or -CONH-R₁₄(R₁₄Is a hydrogen atom,
Alkyl group, amino group, alkyl group derivative, amino group
Derivative, halogen atom, cycloalkyl group, cycloal
Kill group derivative, aryl group or aryl group derivative
Represents ), And R₁₅Is a hydrogen atom or an alk
Represents a group, R₁₁And R₁₂Are joined to form a ring (for example,
5 to 7-membered carbocycle, heterocycle) may be formed, and X is 1
Compound represented by general formula (VI), (VII), (VIII) or (IX)
A monovalent group obtained by removing one hydrogen atom from (for example, the above general formula
R in (VI) to (IX)₁₁~ R_ThirteenOr OH part
, One hydrogen atom is excluded), and J is a divalent chain.
Represents a group. Addition amount of the crystal control compounds (VI) to (X) in the present production method
Is the desired silver halide grain size, emulsion temperature, pH, pAg iodide.
Although it depends on the manufacturing conditions such as the content of silver halide,
10 per mol of silver halide^-Five~ 2 x 10^-1Molar range is preferred
Good The tetrazaindene compound is represented by the general formula (X).
In the case of a compound having a unit
The number of moles of the indene portion is the addition amount. Preliminarily protected as a method of adding the crystal control compounds (VI) to (X)
Method of adding in colloidal solution, silver halide grains
Method of adding gradually as the growth of
There are ways to do it. In the present manufacturing method, the crystal nuclei are grown mainly,
Size and grain distribution are fixed, and subsequent formation of emulsion grain formation
Uses a seed emulsion consisting of the primary crystalline particles (seed particles)
Then, silver halide is further generated on the surface of the grain
May grow. If seed particles are used, their halogen
The silver halide composition will form the silver halide grains of the present invention.
It only needs to be within the range. The period for controlling pAg is the period during which silver halide is produced.
It is optional within the range of
May be midway or end. Also, this period is continuous
It is preferable that the period of time is
It may be intermittent as long as it does not exist. PA in this period
g is preferably 8.0 to 9.5, more preferably 8.4 to 9.
Is 2. And during this period, the pH of the emulsion is in the range of 7-10
It is preferable to keep. PAg of silver halide outside this period
Is appropriately in the range of 4 to 11.5, and preferably in the range of 6 to 11.
The pH is suitably in the range of 2 to 12, preferably
It is in the range of 5-11. In this production method, a halogen which produces silver halide is used.
The process of forming silver halide grains is carried out in the presence of ammonia.
In addition, the ammoniacal silver nitrate aqueous solution and the halide aqueous solution
Is preferably added by the double jet method. Also,
No new crystal nuclei are generated during this grain growth process
It is better to add silver and halide solutions so that
Yes. The characteristics of this manufacturing method are described in Japanese Patent Application No. 59-158111.
As described above, a silver halide emulsion having excellent monodispersity is provided.
To be able to pay. As described above, the silver halide grains having the (110) plane according to the present invention
The outline of the manufacturing method was described. Details are described in JP-A-60-222842.
No. 59-158111. The silver halide grain having (110) plane according to the present invention has a
During the process of silver halide grain formation or physical ripening,
Domium salt, zinc salt, lead salt, thallium salt, rhodium salt or
Or its complex salt, rhodium salt or its complex salt, iron salt or
An iron complex salt, a gold salt, a gold complex salt and the like may coexist. Well
In addition, the addition amount of these is small depending on the target photosensitive material.
However, it may be a large amount. To remove soluble salts from the emulsion after grain formation, a
You can also use the Nudel water washing method, which is performed by gelling ratin.
Inorganic salts, anionic surfactants, anionic
Polymer (eg polystyrene sulfonic acid), or
Gelatin derivatives (eg acylated gelatin, carbamoy
Sedimentation method (floccure)
Method) may be used. The emulsion grains according to the present invention contain silver iodide in the vicinity of the surface.
The lower the percentage, the more desirable it is, and it must consist essentially of silver bromide.
And are preferred. Containing such silver halide grains
Emulsion has high sensitization efficiency, especially surface latent image type emulsion is obtained.
Suitable for And, as a preferred embodiment of the silver halide grain of the present invention,
Include silver iodide in the vicinity of the surface of the grain in an amount of 0 to 4 mol%,
Silver halide containing 2 to 15 mol% of silver iodide inside
Is to be. Having core / shell type silver halide grains in the present invention
When using a silver halide emulsion, a monodisperse halogen
Coating silver with a shell as a core
It may be manufactured by To produce monodisperse silver halide grains of said core
Is determined by the double jet method while keeping pAg constant.
Particles of desired size can be obtained, eg monodisperse
The silver halide emulsion of is described in JP-A-54-48521.
The applied method can be applied. For example, iodobromide
Potassium-gelatin solution and ammoniacal silver nitrate solution
And are added to an aqueous gelatin solution containing silver halide seed grains.
By the method of adding the rate as a function of time
To manufacture. At this time, the time function of the addition rate, pH, pAg,
By appropriately selecting the temperature, etc., it is possible to obtain high monodispersity.
Silver halide grains can be obtained. Regarding the method for producing the core / shell type silver halide grains described above,
For example, West German Patent 1,169,290 and British Patent 1,02
7,146, JP-A-57-154232, JP-B-51-1417, etc.
See the article. Next, the sensitizing dye according to the present invention will be described. Above sensitization
The dye is selected from the general formula [I] or [II]
And at least one selected from the above general formula [III]
One of the sensitizing dyes contained in each general formula can be used in combination.
A specific example is shown. [I] -1[I] -2[I] -3[I] -4[I] -5[I] -6[I] -7[I] -8[I] -9[I] -10[I] -11[I] -12[I] -13[I] -14[I] -15[I] -16[I] -17Specific examples of compounds represented by the general formula [II] [II] -1[II] -2[II] -3[II] -4[II] -5[II] -6[II] -7[II] -8[II] -9Specific examples of the compound represented by the general formula [III] [III] -1[III] -2[III] -3[III] -4[III] -5[III] -6[III] -7[III] -8[III] -9[III] -10[III] -11[III] -12[III] -13[III] -14[III] -15[III] -16[III] -17[III] -18[III] -19[III] -20[III] -21[III] -22[III] -23[III] -24[III] -25[III] -26[III] −27[III] −28[III] −29In the above general formulas [I], [II] and [III] according to the present invention,
For the synthesis of the compounds shown, refer to the following patents and documents.
Can be done with British patents 625,245, 654,690, 841,119, France
Patents 757,767, U.S. Patents 1,846,302, 2,345,094
No., No. 2,369,646, No. 2,378,783, No. 2,385,815,
2,478,366, 2,610,121, 2,238,231, 2,2
13,995, 2,503,776, JP-A-47-9678, 60-784
No. 45, Journal of the American Chemical
Society, Vol. 67, 1875-1889 (1945), FM
By Hama, Cyanine, Soybean and Relayedt
Compounds (1964 Inter Science Publicity)
Journal, 68, 191-194 (1948). The sensitizing dye used in the present invention is a sensitizing dye per mol of silver halide.
1 x 10 each^-FiveMol ~ 5 x 10^-3Mol, preferably 1 ×
Ten^-FiveMol ~ 2.5 x 10^-3Mol, particularly preferably 4 × 10^-FiveMo
Le ~ 1 x 10^-3It is contained in a silver halide photographic emulsion in a molar ratio.
To be The addition of the sensitizing dye used in the present invention to the emulsion can be carried out in the art.
A method well known by those skilled in the art can be used. For example, these sensitizing dyes may be directly dispersed in the emulsion.
Yes, or pyridine, methyl alcohol,
Chill alcohol, methyl cellosolve, acetone, or
Dissolved in a water-soluble solvent such as a mixture of these, or
Dilute with water or dissolve in water and
Can be added to the emulsion in the form of a sensitizing dye.
The time may be any time during the emulsion manufacturing process,
It is preferable during or after the chemical sensitization. Representative specific examples of the sensitizing dye used in the present invention are given below.
However, the sensitizing dye according to the present invention is not limited to these.
Not of. The silver halide grains according to the present invention are
The various chemical sensitization methods applied can be applied. Sanawa
Active gelatin; water-soluble gold salts, water-soluble platinum salts, water-soluble salts
Radium salt, water-soluble rhodium salt, water-soluble iridium salt, etc.
Noble metal sensitizers; Sulfur sensitizers, selenium sensitizers, etc.
Gen sensitizer; independently by chemical sensitizer such as reduction sensitizer
Alternatively, they can be used in combination for chemical sensitization. The chalcogen sensitizer is a sulfur sensitizer, a selenium sensitizer,
It is a general term for tellurium sensitizers.
A sulfur sensitizer and a selenium sensitizer are preferable. Known sulfur sensitizers can be used.
For example, thiosulfate, allylthiocarbamide, thiourine
Element, allyl isothiocyanate, cystine, p-toluene
Examples thereof include thiosulphonic acid salt and rhodanine. So
Other, U.S. Patents 1,574,944, 2,410,689, 2,278,
947, 2,728,668, 3,501,313, 3,656,955
No. 1, West German Published Application (OLS) 1,422,869, JP-A-56-24937
No., 55-45016 and other sulfur sensitizers are also used
You can The amount of sulfur sensitizer added depends on the sensitivity of the emulsion.
The amount is sufficient to effectively increase. This amount is nitrogen-containing
Addition amount of elemental heterocyclic compound, pH, temperature, silver halide grains
Over a considerable range under various conditions such as the size of
Varies, but as a guide, per mol of silver halide
About 10^-7Mole to about 10^-1A molar amount is preferable. Selenium sensitizer can be used instead of sulfur sensitizer
However, as a selenium sensitizer, allyl isoselenocyanate is used.
Aliphatic isoselenocyanates such as selenium urea
, Selenoketones, selenoamides, selenocarvone
Acids and esters, selenophosphates, diethyl
Such as selenide and diethyl diselenide
Can be used, and specific examples thereof can be found in US Pat.
574,944, 1,602,592, 1,623,499
ing. The amount added varies over a wide range, similar to the sulfur sensitizer
However, as a guide, it is about 10 per mol of silver halide.^-7Mo
Le from 10^-1A molar amount is preferable. In the present invention, as the gold sensitizer, the valence of gold is +1
May be +3 valent and various gold compounds may be used. Typical
Examples include chloroaurate, potassium chloroaurate,
Auric trichloride, potassium auric thioshie
Anate, potassium iodoaurate, tetracyanooate
-Ric acid, ammonium aurothiocyanate,
Pyridyl trichloro gold etc. are mentioned. The amount of gold sensitizer added varies depending on various conditions.
About 10 per mol of silver halide^-7Mol to 10^-1Mole
The range of is preferable. Remove gold ions from gold-gelatinate and
Preferred as a compound that promotes the adsorption of gold ions on silver halide grains.
A complex salt of Rh, Pd, Ir, Pt, etc. is effective. Specific compounds include (NH_Four)₂[PtC_Four], (NH_Four)
₂[PdC_Four], K₃[IrBr₆], (NH_Four)₃[RhC₆] 12H
₂O, etc., but particularly preferred is tetrachloropa
Ammonium radium (II) (NH_Four)₂[PdC_Four]
It The stoichiometric ratio (molar ratio) to the gold sensitizer is 10
The range of up to 100 times is preferable. The timing of addition may be at the beginning of the chemical sensitization, during the progress, or after the end.
However, it is preferable that the chemical sensitization is in progress,
Particularly preferably at the same time as before or after the addition of the gold sensitizer
Is. In the present invention, reduction sensitization can also be used in combination.
is there. The reducing agent is not particularly limited, but a known chloride
Istin, thiourea dioxide, hydrazine derivative, polyamine
Etc. The time for reduction sensitization is during the growth of silver halide grains.
However, chalcogen sensitization, gold sensitization and Rh, Pd, Ir, P of the present invention
Sensitization with compounds selected from precious metal compounds such as t
It is preferable to carry out after completion of. The silver halide grains used in the present invention are halogenated.
The chemical sensitization was carried out in the presence of a silver halide solvent.
It is preferable because high sensitivity can be achieved. The silver halide solvent used in the present invention is
U.S. Pat.Nos. 3,271,157, 3,531,289, 3,574,628, and JP
(A) Organic thiols described in JP-A-54-1019 and JP-A-54-15891
Ethers, JP 53-82408, JP 55-77737, JP 55-2
(B) Thiourea derivative described in 982, JP-A-53-144
(C) Oxygen or sulfur atom and nitrogen atom described in No. 319
Silver halide solution containing a thiocarbonyl group sandwiched between molecules
Agent, (d) imidazole described in JP-A-54-100717
And the like, (e) sulfite, (f) thiocyanate and the like. Particularly preferred solvents are thiocyanate and tetra
There is methylthiourea. Also, the amount of solvent used is different
It depends on, but in the case of thiocyanate,
The preferred amount is in the range of 5 mg to 1 g per mol of silver halide.
is there. The silver halide grains used in the present invention have a manufacturing process.
Prevents fogging during storage or development
Or chemical sensitization for the purpose of stabilizing photographic performance.
Various compounds may be included at the end. For example, Azo
Such as benzothiazolium salt, nitroindazo
, Nitrobenzimidazoles, chlorobenzii
Midazoles, bromobenzimidazoles, mercaps
Tothiazoles, mercaptobenzimidazoles,
Minotriazoles, benzotriazoles, nitrobe
Nzotriazoles, mercaptetrazoles (especially 1
-Phenyl-5-mercaptotetrazole), etc.
Mercaptopyrimidines, mercaptotriazines, eg
For example, thioketo compounds such as oxazoline thione,
Is benzenethiosulfinic acid, benzenesulfinic acid,
Benzenesulfonic acid amide, hydroquinone derivative,
Minophenol derivatives, gallic acid derivatives, ascorbin
Known as antifoggants or stabilizers such as acid derivatives
Many of the named compounds can be added. These changes
The compound is preferably added during chemical sensitization or before coating. As a binder for the silver halide emulsion according to the present invention,
Various hydrophilic colloids including ratin are used. Ze
Not only gelatin but also derivative gelatin is included as ratin.
Included, as derivative gelatin, gelatin acid anhydride and
Reaction product of gelatin, reaction product of gelatin and isocyanate
Or a compound containing gelatin and an active halogen atom
The reaction product and the like are included. Anti-gelatin here
Examples of the acid anhydride used in the reaction include maleic anhydride.
Acid, phthalic anhydride, benzoic anhydride, acetic anhydride, anhydrous isa
Tonic acid, succinic anhydride, etc. are included, and isocyanate compounds
Are, for example, phenyl isocyanate, p-promo
Phenyl isocyanate, p-chlorophenyl isocyanate
Nate, p-tolyl isocyanate, p-nitrophenyl
Ruisocyanate, naphthyl isocyanate, etc.
be able to. And a compound having an active halogen atom
For example, benzenesulfonyl chloride, p-medium
Toxybenzenesulfonyl chloride, p-phenoxy
Benzenesulfonyl chloride, p-Promobenzenes
Rufonyl chloride, p-toluenesulfonyl chloride
De, m-nitrobenzenesulfonyl chloride, m-su
Rufobenzoyl dichloride, naphthalene-β-sulfo
Nyl chloride, p-chlorobenzenesulfonyl chloride
Id, 3-nitro-4-aminobenzenesulfonyl chloride
Ride, 2-carboxy-4-promobenzenesulfoni
L-chloride, m-carboxybenzenesulfonyl chloride
Ride, 2-amino-5-methylbenzenesulfonyl chloride
Loride, phthalyl chloride, p-nitrobenzoyl
Chloride, benzoyl chloride, ethyl chlorocar
Bonates, furoyl chloride and the like are included. Also hydrophilic colloids for making silver halide emulsions
As the above, derivative gelatin as described above and ordinary photographic emulsions
In addition to ratin, colloidal albumin and cold
Heaven, gum arabic, dextran, alginic acid, for example
Cellulose hydrolyzed to an acetyl content of 19-26%
Cellulose derivatives such as acetate, polyacrylic amine
, Imidized polyacrylamide, casein, such as
Nyl alcohol, vinyl cyanoacetate copolymer
Such as urethane carboxylic acid group or cyanoacetyl group
Vinyl alcohol polymer, polyvinyl alcohol,
Polyvinylpyrrolidone, hydrolyzed polyvinyl acetate
Having a vinyl group, a protein or a saturated acylated protein
Polymer obtained by polymerization with
Lysine, polyvinylamine, polyaminoethylmethacrylate
You can also use rate, polyethyleneimine, etc.
It Hardening treatment of the emulsion is carried out according to a conventional method. used
Hardeners are conventional photographic hardeners such as formaldehyde.
Alde such as de, glyoxal, and glutaraldehyde
Hydride compounds and their acetals or
Derivative compounds such as sodium sulfate adduct, methanesulfo
Acid ester compounds, epoxy compounds, aziridine
Compounds, active halogen compounds, maleic imide compounds
Compounds, active vinyl compounds, carbodiimide compounds
Compounds, isoxazole compounds, N-methylol compounds
Object, isocyanate-based compound, or chrome alum,
Inorganic hardeners such as zirconium sulfate can be mentioned.
It The silver halide emulsion of the present invention includes a coating aid, an antistatic agent,
Sliding property improvement, emulsion dispersion, adhesion prevention and photographic property improvement (example
For example, development accelerator, contrast enhancement, sensitization)
Other known surfactants may be included. That is, US Patent 2,
240,472, 2,831,766, 3,158,484, 3,210,1
No. 91, No. 3,294,540, No. 3,507,660, British Patent 1,012,
495, 1,022,878, 1,179,290, 1,198,450
U.S. Patents 2,739,891, 2,823,123, 1,179,29
0, 1,198,450, 2,739,891, 2,823,123,
3,068,101, 3,415,649, 3,666,478, 3,7
56,828, British Patents 1,397,218, 3,113,816, 3,
411,413, 3,473,174, 3,345,974, 3,726,6
No. 83, No. 3,843,368, Belgian Patent No. 731,126, British patent
Xu 1,138,514, U.S. 1,159,825, U.S. 1,374,780, U.S.A.
Patents 2,271,623, 2,288,226, 2,944,900,
3,235,919, 3,671,247, 3,772,021, 3,58
No. 9,906, No. 3,666,478, No. 3,754,924, West German application
Open (OLS) 1,961,683 and JP-A-50-117414, 50-5902
5, No. 40-378, No. 40-379, No. 43-13822
It is listed. For example saponin (steroidal), al
Xylene oxide derivatives (eg polyethylene glycol
Polyethylene glycol / polypropylene glycol
Condensation product, polyethylene glycol alkyl or al
Killaryl ethers, polyethylene glycol s
Tells, polyethylene glycol sorbitan ester
, Polyalkylene glycol alkylamine or
Polyimide oxide adducts of amides and silicones
), Glycidol derivatives (eg alkenyl succinic acid)
Polyglyceride, alkylphenol polyglyceride
De), aliphatic esters of polyhydric alcohols, sugar alky
Esters, also urethanes or ethers
Nonionic Surfactant, Triterpenoid Saponi
Amine, alkyl carboxylate, alkyl benzene sulfone
Acid salt, alkyl naphthalene sulfonate, alkyl sulfuric acid
Esters, alkyl phosphates, N-acyl-
N-alkyl taurines, sulfosuccinates,
Sulfoalkyl polyoxyethylene alkylphenyl ether
Ethers, polyoxyethylene alkyl phosphates
Such as carboxy group, sulfo group, phospho group, sulfur group
Ani containing acid groups such as acid ester groups and phosphoric acid ester groups
On-surfactant, amino acids, aminoalkyl sulfone
Acids, aminoalkyl sulfuric acid or phosphoric acid esters,
Ruquilbetaines, amine imides, amine oxides
Such as amphoteric surfactants, alkylamine salts, aliphatic or
Is aromatic quaternary ammonium salt, pyridinium, imida
Heterocyclic quaternary ammonium salts such as zolium and fats
Sulfonium or sulfonium containing group or heterocycles
Cationic surfactants such as salts can be used. In the silver halide emulsion of the present invention, as a development accelerator,
In addition to the above-mentioned surfactant, West German Application Publication (OLS) 2,002,871,
No. 2,445,611, No. 2,360,878, British Patent No. 1,352,196
Imidazoles and thioethers described in
, Selenoethers, etc. may be contained. Again
Apply light silver halide emulsion to color light-sensitive material
Include a red-sensitive silver halide emulsion according to the present invention and a green-sensitive emulsion.
Cyan and silver halide emulsions adjusted to blue and blue
Includes a combination of magenta and yellow couplers.
Techniques and elements used for color light-sensitive materials
It is sufficient to apply a material, and the coupler has a ballast group in the molecule.
A non-diffusible substance having a so-called hydrophobic group is desirable. Mosquito
The puller is a 4-equivalent or 2-equivalent throat for silver ions.
You can use it here. A colored coupler that also has the effect of color correction
-Or a cap that releases a development inhibitor with development
May be included (so-called DIR coupler). Further
The coupler is such that the product of the coupling reaction is colorless
Any coupler may be used. A known open-chain ketomethylene type coupler is known as a yellow color coupler.
A puller can be used. Benzoyl of these
Combination of acetanilide and pivaloyl acetanilide
The thing is 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 Germany
Patent 1,547,868, West German application publication (OLS) 2,213,461, same
2,219,917, 2,261,361, 2,414,006, 2,26
It is described in No. 3,875. Examples of magenta color couplers include pyrazolone compounds,
Using nazolone compounds, cyanoacetyl compounds, etc.
In particular, pyrazolone compounds are 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,
3,834,908, 3,891,445, West German patent 1,810,464,
West German application publication (OLS) 2,468,665, 2,417,945, 2,4
No. 18,959, No. 2,424,467, and Japanese Patent Publication No. 40-6031
belongs to. Cyan color couplers include phenolic compounds and
A futole compound or the like can be used. Specific examples thereof include U.S. Patents 2,369,929 and 2,434,272,
2,474,293, 2,521,908, 2,895,826, 3,03
4,892, 3,311,476, 3,458,315, 3,476,563
No., No. 3,583,971, No. 3,591,383, No. 3,767,411,
West German application publication (OLS) 2,414,830, 2,454,329, JP
It is the one described in Sho-48-59838. Examples of colored couplers include U.S. Pat.
Issue 2, Issue 2,521,908, Issue 3,034,892, JP-B-44-2016
No. 38-22335, 42-11304, 44-32461, Japanese Patent Application
Sho 49-98469, Sho 50-118029, West German Application Publication (OLS) 2,41
Those described in No. 8,959 can be used. As DIR couplers, US Pat. Nos. 3,227,554 and 3,6
17,291, 3,701,783, 3,790,384, 3,632,34
No. 5, West German Application Publication (OLS) 2,414,006, 2,454,301,
No. 2,454,329, British Patent 953,454, Japanese Patent Application No. 50-146570
Those described in No. can be used. In addition to the DIR coupler, a development control agent is added with development.
A releasing compound may be included in the light-sensitive material, for example
U.S. Patents 3,297,445, 3,379,529, West German application publication (O
LS) 2,417,914 can be used. Other, special
Kaisho 55-85549, 57-94752, 56-65134, 56-1
35841, 54-130716, 56-133734, 56-135841
No. 4, U.S. Patent No. 4,310,618, British Patent No. 2,083,640, Lisa
Reach Disclosure 18360 (1979), 14850 (1980)
Year), 19033 (1980), 19146 (1980), 20525 (1981
Year), 21728 (1982) also use the coupler
be able to. Two or more of the above couplers can be contained in the same layer.
Also, the same compound may be contained in two or more different layers.
Yes. To introduce a coupler into a silver halide emulsion layer, a known method is used.
For example, the method described in U.S. Pat.No. 2,322,027 is used.
Can be For example, phthalic acid alkyl ester (dibutyrate
Ruphthalate, dioctyl phthalate, etc.), phosphoric acid
Stell (diphenyl phosphate, triphenyl phosphate
Acetate, tricresyl phosphate, dioctyl butyl
Phosphate, citric acid, ester (eg acetyl)
Tributyl citrate), benzoic acid esters (eg benzo
Octyl perfume), alkyl amides (eg diethyl laur
Rilamide), etc., or organic with a boiling point of about 30 ° C to 150 ° C
Solvents such as lower alkyl such as ethyl acetate, butyl acetate
L-acetate, ethyl propionate, secondary butyl alcohol
, Methyl butyl ketone, β-ethoxyethyl acetate
After being dissolved in sodium acetate, methyl cellosolve acetate, etc.,
Dispersed in hydrophilic colloid. With the above high boiling point organic solvent
You may mix and use with a low boiling point organic solvent. The coupler has an acid group such as carboxylic acid or sulfonic acid
In some cases, as an aqueous alkaline solution in a hydrophilic colloid
Introduce. These couplers are commonly used in silver halide emulsion layers.
2 x 10 per mole^-3Mole to 5 × 10^-1Mol, preferably
1 x 10^-2Mole to 5 × 10^-1Mol added. The light-sensitive material produced by the present invention is used as an antifoggant.
, Hydroquinone derivatives, aminophenol derivatives,
Contains gallic acid derivatives, ascorbic acid derivatives, etc.
Well, specific examples thereof are U.S. Patents 2,360,290 and 2,336,3.
No. 27, No. 2,403,721, No. 2,418,613, No. 2,675,314
No., No. 2,701,197, No. 2,704,713, No. 2,728,659,
2,732,300, 2,735,765, JP-A-50-92988,
50-92989, 50-93928, 50-110337, Japanese Examined Sho 50-
No. 23813, etc. Diacetyl cellulose, styrene-
Perfluoroalkyl sodium maleate copolymer, supra
Tylene-maleic anhydride copolymer and p-aminobenzene
Alkaline salts of the reaction product with sulfonic acid are effective. Ma
Polymethylmethacrylate, polystyrene
And alkali-soluble polymers. Also
It is also possible to use colloidal silicon oxide. Membrane material
Acrylic latex is added to improve the
Have other ethylene groups such as acid ester, vinyl ester, etc.
And a copolymer with one monomer. gelatin
Examples of the plasticizer include glycerin and glycol compounds.
As a thickener, styrene-sodium maleate can be used.
Copolymer, alkyl vinyl ether-maleic acid copolymer
Examples thereof include polymers. Using the silver halide emulsion prepared as above
As a support for the photosensitive material to be made, for example, a baryta
Paper, polyethylene coated paper, polypropylene synthetic paper, glass
Paper, cellulose acetate, cellulose nitrate
Glass, polyvinyl acetal, polypropylene, such as
Polyester film such as polyethylene terephthalate,
There are polystyrene, etc.
It is appropriately selected according to the purpose of use of the optical material. These branches
The holder is subjected to a subbing process, if necessary. The light-sensitive material prepared using the silver halide emulsion of the present invention is
After exposure, it may be subjected to development processing by a known method usually used
You can Black and white developers are hydroxybenzenes, aminopheno
Alkaline-soluble, including developing agents such as
Liquid, other alkali metal sulfites, carbonates,
Can contain bisulfite, bromide, iodobromide, etc.
It When the light-sensitive material is for color, it is usually used.
Color development can be performed by the color development method. In the inversion method
Develop with black and white negative developer first, then give white exposure
Alternatively, it may be treated with a bath containing a fog agent, and the color
Color development is performed with an alkaline developer containing an image main agent. Processing method
There are no particular restrictions on
However, as a typical example, after color development,
Bleach-fixing treatment, washing with water and stabilizing treatment if necessary
Method, or after color development, separate bleaching and fixing
The method of washing with water and stabilizing treatment as needed
Can be applied. The light-sensitive material according to the present invention has high sensitivity and good fog from low fog.
It has a long shelf life, especially stability against heat
Applicable to For example, general black and white, X ray, color
, Infrared, micro, silver dye bleaching method, reversal, expansion
It can be used for various applications such as a dispersion transfer method. When applied to multi-layer color light-sensitive materials,
Various well-known layer constructions, namely forward and reverse layers.
It can be applied to any other layer structure.

【Example】

Next, the present invention will be specifically described with reference to examples. An emulsion EM-2 having a (111) plane having the same average grain size and grain size distribution as the emulsion EM-1 made of silver halide having a (110) plane of silver iodobromide according to the present invention is described below. Prepared as per. : Emulsion EM-1: A seed emulsion containing 0.29 mol of regular octahedral silver bromide grains having an average grain size of 0.68 μm was dispersed in 1000 m of distilled water (containing 30 m of 25% ammonia), and then 1-phenyl-5-mercaptotetrazole. Add 75% of 0.1% methanol solution to 50
1000 m of 0.47 mol / silver nitrate aqueous solution at 0 ° C and a mixed aqueous solution of potassium bromide and potassium iodide containing 5 mol% potassium iodide were used to control pAg10.
It was manufactured by adding for 40 minutes while controlling to 0. Then, after desalting by a conventional method, gelatin was added and redissolved. As a result of electron microscopic observation, the silver iodobromide grains of EM-1 were almost perfect rhombohedral dodecahedrons composed of (110) crystal faces. Emulsion EM-2: Emulsion EM-2 was produced in exactly the same manner as in the above-mentioned production method of EM-1, except that the same amount of methanol was added instead of the 0.1% 1-phenyl-5-mercaptotetrazole aqueous solution. As a result of electron microscope observation, the silver iodobromide grains of EM-2 were
It was a nearly perfect octahedron composed of (111) crystal faces. Dyes in the amounts shown in Table 1 were added to the emulsions EM-1 and EM-2, and chemical sensitization was appropriately carried out by a usual method to obtain a colored coupler, a color coupler, and a color coupler. A DIR coupler may be added.) A cellulose triacetate film base was coated and dried so that the dry film thickness was 5 μm, and comparative samples (1) to (1) were used.
5), practical samples 1 to 6 were obtained. Exposure time of these samples was 1 through a red filter of Ratten NO.26 using a light source with a light source with a color temperature of 5400 ° K.
Low light exposure was performed for / 50 seconds. Further, the same low-illuminance exposure was performed on the same sample as the high-intensity exposure of 1/10 ³ seconds with the same color temperature and exposure amount of the luminescent material but different exposure time. These samples were developed by a usual method, and the density was measured. The reference point of optical density that determines the sensitivity is fog +0.
1 point. Note that the high illuminance exposure sensitivity S _{H with} respect to the low illuminance exposure sensitivity S _L
The ratio S _H / S _L value of was determined for each sample. The results obtained are shown in Table 1 below as relative values. Example-2 Using EM-1 and EM-2 obtained in Example 1, the same chemical sensitization was performed, a sensitizing dye was added as shown in Table 2, and coating was carried out in the same manner as in Example 1, Samples 1 to 6 and comparative samples (1) to (6) were obtained, and the characteristics were measured in the same manner.
Listed in the table. Example-3 Samples and results shown in Table 3 were obtained by the same procedure as in Example. Example-4 The sample results shown in Table 4 were obtained by the same procedure as in Example 1. [Effects of the Invention] As is clear from the above tables, the samples satisfying the requirements of the present invention have high sensitivity, high illuminance, low fogging, and high maximum density.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tomomi Yoshizawa 1 Sakura-cho, Hino-shi, Tokyo Konishi Roku Photo Industrial Co., Ltd. Chieko Goto (56) Reference JP-A-59-116648 (JP, A) JP-A-59-154438 (JP, A) JP-A-60-12541 (JP, A) JP-A-48-5423 (JP, A) JP-A-58-107530 (JP, A) JP-A-60-222842 (JP, A)

Claims (1)

[Claims] 1. A silver halide grain in which the surface of the silver halide grain is a (110) crystal plane consisting essentially of silver bromide or silver iodobromide, is represented by the following general formula (I) or (II) Halogenated having at least one silver halide emulsion layer containing an emulsion spectrally sensitized by the combined use of at least one sensitizing dye and at least one sensitizing dye represented by the following general formula (III) Silver photographic light-sensitive material. General formula (I) [In the formula, R ₁ represents an alkyl group or an atomic group for forming a holopolar. R ₂ and R ₃ represent an alkyl group.
R ₄ , R ₅ , R ₆ and R ₇ each represent a hydrogen atom, a halogen atom, an alkoxy, an alkyl, an alkoxycarbonyl, an aryl, a carbamoyl or a hydroxy group. X ^- ₁ represents an anion, and q represents 1 or 2. R ₄ , R ₅ , R ₆ , and R ₇ may be the same or different. ] General formula (II) [In the formula, R ₁ ′ represents an alkyl group or an atomic group for forming a holopolar. R ₂ ′ and R ₃ ′ represent an alkyl group. R ₈ and R ₉ or R ₉ and R ₁₀ or R ₁₀ and R ₁₁ are bonded to each other to form a condensed ring. R ₁₂ , R ₁₃ ,
R ₁₄ and R ₁₅ each represent a hydrogen atom, a halogen atom, or an alkoxy, alkyl, alkoxycarbonyl, aryl, or carbamoyl group. Also, R ₁₂ and R ₁₃ or R
₁₃ and R ₁₄ or R ₁₄ and R ₁₅ may be bonded to each other to form a condensed ring. X ₂ ⁻ represents an anion, and r represents 1 or 2. R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ ,
R ₁₄ and R ₁₅ may be the same or different. ] General formula (III) Wherein, X is -0- or -NR ₂₂ -, Y is -S -, - 0-
Or represents —NR ₂₃ — (wherein R ₂₂ and R ₂₃ are alkyl groups). R ₁ ″ represents an alkyl group or H. R ₂ ″ and R ₃ ″ represent an alkyl group. When X is −0—, R
₁₆ , R ₁₇ and R ₁₈ are hydrogen atom, halogen atom, alkoxy, alkyl, alkoxycarbonyl, aryl, carbamoyl, hydroxy, carboxy, acylamino,
Represents each group of acyloxy or aryloxycarbonyl. R ₁₆ and R ₁₇ or R ₁₇ and R ₁₈ may combine to form a condensed ring. When Y is -S- or -0-, R ₁₉ ,
R ₂₀ and R ₂₁ represent each atom of hydrogen and halogen, and each group of alkoxy, alkyl, alkoxycarbonylaryl, carbamoyl, hydroxy, carboxy, acylamino, acyloxy or aryloxycarbonyl. R ₁₉ and R ₂₀ or R ₂₀ and R ₂₁ may combine to form a condensed ring. When, R _16, R ₁₇ is a chlorine atom, R ₁₈ a hydrogen atom, also Y is -NR ₂₃ is - - X is -NR ₂₂ when, R _19, R ₂₀ is a chlorine atom,
R ₂₁ represents a hydrogen atom. X ₃ ⁻ represents an anion, and s represents 1 or 2. R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , and R ₂₁ may be the same or different. ]