JPH0361943A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sensitivity, especially to blue light, and to reduce fog by forming at least one silver halide emulsion layer containing normal crystal grains having substantially >=2 crystal faces same in Miller indices and sensitized by a specified spectral sensitizing dye. CONSTITUTION:At least one of the silver halide emulsion layer contains the normal silver halide crystal grains having their external forms characterized by the presence of >=2 crystal faces same in Miller indices, and these grains are sensitized by at least one of the sensitizing dyes represented by formula I in which each of Y1 and Y2 is S, Se, Te, or O; each of W1 - W8 is H, alkyl, alkoxy, or the like; each of R1 and R2 is alkyl; X is an acid anion; and n is 0 or 1, thus permitting satisfactory high sensitivity and satisfactory low fog to be ensured and high blue sensitivity to be obtained even at the time of spectral sensitization in the blue wavelength region.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a silver halide photographic material which has high sensitivity and low fog, and particularly has excellent blue light sensitivity.

[Background of the invention]

In recent years, demands on silver halide photographic light-sensitive materials have become increasingly strict, and higher standards have been made for photographic performance such as high sensitivity, low fog, excellent graininess, and high sharpness.

In order to meet these demands, Japanese Patent Application Laid-Open No. 61-246740
The publication describes a silver halide that uses specific silver halide grains and a specific sensitizing dye to improve the sensitivity-capri relationship, particularly increases blue light sensitivity, and improves graininess and sharpness. Photographic materials have been proposed.

Although this conventional technique achieves each of the above-mentioned effects to a certain extent, it is insufficient in terms of high sensitivity and low fog, and further improvement in blue light sensitivity is desired.

On the other hand, JP-A-1-101541 discloses a technique that achieves high sensitivity and low fog by using silver halide grains with a specific structure.

However, this conventional technique is not necessarily satisfactory in terms of high sensitivity and low fog, and blue light sensitivity.

[Purpose of the invention]

The present invention solves the above-mentioned problems of the prior art, achieves a satisfactory high sensitivity and low fog, and provides a silver halide photograph that can obtain high blue light sensitivity even when spectral sensitization is performed in the blue light region. The purpose is to provide photosensitive materials.

[Means and effects for solving the problems] The object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support. The first layer contains silver halide normal crystal grains whose outer shape is characterized by the presence of substantially two or more types of plane shapes having the same Miller index, and which have the general formula (1) ( This can be achieved by a silver halide photographic material containing normal crystal grains of silver halide sensitized with at least one sensitizing dye represented by (described in detail below).

The present invention will be explained in more detail below.

The silver halide photographic light-sensitive material of the present invention comprises silver halide normal crystal grains (hereinafter appropriately referred to as "the silver halide grains of the present invention") whose grain shape is characterized by the presence of substantially two or more types of surface shapes having the same Miller index. (also sometimes referred to as "normal crystal grains")
has.

The normal crystal particles of the present invention will be explained as follows.

In general, the crystal planes of silver halide crystal grains contained in a silver halide emulsion include the dense density, lattice energy, surface energy, or growth conditions of silver ions and halide ions arranged in several planes. Crystal planes with specific Miller indices are dominantly expressed and give the crystal a specific crystal phase. Furthermore, when there is a difference in the growth conditions surrounding each crystal grain on a grain size scale, the grains will have different crystal habits even though they have the same Miller index.

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

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

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

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

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

At this point, the only planes on which the additionally precipitated silver halide should be deposited are trioctahedral crystal planes that grow slowly, that is, do not readily accept deposition. A second particle population of crystals is formed. It is necessary to suppress the rate of additional precipitation of silver halide when it is necessary to avoid the formation of a second grain population. Various known techniques can be used as the suppression system.

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

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

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

However, at present, there is a lack of theory that relates the various factors that affect crystal growth as described above and the crystal form produced, and in particular, for example, in a free suspension system as in the present invention, the shape of surfaces with the same Miller index is At present, no theoretical consideration has been made regarding particles having substantially two or more types of external shapes. The formation of such crystal grains, for example, promotes the growth of at most two crystal planes in the normal direction from among crystal planes with the same Miller index, degenerating the size of the line planes, while degenerating the size of the other crystal planes. The development of crystal grains can be achieved at least by keeping it within the normal range and by creating a unique crystal habit in the crystal grains, but there is almost no theoretical support for such methods, and most of the time it is not possible to achieve the intended goal through trial and error. I have no choice but to search for ways to embody the crystalline form.

In the present invention, conditions for preparing crystal particles include, for example, pAg,
Through trial and error on temperature, silver halide addition rate, and fluctuation of conditions, normal crystal grains that were able to provide a unique crystal habit were first evaluated as being favorable for increasing sensitivity (100)
Two (111) faces of a tetradecahedron consisting of a face and a (111) face.
It is possible to provide normal crystal grains exhibiting a crystal habit with degenerate planes.

The crystal of the present invention having a crystal habit characterized by the presence of substantially two or more types of planes having the same Miller index has, for example, three square planes and three rectangular planes, a total of six planes. 1 consisting of (100) plane, 4 highly developed 3 large planes, and 8 (111) planes in total.
It is a normal tetrahedral crystal.

Schematic diagrams and electron micrographs of normal crystal particles having the crystal habit of the present invention are shown in FIGS. 3 to 8.

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

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

Furthermore, it is preferable to use the particles as core/shell type particles, particularly multiple core/shell type particles.

The silver halide composition of the normal crystal grains of the present invention is arbitrary,
For example, the silver halide may be any of those used in conventional silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloride, or mixtures thereof. can. Particularly preferred are silver bromide, silver iodobromide, and silver chloroiodobromide.

Particularly preferred are silver bromide, silver iodobromide, and silver chloroiodobromide. More preferably, the silver halide grains are core/shell type silver halide grains having the following silver iodide content.

That is, for such core/shell type grains, the silver iodide content of the core is preferably 5 to 40 mol%, more preferably 8 to 35 mol%, still more preferably 10 to 40 mol%. It is 35 mol%. The silver iodide content of the shell is preferably less than 6 mol%, more preferably 0 to 4 mol%.
It is. The proportion of the shell in particles with such a core/shell type structure is preferably 10 to 80% of the entire particle, more preferably 15 to 70%, particularly preferably 10 to 80%.
%, more preferably 20 to 50%.

Further, those having an intermediate layer having a silver iodide content between the core and the shell between the core and the shell are preferably used.

In the case of core/shell type silver halide grains having the intermediate layer, the volume of the intermediate layer is preferably 5 to 60%, more preferably 10 to 55%, of the entire grain.

The difference in silver iodide content between the shell and the intermediate layer is preferably 2 mol % or more, and the difference in silver iodide content between the intermediate layer and the core is preferably 3 mol % or more.

Furthermore, the difference in silver iodide content between the shell and the core is preferably 5 mol % or more.

In obtaining core/shell type particles, Japanese Patent Application Laid-Open No. 1986-
It is also possible to use a method of growing a core/shell type silver halide emulsion starting from seed grains, as in the method described in Japanese Patent No. 138538, and in this case, the center of the grains must have a halogen composition region different from that of the core. is possible. In such cases, the halogen composition of the seed grains is silver bromide, silver iodobromide,
Silver iodobromide or silver bromide having a silver iodide content of 10 mol % or less is preferable, although silver chloroiodobromide, silver chlorobromide, silver chloride, etc. having any composition can be used.

In this case, the proportion of the seed grains in the total silver halide is preferably 50% or less, particularly preferably 10% or less.

The distribution state of silver iodide in such core/shell type silver halide grains can be detected by various physical measurement methods. It can be investigated by measurements of luminescence at low temperatures or by X-ray diffraction.

The standard X-ray diffraction method uses C as a target.
u, using α ray as a radiation source for Cu, tube voltage 40kV
In this method, the diffraction curve of the (420) plane of silver halide is obtained by a powder method with a tube current of 100 mA. Generally, in order to improve the resolution of the measuring instrument, it is necessary to appropriately select the slit width and scanning recording speed, set the step angle of the goniometer to 0.02 degrees, and correct the diffraction angle by containing a standard sample such as silicon. Further, silver halide emulsion samples are usually used after removing gelatin with oxygen and drying.

For example, the fact that the core has a silver iodide content of 5 mol% or more means that in the X-ray diffraction curve of the silver halide emulsion, the diffraction intensity region corresponds to α, vA for Cu of 5 mol% or more of silver iodobromide. This can be confirmed by the presence of a diffraction angle of 10% or more with respect to the peak intensity at any one point.

Next, the normal crystal particles of the present invention are sensitized with at least one kind of spectral sensitizing dye represented by the following general formula (1). This spectral sensitizing dye will be explained below.

Below is the blank general formula (1) % formula % W, , W, is H, alkyl group, alkoxy group, aryl group, halogen atom, amino group, acylamido group, acyloxy group, alkoxycarbonylamino group, alkoxycarbonyl group or hydroxy is the group, Wl and wt
, Wl and Ws, Wa and W3, W, and W6, W, and W
9. W4 and W8 may be bonded to form an aromatic carbocycle or an aromatic heterocycle.

R+ and Rz are alkyl groups.

X is an acid anion.

n is 0 or l, and when forming an inner salt,
nxQ.

In the above general formula (1), at least one of R6 and R2 is preferably an alkyl group having a carboxyl group or an alkyl group having a sulfo group, and R3
Alternatively, when R2 represents the above group, the remaining one is preferably an unsubstituted alkyl group, and this alkyl group is preferably a lower alkyl group, such as methyl, ethyl, propyl, butyl, and the like.

Examples of the anion represented by e include chloride, bromide, iodide, thiocyanate, sulfamate, methyl sulfate, ethyl sulfate, verchlorate, and p-toluenesulfonate.

In the general formula (1), Yl and Y2 may be the same or different and represent a sulfur atom, an oxygen atom, a tellurium atom, and a selenium atom, and w and -we are a hydrogen atom and a halogen atom ( (e.g., chlorine, bromine, iodine, fluorine), hydroxyl group, alkoxy group (e.g., methoxy, ethoxy, propoxy, butoxy, etc.), amino group (e.g., aξ)
, methylamino, dimethylamino, diethylamino, etc.)
, acylamido groups (e.g. acetamide, propionoxy, etc.), acyloxy groups (e.g. acetoxy, propionoxy, etc.), alkoxycarbonyl groups (e.g. ethoxycarbonyl, propoxycarbonyl, etc.), alkoxycarbonylamino groups (e.g. ethoxycarbonylamino,
propoxycarbonylamino, butoxycarbonylamino, etc.), alkyl groups (eg, methyl, ethyl, propyl, etc.), and aryl groups (eg, phenyl, tolyl, etc.).

Wl and Wt, Wt and W8, W4 and W, , W, and W, ,
W, and Wt, and W, and W may be connected to each other to form, for example, a benzene ring. This benzene ring may have a substituent.

Typical specific examples of the sensitizing dye represented by general formula (1) that can be used in the present invention are described below, but the dye that can be used in the present invention is limited only to these compounds. isn't it.

The sensitizing dye represented by the general formula (1) as exemplified above is a known compound, for example, U.S. Pat. .14
9.105, British Patent No. 2,238.231, British Patent No. 742.112 or "The
"Cyanine Soybean and Related Compounds" (Interscience Publishing As, N.
Y., 1964〉55, et al. et seq., those skilled in the art can easily synthesize those not described by similar methods.

The sensitizing dye represented by the above general formula (1) may be used alone or in combination of two or more types. (For example, see Japanese Patent Application Laid-Open No. 59-116645). Furthermore, the sensitizing dye according to the present invention can also be used together with a sensitizing dye other than the sensitizing dye represented by formula (1) or a substantially colorless compound known as a supersensitizer. . For example, U.S. Patent No. 2,933.390;
No. 511.664, No. 3゜615, No. 613, No. 3
, 615.632, 3,615,641, etc., compounds having a pyrimidinylamino group or triazinylamino group, British Patent No. 1,137.580
It may also contain an aromatic organic acid-formaldehyde condensate or a cadmium salt as described in the above.

In addition, various conventionally proposed methods can be used to add the above-mentioned sensitizing dyes to the photographic emulsion. For example, as described in U.S. Pat. No. 3,469,987, a sensitizing dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and this dispersion is added to an emulsion. You can. Furthermore, the sensitizing dyes according to the present invention may be individually dissolved in the same or different solvents,
These solutions can be mixed or added separately before being added to the emulsion.

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

When the sensitizing dye is added to the silver halide emulsion, the preferred amount thereof is 2.times.10-' mol to 1.times.10-' mol per mol of silver halide.

In addition to the normal crystal grains of the present invention, the light-sensitive material of the present invention includes silver halide grains having regular crystal shapes such as cubic, octahedral, and tetradecahedral, as well as silver halide grains having regular crystal shapes such as spherical and plate shapes. It is also possible to use a substance with an irregular crystal shape.

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

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

The normal crystal grains of the present invention are contained in at least one of the silver halide emulsion layers constituting the light-sensitive material of the present invention, but silver halide grains other than the normal crystal grains of the present invention are not contained in the same layer. You can leave it there.

Further, when the light-sensitive material of the present invention has two or more silver halide emulsion layers, there may be an emulsion layer consisting only of silver halide grains other than the normal crystal grains of the present invention.

Preferably, the emulsion layer of the light-sensitive material is composed only of the silver halide emulsion layer comprising only normal crystals of the present invention.

The normal crystal particles of the present invention can be sensitized by using the sensitizing dye represented by the above general formula (1) in combination with other sensitizing dyes. Further, silver halide grains other than the normal crystal grains of the present invention, which are used as necessary in the light-sensitive material of the present invention, can be optically sensitized to a desired wavelength range as appropriate. In that case, there are no particular restrictions on the optical sensitization method, and for example, cyanine dyes such as xeromethine dyes, monomethine dyes, dimethine dyes, trimethine dyes, cyanine dyes such as merocyanine dyes, or optical sensitizers such as merocyanine dyes are used alone or in combination. can be optically sensitized. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that exhibits supersensitization, such as '#Jx' that does not substantially absorb visible light. These technologies are described in U.S. Patent No.
688.545, 2,912.329, 3,3
No. 97,060, No. 3.615.635, No. 3,62
No. 8,964, British Patent No. 1,195.302, No. 1
, 242,588, 1,293.862, West German Patent (OL S) 2,030.326, 2,12
No. 1.780, Special Publication No. 43-14030, Research
Research Disclosure
ure) Volume 176, 17643 (published December 1978), page 23, item 5, etc.

The selection can be arbitrarily determined depending on the wavelength range to be sensitized, sensitivity, etc., and the purpose and use of the photosensitive material.

In the present invention, various commonly used chemical sensitization treatments can be performed. Chalcogen sensitizers used in chemical sensitization include sulfur sensitizers, selenium sensitizers, and tellurium sensitizers, and sulfur sensitizers and selenium sensitizers are preferred for use in photography. As the sulfur sensitizer, known ones can be used. For example, thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine,
Examples include p-toluenethiosulfonate and rhodanine. Others: U.S. Patent Nos. 1,574,944 and 2
．． No. 410.689, No. 2,278,947, No. 2,
No. 728.668, No. 3,501.313, No. 3,6
No. 56.955, OLS 1,422,
No. 869, JP-A-56-24937, JP-A No. 55-450
Sulfur sensitizers described in No. 16 and the like can also be used. The amount of sulfur sensitizer added may be sufficient to effectively increase the sensitivity of the emulsion. This appropriate amount varies over a considerable range under various conditions such as pH, temperature, and size of silver halide grains, but as a guide, it is preferably about 101 moles to about 10 moles per mole of silver halide. .

Examples of selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenoamides, selenocarboxylic acids and esters, selenophosphates, diethylselenide, diethylselenide, etc. Selenides etc. can be used, and specific examples thereof are described in U.S. Pat. No. 1,574.
, No. 944, No. 1,602.592, No. 1,623,
No. 499.

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

In the present invention, various gold compounds are used as the gold sensitizer, and the valence of gold may be +1 or +3. Typical examples include chloroauric acids, potassium chloroaurate,
Auric trichloride, potassium aurinthiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate,
Examples include pyridyltrichlorogold.

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

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

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

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

Further, complexes of Rh, Pd, Ir, pt, etc. are effective as compounds that release gold ions from gold-gelatinate and promote adsorption of gold ions onto silver halide grains.

As a specific compound, (Nl(4)z (ptCl
4], (NH4) z (PtCt!4), Ks [I
rBra], (NH4) x [RhCI! b)
12820, etc., but particularly preferred is ammonium tetrachloropalladate(II) (NH4).
zP tCl a. The amount added is preferably 10 to 100 times the stoichiometric ratio (mole ratio) to the gold sensitizer.

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

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

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

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

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

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

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

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

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

When the present invention is applied to a light-sensitive material for color photography, a coupler is used for -a in the emulsion layer.

Furthermore, by coupling with a colored coupler having a color correction effect, a competitive coupler, and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, Compounds that release photographically useful fragments can be used, such as fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers.

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

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

Images can be obtained from the light-sensitive material of the present invention by appropriate processing. For example, in the case of obtaining a dye image, commonly known color photographic processing can be performed after exposure.

The following margin [Examples] Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited by these.

Prior to the examples, first let's look at the emulsion tone for comparison! ! ! (Comparative example 1
) is shown.

Comparative Example 1 Comparative emulsion EM-1 was prepared using seven types of solutions shown below.

(Solution A) Ossein gelatin 10.9 g 10% aqueous ethanol solution of polyisopropylene polyethyleneoxy disuccinate sodium salt
3.5-4-hydroxy-6-methyl-1,
3゜3a,7-chitrazaindene 0.5% aqueous solution 45.2m! 28
%Ammonia water 164m756%
Acetic acid aqueous solution 258-seed emulsion (0,
8 μm, octahedral bromide iJl, Agl content 2.6 mol%
) 67.2 mj (contains 0.158 mol of silver halide) Distilled water 2333 ta (Solution B) Ossein gelatin 3.5 g K B
r 121.4gK I
30.49g 4-hydroxy-6-methyl-1,3゜3a,7-chitrazaindene 0.5% aqueous solution 75.6ml Make up to 350% with distilled water.

(Solution C) Ossein gelatin 4.7g K B
r 180.9gK1
13.6g4-hydroxy-6-methyl-1,3゜3a,7-chitrazaindene 0
．． 5% aqueous solution Make 466.7- with 100.8ml distilled water.

(Solution D) Ossein gelatin 4.7gKBr
190gKI
0.81g4-hydroxy-
6-methyl-1,3°3a,7-chitrazaindene 0.
5% aqueous solution 100.8a/N
Make it 466.7- with 1 yen water.

(Solution E) AgNOi 407g28%
Ammonia water 362.8mZ Make 684.6- with distilled water.

(Solution F) 50% KBr aqueous solution Required amount for pAg adjustment (Solution G) 50% acetic acid aqueous solution p) Required amount for l adjustment At 50°C, JP-A-57-92523, JP-A-57-9252
Using the mixing stirrer shown in No. 4, add solutions E and B to solution A.
were added for 98 minutes by a simultaneous mixing method, C was added at the same time as the addition of B was completed, D was added at the same time as the addition of C was completed 50 minutes later, and the addition was completed after 42 minutes.

pAg, pH and solutions E, B, C during simultaneous mixing.

The addition rate of D was 'MHH' as shown in Table 1. pA
g and pH were controlled by changing the flow rates of solution F and solution G using a variable flow rate roller tube pump. Two minutes after the addition of solution E is finished, the pH is adjusted to 6 with solution G.
．． Adjusted to 0.

Next, wash with demineralized water in the usual manner, and use Ossein Gelatin 44.
．． After dispersing in an aqueous solution containing 3 g, add distilled water to reduce the total amount to 1
Finished to 0105O.

Electron microscopic observation revealed that this emulsion EM-1 was a highly monodispersed octahedral emulsion with an average grain size of 2.0 μm and a coefficient of variation of grain size distribution of 12%.

This emulsion is a core/shell type silver iodobromide emulsion with a silver iodide content of 15 mol %, 5 mol % and 0.3 mol % sequentially from the inside of the grain.

table Next, each example will be explained.

Example 1 An anisotropic normal crystal silver halide emulsion EM-2 of the present invention was prepared in the same manner as in Comparative Example 1, except that the following two types of photosensitive dye aqueous solutions were added 141 minutes after the start of addition.

0.2% methanol aqueous solution of photosensitive dye (I) 128.
0.2% methanol aqueous solution of 8mZ photosensitive dye (II)
151.0+af Photosensitive dye (I) Photosensitive dye (II) According to electron microscopic observation, the above emulsion according to the present invention has the following properties:
14 consisting of 6 (100) planes and 3 (111) planes
It was found that of the three (111) normal directions of the hedral crystal, it consists of an anisotropic tetradecahedral normal crystal that is abnormally elongated in only one or two directions.

Next, this emulsion was subjected to extraction treatment with a solvent to remove the adsorbed photosensitive dye. First, methanol was added under acidic conditions, followed by precipitation of the emulsion, and the supernatant liquid was discarded. This process is repeated several times to obtain E, which has no spectral sensitization sensitivity.
M-2 was created.

Schematic diagrams and electron micrographs of crystals of EM-1 and EM-2 are shown in FIGS. 1 to 8.

1 and 2 are for EM-1, and the others are for EM-2. As can be understood from the comparison between FIGS. 1 and 2 and FIGS. 3 to 8 (present invention), although the grains in the emulsion of the present invention are normal crystals without twins,
It can be seen that the crystal satisfies the specific requirements of having one or two sites that give a specific crystal habit.

Example 2 Emulsions EM-1 and EM-2 described in Comparative Example 1 and Example 1
Each was optimally gold-sulfur sensitized and blue-sensitized spectral sensitized. The types and amounts of the sensitizing dyes used are shown in Table-2.

Then, TAI\(4-hydroxy-6-methyl-1,
3,3a,? -tetrazaindene) and 1 phenyl-5
- Stabilized by adding mercaptotetrazole. Common photographic additives such as spreading agents and hardeners are added to each of the above emulsions to prepare a coating solution, which is coated onto the subbed film base by a conventional method and dried.
i14 was created.

Below is a margin table for comparison dyes - 8 samples + each of 4 from 1 through a blue filter.
Wedge exposure was performed under the exposure condition of /12.5 seconds. After exposure, the sample was processed for 90 seconds using the following processing solution in the following processing step (I) using a KX-500 automatic processor manufactured by Konica ■, and fog and sensitivity were determined.

Treatment step (1) (35℃) Developing 25 seconds Fixation 25 seconds Wash with water 25 seconds Drying 15 seconds The composition of the treatment liquid used in each treatment step is shown below.

Developer solution> Potassium sulfite 55.0 g Hydroquinone 25.0 g l-Phenyl-3-pyrazolidone 1.2 g Boric acid
10.0 g sodium hydroxide
21.0 g triethylene glycol
17.5 g5-methylbenzotriazole 0.07g5-nitroindazole
0.14 g 1-phenyl-5-mercaptotetrazole 0.015 g Glutaraldehyde bisulfite 15.0 g Ice vinegar M
16. Og Potassium bromide 4.0g Triethylenetetraξanehexaacetic acid fa 2.5g Add water to make up to TL and adjust pH to 10.20.

Fixing solution> Ethylenecyamine tetranodic acid di-sodium salt 5.0g Tartaric acid 3.0g Ammonium thiosulfate 130.9g Anhydrous sodium sulfite 7.3g
Acid 7.
0 g acetic acid (90 nt%) 5.5 g sodium acetate trihydrate 25.8 g aluminum ξ sulfate 18 hydroxide 14.6 g sulfuric acid (500%
) Add 6.77g of water and finish to 11, p.
Adjust to H=4.20.

The calculated fog and sensitivity are as follows.

Fog: The lowest optical density on the so-called characteristic curve obtained by sensitometry (the larger the value, the higher the fog is, which is undesirable) Sensitivity: Exposure that gives an optical density of fog + 0.1 on the characteristic curve Reciprocal of it (exact value). Table of results of examples (
In Table 2), the sensitivity of Sample 1 is set as 100, and the sensitivity is expressed as a relative value.

As is clear from the results in Table 2, the emulsions of the present invention have low fog and high sensitivity.

In addition, in sample N [L4, the amount of hardener used was changed to increase the swelling degree of the developed film thickness to 220 and 250%, respectively.
Each sample was prepared as follows.

When each of these samples was evaluated in the same manner as Sample Ko4, the effects of the present invention were recognized.

Furthermore, samples 11 and 14 were prepared with relative humidity at the time of packaging of 50% and 40%, respectively, and stored for 3 months.

When similar evaluations were performed on each of these samples, the effects of the present invention were obtained.

Example 3 Next, an example of a silver halide color light-sensitive material using the emulsion according to the present invention will be shown.

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

In this example, a yellow coloring coupler was used.

Specifically, in this example, a coupler represented by the following formula (A) was used as a yellow coloring coupler, and sample M
ail~14 was created.

Margin (A) below: As the high boiling point solvent for dissolving the formula coupler, tricresyl phosphini (TCP) was employed.

The coupler was oil-protected and dispersed according to a conventional method.

Next, the silver iodobromide emulsion (
EM-1 and EM-2) were optimally chemically sensitized using an unstable sulfur compound and a gold salt according to a conventional method. Also, during chemical sensitization, a sensitizing dye was added to achieve blue sensitivity.

The types and amounts of the sensitizing dyes used are shown in Table 3.

Silver iodobromide emulsion 1.8 subjected to the above chemical sensitization and color sensitization
A high-speed blue-sensitive emulsion layer was prepared containing 1.9 g of gelatin and 0.06 g of TCP (1-licresyl phosphate) dispersion in which 0.20 g of yellow coupler was dissolved.

Each sample was wedge exposed using blue light according to a conventional method and subjected to sensitometry.

Each exposed sample was processed in the next processing step.

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

Color developer> 4-Amino-3-methyl-N-(β-hydroxyethyl)-aniline sulfate 4.75g Anhydrous sodium sulfite 4.25g 5g Hydroxylaminate 2.0g Anhydrous potassium carbonate Sodium bromide Nitrilotriacetic acid - Add trisodium salt potassium hydroxide water to make il.

bleaching solution Iron ethylenecyaminetetraacetate ammonium salt Ethylenediaminetetraacetic acid 2 ammonium salt ammonium bromide glacial acetic acid Add water II! year, Adjust the pH to 6.0.

Fixer> ammonium thiosulfate Anhydrous ammonium sulfite sodium metasulfite Add water to make 11, 10.0 g 150.0 g 10.0 sl using ammonia water 175.0g 8.6g 2.3g pH 6.0 using acetic acid 37.5 g 1.3g (monohydrate salt) 2.5g 1.0 g 100, 0g adjust.

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

The developed sample was subjected to sensitometry using blue light.

The determined sensitivity and fog are as follows.

Fog: The lowest optical density of the so-called characteristic curve obtained by sensitometry (the larger the value, the higher the fog, which is undesirable).

Sensitivity: the reciprocal of the exposure amount (antilog value) that gives an optical density of fog + 0.1 on the characteristic curve (in the table of results of Examples (Table 3), the normal exposure (1150 seconds exposure) of sample IVk11 It is expressed as a relative value with the sensitivity at 100 as the value is higher (the higher the value, the faster the sensitivity, which is preferable).

The results are shown in Table-3.

As is clear from the results in Table 3, the emulsion of the present invention was found to have low fog and high sensitivity.

Example 4 Preparation of multilayer color photosensitive material (referred to as multilayer sample) rIi,
: Using the same chemically sensitized and color sensitized silver iodobromide emulsion used to prepare the single color sensitive coating sample mentioned above,
A color photosensitive material consisting of nine layers having three types of photosensitive layers: a blue photosensitive layer, a green photosensitive layer, and a red photosensitive layer was prepared in the following manner. EM-1 subjected to chemical sensitization and color sensitization,
The emulsion of EM-2 was changed only in blue sensitivity high sensitivity N (eighth layer). For the other photosensitive layers, the same emulsion was used in each sample.

It consists of a subbed cellulose triacetate film with an antihalation layer (black colloid jJi10.
40g and 3.0g gelatin. ) A sample was prepared by coating each of the following layers in order on a transparent support. In all of the following Examples, the amounts added to the light-sensitive materials are shown per one durability, and are shown in terms of silver halide emulsion and colloidal silver.

Layer 1: 1.4 g of low-sensitivity red-sensitive silver iodobromide (containing 7 mol% silver iodide) emulsion color-sensitized to red sensitivity and 1.2 g
of gelatin and 0.8 g of 1-hydroxy-4-(β
-methoxyethylaminocarbonylmethoxy)-N-(
α-(2,4-di-t-amylphenoxy)butyl]-
2-naphthamide [hereinafter referred to as C1-1. ], 0.0
75 g of 1-hydroxy-4-(4-(1-hydroxy-δ-acetamido-3,6=disulfo-2-naphthylazo)phenoxy)-N-(α-(2,4-di-t-
amylphenoxy)butyl-2-naphthamide disodium [hereinafter referred to as colored cyan coupler (CC''-1)
It is called. ] and 0.015 g of 1-hydroxy-2
-[α-(2,4-di-t-amylphenoxy)butyl]naphthamide, 0.07 g of 4-octadecylsuccinimide-2-(1-phenyl-5-tetrazolylthio)-1-indanone [hereinafter DIR compound'* (D”-1)
It is called. ] A low-speed red-sensitive emulsion layer containing 0.65 g of a tricresylphosphate-1-(TCP) dispersion in which these were dissolved.

Layer 2...1.3g of highly sensitive red-sensitive silver iodobromide emulsion 1.2
g of gelatin and 0.21 g of cyan coupler (C'
−1> and 0.02 g of colored cyan coupler (C
A high-speed red-sensitive emulsion layer containing 0.23 g of TCP dispersion in which C''-1) was dissolved.

Layer 3: 0.07 g of 2,5-di-t-octylhydroquinone [hereinafter referred to as antifouling agent (HQ-1)]. ] is dissolved in 0.04 g of dibutyl phthalate c, hereinafter referred to as DBP. 9 dispersion and 0.8 g of gelatin.

Layer 4: 0.80 g of low-sensitivity silver iodobromide (containing 6 mol% silver iodide) emulsion sensitized to green sensitivity, 2.2 g of gelatin and 0.8 g of 1-(2, 4゜6-dolychlorophenyl)3-(3-(2゜4-di-tert-aryphenoxyacetamideξdo)benzado]-5-pyrazolone, 0.15 g of 1-(2, 4,6-Dolichlorophenyl)-4-(1-naphthylazo)-3-(2-chloro-5-octasecenylsuccinidoanilino)-5-
Pyrazolone [hereinafter referred to as colored magenta coupler (CM')
1). ) 0.016 g of DIR compound (
A slow green-sensitive emulsion layer containing 0.95 g of TCP dispersion in which D'-1) was dissolved.

N5...1.8g chemically sensitized and color sensitized to green sensitivity
High-sensitivity green-sensitive silver iodobromide emulsion, 1.9 g of magenta, 0.20 g of a pyrazolotriazole coupler represented by M-1 below, and 0.049 g of colored magenta coupler (CM'-1). 0.06g DNP dissolved
A highly sensitive green-sensitive emulsion layer containing a dispersion.

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

Ji17...0.2 g of low-sensitivity iodobromide vA (containing 4 mol% silver iodide) emulsion sensitized to blue sensitivity, 1.9 g of gelatin, and 1.5 g of α-pivaloyl-α- (1
-benzyl-2-phenyl-3<5-dioxoimidasiridin-4-yl)-2'-chloro-5'-[α-dodecyloxycarbonyl)ethoxycarbonyl]acedoanilide [hereinafter referred to as Y-1]. ] dissolved in 0,6
A low-speed blue-sensitive emulsion layer containing a TCP dispersion of g.

N8...1.0g chemically sensitized and color sensitized to blue sensitivity
The high-speed blue-sensitive silver iodobromide emulsions (EM-1, EM-2
), a high-speed blue-sensitive emulsion layer containing 0.65 g of TCP dispersion in which 1.5 g of gelatin and 1.30 g of yellow coupler (Y-1) were dissolved.

Layer 9: Protective layer with 2.3 g of gelatin.

Measurement of multilayer sensitivity: The thus prepared multilayer color photosensitive material was exposed to white wedge light according to a conventional method, processed in the above processing steps, and blue light sensitivity was obtained by sensitometry (the definition of sensitivity is based on the above single (same as for color-sensitive coated samples).

The results are shown in Table 4.

As shown in the margin table 4 below, the samples of the present invention have little fog and high sensitivity. As described above, it was found that the effects of the present invention can be obtained even with a sample having a multilayer structure, as in Example 2.

Furthermore, in sample seed 24, by changing the amount of gelatin in each layer, the dry film thickness was increased to 15 or 1, respectively.
Each sample was created in the same manner as sample Flh24 except that the thickness was reduced to 3 μm.

When similar evaluations were performed on each of these samples, the improvement effect of the present invention was recognized.

Furthermore, in samples N1121 to 11kL25, the amount of silver halide emulsion in each layer was changed, and the amount of photosensitive silver halide (in terms of silver) in all emulsion layers was 3.5 g/rrf.
Sample fish 26 to sample fish 30 were prepared in the same manner as samples 21 to 25, respectively, except that the amount was reduced to .

When similar evaluations were performed on each of these samples, it was found that sample N [L29. In Ik30, a clear improvement in graininess was observed compared to the comparison samples Nt126 to Nt28.

Example 5 A silver iodobromide emulsion having an average grain size of 0.27 μm and containing 2.0 mol % of silver iodide was used as a seed emulsion, and this seed emulsion and the following 7
EM-3 was created using different types of solutions.

The grains in emulsion EM-3 are core/shell type silver iodobromide with an average grain size of 0.8 μm and an average Agl content of 4.2 mol %.

(Solution A-5) Ossein gelatin 51.93g110
→CHtCHzOh-→C1(CI!0suMCLCLO
eT-OH\H3 Average molecular weight 11700 Pronone (NOF type) 10% ethanol solution 30.0mZ distilled water
9112a/(?Liquid B-5
) Seed emulsion AgX 0.4072 mol equivalent 56% acetic acid aqueous solution 1590d28
% Ammonia water 1056a/(Solution C-5> Ag N 031656.3 g 28% Ammonia water 1297mZ Make to 2785- with distilled water.

(?Liquid D-5) Ossein gelatin 34.93 gK
B r 1454.7
g Make 3493- with distilled water.

(Solution E-5) Gelatin solution in which 0.05 μm Ag1 fine particles are dispersed
AgX O, 4391 mole equivalent 4-hydroxy-6-methyl-1,3゜3a, 7-chitrazaindene
Make 918- with 1.379 g distilled water.

(?Volume Solution F-5) 3.5 (mol/1KBr aqueous solution Required amount for pAg adjustment (Solution G-5) 56% acetic acid aqueous solution Required amount for pH adjustment Shown in JP-A-57-92523 and JP-A-57-92524 Using a mixing stirrer, add solution B to solution A, and then mix solution C, solution and solution E simultaneously in Table-5.
-39 It was added under control as shown in Table 5-b.

During this period, pAg was adjusted to 7.0 to 11 using solution F and warm solution.
．． It was added while controlling the pH in the range of 5.0 to 11.0.

If solution C and only solution are mixed simultaneously, silver bromide will be produced, but since solution E contains Agl fine particles, solution C1
In addition to the solution, by simultaneously mixing solution E,
Silver iodobromide grains are formed.

Furthermore, by controlling the rate of addition of solution E, it is possible to form phases with different silver halide compositions. Therefore, when simultaneously mixed at the addition rates shown in Tables 5-a and 5-b, the resulting grains have a core/shell structure with a high silver iodide content inside and a low silver iodide content on the surface. It becomes a type emulsion. Ag If contained in solution E used here
As a result of electron microscopic observation, the particle size of i particles is approximately 0.05μ.
It was m.

Next, the ossein gelatin 12
After dispersing it in an aqueous solution containing 9.7 g, add distilled water to bring the total amount to 4500@! Emulsion EM-3 was obtained.

Table 5-a: Particle growth conditions (EM-3) Table 5-b: Particle growth conditions (EM-3) In the same manner as in Example 3, EM-3 was optimally chemically sensitized and spectroscopically turned into blue color. Sensitization was performed (see Table 6 for the type and amount of sensitizing dye), and exposure and development were performed.

The results are shown in Table-6.

Margin Table-6 Below: Sensitivity is expressed as relative sensitivity with the sensitivity of sample IIkL31 as 100.

As can be seen from Table 6, it was shown that the fog was low and the sensitivity was high when compared with the comparison sample according to the present invention.

Example 6 The following layers were coated sequentially from the support to form samples 41 and 42.
It was created.

1st layer Antihalation layer 2nd layer Intermediate layer 3rd layer Low-sensitivity red-sensitive emulsion layer 4th layer Intermediate layer 5th layer Low-sensitivity green-sensitive emulsion layer 6th layer Intermediate layer 7th layer Low-sensitivity blue-sensitive emulsion layer 8th layer Layers Intermediate layer 9th layer Highly sensitive red-sensitive emulsion layer 10th layer Intermediate layer 11th layer Highly sensitive green-sensitive emulsion layer 12th layer Intermediate layer 13th layer Highly sensitive blue-sensitive emulsion layer 14th layer First protective layer 151st layer 2 Protective Layer For each layer of the samples 41 and 42, layers having the same composition as those used in the samples 22 and 1lh24 of Example 4 were used, respectively.

That is, the 3rd layer, 5th layer, 7th layer, 9th layer, 11th layer, and 13th layer of samples Na41 and Hiro42 are respectively Example 4.
1st layer, 4th layer, 7th layer of sample m22 and Na24,
It consists of the same constituent components as the second layer, fifth layer, and eighth layer.

In addition, the antihalation layer of sample N141 and floor 42,
The first protective layer and the second protective layer are the sample floors 22 and 1 of Example 4.
It consists of the same constituent components as 1h24.

When each sample was subjected to the same exposure and development treatment as in Example 4 and evaluated in the same manner, it was found that samples 1' and 42 of the present invention exhibited the sensitization and fog improvement effects of the present invention compared to comparative sample Hiro 41. .

〔Effect of the invention〕

As described above, it is an object of the present invention to provide a silver halide photographic material that can realize satisfactory high sensitivity and low fog, and can also obtain high blue light sensitivity when spectral sensitization is performed in the blue light region. I can do it.

[Brief explanation of drawings]

Figures 1 and 2 relate to the comparative emulsion EM-1. Figure 1 shows the normal crystal tetradecahedron of the grains, and Figure 2 shows the comparative emulsion EM-1 (normal crystal tetradecahedron). 3 is an electron micrograph of a grain structure. FIGS. 3 to 8 relate to emulsion EM2 according to the present invention. FIG. 3 is a diagram showing an anisotropic tetradecahedral crystal of the present invention, A crystal extending only in the normal direction of one (111) is viewed from the normal direction of the adjacent (111) plane (the normal direction in which the arrow extends anisotropically).
The figure is an electron micrograph of crystal grains corresponding to FIG. 3. FIG. 5 is a diagram of the anisotropic tetradecahedral normal crystal of the present invention,
A crystal extending only in one (111) normal direction is viewed from the normal direction (the normal direction is almost perpendicular to the plane of the paper). FIG. 6 is a photograph of a normal crystal grain of the present invention, and the symbol a in FIG. 6 is an electron micrograph of the crystal grain corresponding to FIG. 5, and the symbol b is a photograph of the crystal grain corresponding to FIG. This is an electron micrograph of crystal particles corresponding to No. 8. Figure 7-A and B are
1 is a diagram showing an anisotropic tetradecahedral crystal of the present invention, with two
1, 11) This shows a crystal that extends only in the normal direction. FIG. 8 is an electron micrograph of the crystal corresponding to FIG. 7-B.

Claims (1)

[Claims] 1. In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has the same mirror index. Silver halide normal crystal grains whose outer shape is characterized by the presence of substantially two or more types of surface shapes, and which are at least one type of sensitizing dye represented by the following general formula (1). A silver halide photographic material containing sensitized silver halide normal crystal grains. General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ However, Y_1 and Y_2 are S, Se, Te, or O. W_1, W_2, W_3, W_4, W_5, W_6
, W_7, W_8 are H, alkyl group, alkoxy group,
An aryl group, a halogen atom, an amino group, an acylamido group, an acyloxy group, an alkoxycarbonylamino group, an alkoxycarbonyl group, or a hydroxy group, W_1
and W_2, W_2 and W_3, W_4 and W_5, W_5 and W_6, W_1 and W_7, and W_4 and W_■ may be bonded to form an aromatic carbon ring or an aromatic heterocycle. R_1 and R_2 are alkyl groups. X is an acid anion. n is 0 or 1, and when forming an inner salt,
n=0.