JPH0743507B2 - Silver halide photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material. More particularly, it relates to a silver halide photographic light-sensitive material containing a high-sensitivity silver halide emulsion which has been chemically and spectrally sensitized by a highly controlled method and in which fog generation due to pressure or friction is improved.

(Prior Art) A silver halide emulsion used in a silver halide photographic light-sensitive material is a sulfur sensitizer, a selenium sensitizer, a reduction sensitizer, a noble metal sensitizer, or the like in order to obtain a desired sensitivity gradation. Are chemically sensitized alone or in combination. Among them, sulfur sensitizers,
Selenium and noble metal sensitizers are important.

Further, in order to obtain excellent color reproduction, it is spectrally sensitized by a sensitizing dye so that the silver halide has sensitivity to light having a long wavelength, which is essentially not absorbed by light.

In recent years, it has been eagerly desired to increase the sensitivity of silver halide emulsions. In particular, however, in the spectral sensitization wavelength region, the amount of the sensitizing dye added to the silver halide emulsion is increased to increase the amount of light trapping. Has been tried.

The color sensitization sensitivity Sλ (at wavelength λ) when a dye is added is determined by the following formula.

Here, S ° 400 and S400 are 400 of main milk and spectrally sensitized emulsion.
Photographic sensitivity in nm. Φr is the relative quantum yield, Aλ
And A400 are the optical absorptances at wavelengths of λ and 400 nm, respectively. It is preferable to use a large amount of dye for light absorption, but φ
The photographic sensitivity is lowered because r is lowered or S400 / S ° 400 is lowered (usually called intrinsic desensitization).

In a silver halide grain called a normal crystal, (11
Since cubic particles composed of (100) planes have smaller intrinsic desensitization by dyes than octahedral particles composed of 1) planes,
It is often the case that silver halide grains having a large proportion of (100) plane are used for spectral sensitization with a large amount of dye.

By the way, a high-sensitivity silver halide photographic light-sensitive material containing such a silver halide emulsion is fogged by being subjected to physical pressure or friction during the manufacturing process, handling by the user, development processing, etc. Hereinafter, pressure fog is often generated, and such pressure fog greatly impairs the quality of the obtained image. This pressure fog is particularly likely to occur particularly in a chemically sensitized and spectrally sensitized light-sensitive material with a sensitizing dye,
There has been a longing for improvement.

Various measures have heretofore been proposed as measures for preventing such pressure fog. For example, a high boiling organic solvent, polymer latex, or a method of incorporating a 5-nitrobenzotriazole or mercaptoazole compound and a pressure fog inhibitor, a method of reducing the silver halide to gelatin ratio of a silver halide emulsion, Or
There is a method in which the structure of the silver halide grain itself is devised by a precipitation forming method.

However, high-boiling organic solvents and polymer latices weaken the mechanical strength of the emulsion layer, and pressure fog inhibitors are liable to lower sensitivity, increasing the amount of gelatin and decreasing the silver halide to gelatin ratio. If it is set to 1, the drying time after the development processing becomes long and it becomes difficult to perform the rapid processing, which is a drawback.

Further, changing the structure of the silver halide grains itself has a drawback that the photographic properties such as photographic sensitivity are greatly changed.

Therefore, at least 60 without the drawbacks mentioned above.
It has been desired to develop a means for improving the pressure fog at the same time as obtaining a high photographic sensitivity in the normal crystal grains of (100) plane.

Further, conventionally, it is hardly known to control the position of the chemically sensitized nucleus where the latent image is formed, but the chemically sensitized nucleus is positively dispersed without arbitrarily dispersing it on the surface of the silver halide grain. In addition, it is expected that it is preferable to form the dye in a limited position and range so as to separate the dye and the latent image forming position, which is also preferable for increasing the sensitivity of the silver halide emulsion. The high-sensitivity silver halide emulsion has been eagerly awaited.

(Object of the Invention) The present invention provides a novel method for producing a highly sensitive silver halide emulsion which has been chemically and spectrally sensitized by a highly controlled method and has improved occurrence of pressure fog, and The present invention relates to a silver halide light-sensitive material containing a highly sensitive silver halide emulsion prepared by using.

DISCLOSURE OF THE INVENTION The above object is achieved by the following light-sensitive material of the present invention. That is, in a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, 50% or more of the total projected area of all silver halide grains in the emulsion layer satisfies the following conditions. A silver halide photographic light-sensitive material characterized by being normal crystal grains, and 70% or more (number) of the normal crystal grains satisfy the following conditions.

60% of the surface of the silver bromide or silver iodobromide grains which are substantially normal crystals of (111) and (100) faces.
The above is the (100) plane.

It is chemically sensitized in the presence of a sensitizing dye that is more selectively adsorbed to the (100) plane than the (111) plane, and a latent image is preferentially formed on the (111) plane.

The essence of the present invention is to achieve the object by highly controlling and separating the chemical sensitizing nuclei, that is, the latent image forming position and most of adsorbed dyes on the surface of silver halide grains. To do.

As a specific method therefor, the method newly devised by the present invention is as follows.

That is, by the method described later, (11
A dye which is more easily adsorbed to the (100) face than to the (1) face is selected and chemically sensitized in the presence of the dye (more preferably, a large amount of the dye is used to cover the (100) face).
As a result, the used dye did not adsorb (111)
A latent image can be formed on the surface and the purpose can be achieved.

Of course, within the range where the latent image forming position is controlled, it is easy to selectively adsorb to other surfaces together with the dye which is selectively adsorbed to the (100) surface of the silver halide grain in the present invention. If necessary, a dye or a dye that is uniformly adsorbed may be used during the chemical sensitization, before the chemical sensitization, or after the chemical sensitization is completed.

As in the method of the present invention, it has been known in the past to add a methine dye or the like during chemical sensitization of a silver halide emulsion. It is just a method of adding without seeing any adsorption property to.

In comparison with these, in the present invention, as will be described later, the sensitizing dye to be used determines which index plane of the silver halide grain surface is selectively adsorbed, and also the plane index of the silver halide grain surface. After grasping this, by positively utilizing this to control and generate the position of the chemical sensitization nucleus (that is, latent image formation) in a limited place, the occurrence of pressure fog is improved and the spectral sensitization is improved. This is to obtain a high-sensitivity silver halide emulsion which is also felt, which is completely different from the conventional technique.

It has heretofore been known to add a sensitizing dye as in the present invention at the start of chemical sensitization. For example, those described in U.S. Pat. No. 4,345,501 and Japanese Patent Application No. 62-141112 are twin (tabular) grains different from the present invention.

In addition, JP-A-61-133941, JP-A-59-9153 and JP-A-58-28738.
No. 62-7040, the sensitizing dye is simply allowed to coexist at the time of chemical sensitization, and the present invention used for advanced control by accurately determining the selectivity of dye adsorption. Is completely different.

Further, Japanese Patent Application No. 61-311131 describes that a dye is used to control the development center position, that is, the chemical sensitization position, and similarly to the present case, the development center, that is, the chemical sensitization is performed on the (111) plane. Although it was carried out, the dye used was not an accurate judgment of adsorption selectivity, and the silver halide used was an emulsion having a high silver chloride content and a halogen conversion was used. However, it is different from the present invention.

In contrast to this, the present invention determines the adsorption selection of the dye,
The present invention is a much more sophisticated technique in which the (0) plane is more positively coated and the (111) plane is selectively chemically sensitized.

It is also known to add a dye at the time of grain formation before the start of chemical sensitization. For example, U.S. Pat.
No. 3, No. 3628960, No. 4183756, No. 4225666, JP-A No. 60-196749, No. 61-103149, No. 61-165751, Research Disclosure Magazine 19227, 192, 155, 198.
There are 0 years, etc., but in most cases, the dye used is present at the time of chemical sensitization, but all of them are merely to make the dye coexist appropriately, and are different from the intention and result of the present invention. Is.

See also DC Birch et al., Journal of Photographic Science.
23, 249 (1975), (111) plane and (100) plane
It has been reported that when a tetrahedron having a face ratio of about 50:50 is subjected to excessive sulfur sensitization with sodium thiosulfate, it is selectively chemically sensitized on the (111) face. In the place where the aging time is short, many are formed on the (100) plane, and gold / sulfur sensitization is not known at all, and pressure fog when a dye is used is not known at all.

The present invention uses particles having much more (100) faces than Birch et al., And particularly selects and uses a dye that selectively adsorbs to (100) faces, and is not limited to sodium thiosulfate and other chemical sensitizers. Is a highly sensitive halogenated compound which has a sophisticated effect of positively forming chemical sensitized nuclei only on the (111) plane and also has an unexpected effect of remarkably improving the occurrence of pressure fog caused by the dye. This is to obtain a silver emulsion.

The high level control of the latent image forming position in the present invention is estimated as follows.

Since the (100) face, which occupies 60% or more of the surface of the silver halide grain, is coated with the sensitizing dye that is selectively adsorbed by this face, the chemical sensitizer is added. The formation of effective chemical sensitized nuclei is suppressed, while the effective chemical sensitized nuclei are preferentially formed on the (111) plane which is not coated or has a small degree of coating. As a result, it is considered that latent images can be formed only at a limited position.

In the silver halide emulsion consisting essentially of normal crystal grains used in the present invention, at least 60% or more of the grain surface is (100).
Surface, and preferably 65% or more. (111) plane is 3
It is preferably 5% or less.

The surface of a silver halide grain is generally (100) plane, (11
It consists of 1) and (110) planes, especially (100) and (111) planes.
Most of them consist of faces.

The surface ratio can be directly observed from an electron micrograph of a silver halide emulsion grain by a carbon replica method, or more accurately, a method described in Chemical Society of Japan 1984, No. 6, 942 can be used. . Different amounts of dye (anhydro-3,3'-bis- (sulfobutyl))
-9-Methylthiacarbocyanine hydroxidepyridinium salt) was added to measure the reflection spectrum of a thick liquid emulsion layer, and paying attention to the fact that the above-mentioned dyes give significantly different spectra on the (100) plane and the (111) plane. By using the Kubelka-Munk equation, the ratio of (100) face and (111) face can be obtained.

The determination of the latent image forming position in the present invention is performed as follows.

The characteristic image of a silver image obtained by exposing a light-sensitive material coated with a target silver halide emulsion on a support for 1 second and developing it with a Kodak formulation MAA-1 developer at 20 ° C. for 10 minutes ( The exposure amount corresponding to (maximum density-minimum density) x 1/2 or exposure up to 1000 times is performed. Next, development is carried out at 20 ° C. for 10 minutes with the following suppressed developer. However, the development time, the pH of the developing solution and the amount of the surfactant are changed according to the particle size and the halogen composition, and the fine silver indicating the development starting point is adjusted so that it can be easily observed.

For example, when the iodide content is high or the development inhibitor works strongly due to the sensitizing dye used, the pH is slightly increased with caustic soda or the development time is extended.

Further, the surfactant in the retarded developer makes the developed silver, which easily spreads like filaments, into a lump and makes it easy to determine the position where the developed silver is formed.

After such development, the development was stopped with a 5% aqueous solution of glacial acetic acid, and without fixing, pronase was enzymatically decomposed to collect silver halide grains, and a small amount was placed on a micromesh for an electron microscope. After carbon was vapor-deposited so that silver could not be printed out, it was fixed with a fixing solution to make a carbon replica, and the position of the developed silver remaining, that is, the position of latent image formation was observed with an electron microscope.

In the present invention, the preferential formation of a latent image on the (111) plane means that a plurality of fine silver particles developed by the above-described suppression development method are present in each particle, preferably 3 or more and 15 or less. When counted under the condition that the developed silver within is pasted, (1
11) Many depending on the surface, for example 80% or more is preferable 90%
It means that the above is formed. Most preferably, fine silver is formed only on the (111) plane. 50% of the total projected area of all silver halide grains in the emulsion layer of the light-sensitive material of the present invention
The above are normal crystal grains that satisfy the conditions, but preferably 70% or more, particularly 90% or more of the total projected area are normal crystal grains that satisfy the conditions.

Further, 70% or more (number) of the normal crystal particles satisfying the condition satisfy the condition, but preferably 80% or more, particularly 90% or more of the particles satisfy the condition.

The (1 1) plane of the silver halide grain referred to in the present invention is (1
There are the following three methods for determining the sensitizing dye that is more selectively adsorbed on the (00) surface.

(Part 1) Discrimination method based on absorption spectrum.

Prepare silver bromide octahedral grains having a (111) plane and silver bromide cubic grains having a (100) plane. The surface area of each particle is calculated from the electron micrograph of each particle, and the (111) plane and (1
A silver halide emulsion is prepared in which octahedral grains and cubic grains are mixed so that the areas of (00) planes are equal.

Of the methine dyes, which are photographically useful dyes and are also preferred in the present invention, which of the methine dyes has a different absorption spectrum depending on whether the surface of the silver halide grain to which the dye adsorbs is (111) face or (100) face, It can be determined from the absorption spectrum whether or not it is selectively adsorbed from the surface. That is, on the cubic particles beforehand,
The absorption spectrum of the adsorbed dye on the surface grains is determined in advance, and the absorption spectrum of the dye when added to the above mixed emulsion is measured. From the absorption wavelength peak, the (111) plane and (1
It is possible to determine which of the (00) planes to selectively adsorb.

Further, from which spectrum, which surface is to be selectively adsorbed can be quantitatively measured by the method described in the above-mentioned Journal of Chemical Society of Japan 1984, No. 6, 942.

(Part 2) Discrimination Method by Emulsion Separation Silver bromide octahedral grains and silver bromide cubic grains having greatly different grain sizes are mixed so that the (111) face-to-face product and the (100) face-to-face product are equal.

Dyes are added to this mixed emulsion to be adsorbed, and then octahedral grains and cubic grains are separated with a filter, and the amount of the dye in each emulsion is quantified.

This is specifically shown in Example 1.

(Part 3) Discrimination Method by Photographic Method A silver halide emulsion is prepared in which octabromide bromide grains and cubic bromide grains are mixed so that the (111) face and the (100) face are the same. Of course, silver iodobromide, silver chlorobromide and the like may be used.

However, the cubic grains are remarkably low in sensitivity as compared with the octahedral grains, and only the octahedral grains contribute to the photographic sensitivity of this mixed emulsion. Specifically, rhodium is doped only on the cubic particle side. No matter how much dye is adsorbed on the cubic particles, the spectral sensitivity due to the dye is not seen,
It is only when the dye is adsorbed on the octahedral grains that the spectrophotometric sensitivity of the dye is obtained in this mixed emulsion.

As can be seen from the above, the dye that is selectively adsorbed on the (100) face over the (111) face in the present invention is adsorbed on the cube first when added to this mixed emulsion. Spectral sensitivity cannot be obtained until it is saturated.

Of course, after the cube is completely saturated, it is adsorbed on the octahedral particles to obtain the spectral sensitivity.

Correspondence between the amount of dye added and the spectral sensitivity with an emulsion containing only octahedral grains having the same surface area as the mixed emulsion (however, half of the grains are doped with rhodium into the grains to make it extremely insensitive). Is prepared in advance, and the dye addition amount (a) in the mixed emulsion which gives the same sensitivity as the spectral sensitivity at a certain dye addition amount (referred to as b) obtained in this emulsion is obtained.

With this dye addition amount (a), the dye amount on the octahedral grains and cubic grains in the mixed emulsion is Therefore, quantitative measurement can be performed.

The present inventors have used these methods to select a dye that is more easily adsorbed to the (100) plane than the (111) plane of the present invention.

The sensitizing dye which is more easily selectively adsorbed on the (111) plane of the silver halide grain in the present invention is preferably selected from methine dyes.

Specifically, it includes a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye and a hemioxonol dye. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus,
A tetrazole nucleus, a pyridine nucleus, etc .; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus , Benzoxadol nucleus,
A naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

The merocyanine dye or the complex merocyanine dye has a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-2, as a nucleus having a ketomethylene structure.
5- to 6-membered heterocyclic nuclei such as 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus can be applied.

For example, it can be used by selecting from the compounds described in RESERCH DISCLOSURE Item. 17, 643, page 23, page IV (December 1978) or the compounds described in the cited documents.

(10) rather than (111) plane of the silver halide grain in the present invention.
Preferred methine dyes as dyes that are more easily adsorbed to the (0) surface are cyanine dyes and merocyanine dyes,
Particularly, a cyanine dye is preferable.

Among them, benzoxacyanine, benzimidazoline, benzoxa-imidazoline, benzoxa-thiacyanine, benzimidazole-thiacyanine, benzoxa-selenacyanine, benzimidazole-selenacyanine, and a substituent other than a halogen atom at the 5-position of the benzene nucleus or no substituents. Substituted benzthiacyanine, benzselenacyanine and benzthia-selenacyanine are preferred.

Further, more preferable among these dyes are those that form a J-aggregate on the surface of the silver halide grain.

The following methine dyes are mentioned as typical specific examples.

The amount of the sensitizing dye to be used is preferably an amount that saturates or adsorbs the (100) plane or more, and preferably an amount that saturates or adsorbs all the (111) faces and the (100) face.

The silver halide used in the photographic emulsion of the present invention is silver bromide and / or silver iodobromide, but it may contain a trace amount of silver chloride.

Particularly preferred is silver iodobromide having a silver iodobromide content of 0.1 to 38 mol%, particularly 0.5 to 30 mol%.

The conditions for chemical sensitization in the present invention are not particularly limited, but pAg is 6 to 11, preferably 7 to 10, more preferably 7 to 9.5, and temperature is 40 to 95 ° C, preferably 50. ~ 85 ℃.

The chemical sensitization method used is a so-called gold sensitization method using a gold compound (for example, US Pat. Nos. 2,448,060 and 3,320,069).
) Or a sensitization method using a metal such as iridium, platinum, rhodium or palladium (for example, US Pat. No. 2,448,060,
No. 2,566,245, No. 2,566,263) or a sulfur sensitizing method using a sulfur-containing compound (for example, US Pat. No. 2,222,264), a selenium sensitizing method using a selenium compound, or a reduction sensitizing method using tin salts, thiourea dioxide, polyamine and the like ( For example, U.S. Patent Nos. 2,487,850, 2,518,698, and 2,521,925.
No.) or a combination of two or more of these.

In particular, the silver halide grain of the present invention is preferably gold-sensitized or sulfur-sensitized, or a combination thereof.

As the sulfur sensitizer, in addition to sodium thiosulfate,
The following compounds can also be preferably used.

As the gold sensitizer, any known one such as chloroauric acid salt can be used.

The amount of the sulfur sensitizer and the gold sensitizer is 10 ⁻⁸ to 10 ⁻³ mol, preferably 10 ⁻⁷ to 10 ⁻⁴ mol, per mol of silver halide.

The silver halide grains may have different phases in the inside and the surface layer, or may be composed of a uniform phase.

Further, for example, a junction type silver halide crystal in which an oxide crystal such as PbO and a silver halide crystal such as silver chloride are combined,
It may also be an epitaxially grown silver halide crystal (for example, silver chloride, silver iodobromide, silver iodide, etc. are epitaxially grown on silver bromide).

The grain size distribution of silver halide grains in the photographic emulsion is arbitrary, but monodisperse grains are preferred. Here, monodisperse refers to a dispersion system in which 90% of particles fall within ± 60% of the number average particle size, preferably within 40%. Here, the number average grain size is the number average diameter of the projected area diameters of silver halide grains.

The photographic emulsion of the present invention is described by P. Glafkides, Chemie et Physiq.
ue Photographique (Published by Paul Montel, 1967), GF
Photographic Emulsion Chemistry (The Foc
Al Press, 1966), by VL Zelikman et al Making
and Coating Photographic Emulsion (The Focal Pres
S., 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. .

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. PAg in the liquid phase in which silver halide is formed as a form of simultaneous mixing method.
To keep constant, that is, so-called controlled
It is preferable to use the double jet method.

According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Two or more kinds of silver halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt may coexist. Among them, iridium salt, rhodium salt and iron salt are preferable. Further, the addition amount thereof may be a small amount or a large amount depending on the intended light-sensitive material.

In addition, depending on the purpose, there are already known silver halide solvents (for example, ammonia, rodancali, and US Pat.
71157, JP-A-51-12360, JP-A-53-82408, JP-A-53-144319, JP-A-54-1007, 17, JP-A-54-15582
The thioethers and thione compounds described in No. 8 etc. can be used. In addition, JP-A-60-136736 and JP-A-60-163042
No. 60-222843, No. 61-3135 and the like may be used to form particles.

The above-mentioned various additives are used in the light-sensitive material of the present technology, but various additives other than the above can be used depending on the purpose.

These additives are described in more detail in Research Dice Closure Item 17643 (December 1978) and Item 187
16 (November, 1979), and the relevant places are summarized in the table below.

Further, the description of the Research Disclosure can be considered later regarding the method for producing the photosensitive material and the developing method of the present invention.

Example 1 After preparing monodisperse silver iodobromide (Iode 1 mol%) octahedral grains having a particle size of 2 microns and monodisperse silver iodobromide (Iode 1 mol%) cubic grains having a particle size of 0.5 μm, respectively. , (111) face area product and (100) face area product were mixed.

As shown in Table 1, sensitizing dye was added to the mixed emulsion to obtain pH 6.5, p
After adsorbing with Ag8 for 30 minutes at 60 ° C., the amount of dye in the cubic emulsion filtered through a filter having a pore size of 0.8 μm was measured, and the ratio to the amount of dye originally added is shown in Table 1.

However, the amount of the added dye is 10 × 10 ⁻⁵ mol / mol AgBr, and when the contained area is 70Å ² per molecule, it corresponds to the amount of the dye containing approximately 20% of the total surface area.

As is clear from Table 1, the dyes D-1, 2 of the present invention,
3,7,11,13,14,16,20,21,22,25,27 are hardly adsorbed on the octahedron, or slightly adsorbed on the octahedron. From this, it could be determined that the adsorption was more selective.

In this way, it can be quantitatively determined from which of the (100) / (111) faces of the AgX particles the dye is more selectively adsorbed.

"-" In Table 1 means "about".

However, in the case of the experiment of Dye D-3, D-3 is added.
Minutes before, potassium iodide was added to the 216 mg / mol Ag emulsion.

Example 2 While vigorously stirring a gelatin aqueous solution maintained at 60 ° C., ammonia was added, and then a silver sulfate aqueous solution and a potassium bromide aqueous solution were simultaneously added. The pAg was kept at 7.7 during the addition.

Then, after washing and desalting by the flocculation method according to the usual method, the pH was adjusted to 6.3 pAg to 8.5.

What was obtained was a monodisperse tetradecahedral silver bromide emulsion (grain size: about 0.8μ).

When the ratio of the (100) face to the (111) face of this emulsion was examined by the method described in No. 6,942 page of the Chemical Society of Japan in 1984, 72% of the (100) face was 28% of the (111) face. Atsuta

This emulsion was divided into Emulsion A and Emulsion B in 2 minutes. Emulsion A was optimally heated with sodium thiosulfate, chloroauric acid and potassium thiocyanate at 60 ° C., and then Dye D-2 was added (addition amount 5 × 10 ⁻⁴ mol / mol Ag). On the other hand, Emulsion B was optimally heated at 60 ° C. with sodium thiosulfate, chloroauric acid and potassium thiocyanate after addition of Dye D-2.

Stabilizer (4-hydroxy-6-methyl-1,3,3a-7-tetrazaindene) and antifoggant (1- (m-sulfophenyl) -5-mercaptotetrazole mono Na salt) were added to each emulsion. In addition, a coating aid (dodecyl
Benzene / sodium sulfonate), thickener (poly (4-sulfostyrene) potassium salt), hardener (2,4-
Dichloro-6-hydroxy-s-triazine sodium) was added, and the mixture was coated on the cellulose acetate film support together with the gelatin protective layer by the coextrusion method and dried to obtain a sample.

The obtained sample is 6m in diameter at 25 ° C and 45% relative humidity.
It was bent 180 ° along the m bar. Immediately after that, the wafer was exposed to light for 10 ^-2 seconds, and was exposed to 20 with the Kodak recipe MAA-1 developer.
It was developed for 10 minutes at ℃.

Table 2 shows the increase in fog on the bent part (ΔFo
g) is shown. In addition, the relative sensitivity of the unbent portion is also shown. Here, the relative sensitivity is the relative ratio of the reciprocal of the exposure amount required to obtain the blackening degree of +1.0, and the emulsion (A) was set to 100.

In addition, the characteristic curve (Dmax-Fo
g) × 1/2 the exposure amount which is 100 times the exposure amount that gives the midpoint density is uniformly given, and after development with the inhibitor developer in the specification for 10 minutes at 20 ° C., after stopping with 5% acetic acid, With Pronase,
The emulsion was peeled off from the coating film, and undeveloped silver halide was removed to prepare a carbon replica.

Table 2 also shows the surface where developed silver is located, as observed with an electron microscope.

As is clear from Table 2, the emulsion (B) of the present invention chemically sensitized in the presence of the dye D-2 which is selectively adsorbed on the (100) plane and chemically sensitized only on the (111) plane. ), The relative sensitivity is equal to or higher than that of the emulsion (A) which is not.
It is also clear that the pressure fog sensitization is significantly suppressed.

Example 3 As in Example 2, except that the pAg at the time of grain formation was kept at 7.4, and potassium iodide was also added at the same time as potassium bromide, a silver iodobromide emulsion having a grain size of about 0.9 μ (iodination Silver (2 mol%). The (100) plane was 95% and the (111) plane was 5%, which was a substantially cubic emulsion.

This emulsion was divided into four parts (C, D, E, F). Emulsion C was sensitized with D- (4 × 10) sensitizing dye after gold and sulfur sensitization with sodium thiosulfate, chloroauric acid and potassium thiocyanate. ^-Four
Mol / mol Ag) and D-9 (1.5 × 10 ⁻⁴ mol / mol Ag). Emulsion D was sensitized with sulfur sensitizer S-3, chloroauric acid and potassium thiocyanate, and then dye D-
1 and D-9 were added. Emulsions E and F are dyes D-1 and D
After adding -9, E is sodium thiosulfate, F
Was sensitized with gold and sulfur using chloroauric acid and potassium thiocyanate.

Couplers (C-1, C-11, C-12, C) were added to each emulsion.
-13, C-15), dispersed oils (Oil-1, Oil-2) and the same stabilizers, antifoggants, thickeners, coating aids and hardeners as in Example 2 were added together with the gelatin protective layer. It was coated on a cellulose acetate film support. (Sample 3 ~
6) After uniform exposure at 10 ^-2 , the tip radius is about 30μ.
With a needle made of sapphire of m, a load of 4g is applied every second.
The emulsion side of each sample was scratched at a speed of 5 cm. Subsequently, the following color development processing was performed at 38 ° C. The density of scratches generated by scratching with a needle was measured with a microdensitometer to determine the density difference from the non-scratched area. The results are shown in Table 3.

In addition, the results of performing the same suppressed development process as in Example 2 are also shown. The grains are almost cubic and the (111) plane corresponds to a corner.

Color development 2 minutes 45 seconds Bleach 6 minutes 30 seconds Water washing 2 minutes 10 seconds Settling 4 minutes 20 seconds Water washing 3 minutes 15 seconds Stability 1 minute 05 seconds The treatment liquid composition used in each step is as follows. It was

Color developer Diethylenetriaminepentaacetic acid 1.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate 30.0g Potassium bromide 1.4g Potassium iodide 1.3mg Hydroxylamine sulfate 2.4g 4- (N- Ethyl-N-β-hydroxyethylamino)
-2-Methylaniline sulfate 4.5g Add water 1.0l pH10.0 Bleaching solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium bromide 150.0g Ammonium nitrate 10.0g Add water 1.0l pH 6.0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0ml Sodium bisulfite 4.6g Water is added 1.0l pH 6.6 Stabilizer Formalin (40%) 2.0ml Poly Oxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3g Water added 1.0l As is clear from Table 3, the samples 5 and 6 in which the suppressed development centers are positively formed in the corners, that is, in the (111) plane, have significantly higher pressure due to needle scratching than those of the other samples (samples 3 and 4). It can be seen that the fogging is small and the pressure resistance is excellent.

An electron micrograph of the suppressed development of Sample 5 (approximately 15600 times)
Is shown in FIG.

Example 4 In Example 3, D-14 and D were used instead of D-1 / D-9.
Using -15, D-21, D-22, and D-27, the same experiments as for emulsion (C) and emulsion (E) were carried out.

Of all the dyes, emulsion (E) is emulsion (C)
The increase in pressure fog due to needle scratching was smaller than that.

Example 5 Emulsion G, which is a double-structured grain in which silver bromide is attached to the shell portion, was prepared using 20 mol% iodide of silver iodobromide as a seed crystal. It is a monodisperse emulsion having a silver iodide content of 5 mol%, a grain size of about 0.7 μm, a (100) plane of 65%, and a (111) plane of 35%.

Adjust the pH to 6.2 pAg to 8.9 and mix the emulsion for 2 minutes (G-1, G-
2) I did.

Emulsion G-1 contained sodium thiosulfate and dyes VII and VIII after gold and sulfur sensitization with chloroauric acid and potassium thiocyanate.

Emulsion G-2 was sensitized by gold and sulfur with sodium thiosulfate, chloroauric acid and potassium thiocyanate after adding dyes VII and VIII.

When the emulsion was coated in a single layer and the latent image formation site was examined by the suppression development method, it was found that in the emulsion G-1, minute developed silver was formed not only on the (111) plane but also on the (100) plane. On the other hand, emulsion G-2
Was formed only on the (111) plane.

Further, in a multilayer color light-sensitive material having the composition shown below, Sample 7 in which Emulsion G-1 was incorporated in the ninth layer.
After making Sample 8 incorporating Emulsion G-2, this photographic element was exposed to 25 CMS with a tungsten light source and a filter adjusted to a color temperature of 4800 ° K, followed by the following processing steps: Then, development processing was performed at 38 ° C.

Also, as in Example 3, the increase in pressure fog with the sapphire needle was observed.

The results obtained are shown in Table 4.

In the table, the relative sensitivity is the reciprocal of the exposure amount that gives a color density of fog value +0.1, and the value of Sample 7 was set to 100.

As is clear from the table, the present invention in which a latent image is positively and selectively formed on the (111) plane is superior to the emulsion in which the latent image is not formed, and it is excellent in that the increase in fog due to needle scratching is small. It is clearly pressure resistant.

Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water washing 2 minutes 10 seconds Settling 4 minutes 20 seconds Water washing 3 minutes 15 seconds Stability 1 minute 05 seconds The composition of the treatment liquid used in each step is the same as in Example 3. It was.

(Composition of photosensitive layer) The coating amount of silver halide and colloidal silver is silver.
The amount represented in units of g / m ^2, also couplers, moles per 1 mol of silver halide in the same layer for the amount for the additives and gelatin represented in units of g / m ^2, also the sensitizing dye Indicated by.

1st layer (anti-halation layer) Black colloidal silver ・ ・ ・ 0.2 Gelatin ・ ・ ・ 1.3 Colored coupler C-1 ・ ・ ・ 0.06 UV absorber UV-1 ・ ・ ・ 0.1 Same as above UV-2 ・ ・ ・ 0.2 Dispersion oil Oil-1 ・ ・ ・ 0.01 Same as above Oil-2 ・ ・ ・ 0.01 Second layer (intermediate layer) Fine grain silver bromide (average particle size 0.07 μm) ・ ・ ・ 0.15 Gelatin ・ ・ ・ 1.0 Colored coupler C-2 ・ ・-0.02 Dispersion oil Oil-1 ... 0.1 Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 2 mol%, average grain size 0.3 µ) ... Silver 0.4 gelatin ... 0.6 sensitizing dye I ・ ・ ・ 1.0 × 10 ^-4 sensitizing dye II ・ ・ ・ 3.0 × 10 ^-4 sensitizing dye III ・ ・ ・ 1 × 10 ^-5 coupler C-3 ・ ・ ・ 0.06 coupler C-4 ・・ ・ 0.06 Coupler C-8 ・ ・ ・ 0.04 Coupler C-2 ・ ・ ・ 0.03 Dispersion oil Oil-1 ・ ・ ・ 0.03 Same as above Oil-3 ・ ・ ・ 0.012 Fourth layer (second red-sensitive emulsion layer) Odor Silver halide emulsion (5 mol% silver iodide, average grain size 0.5 μ) ・ ・ ・ 0.7 Gelatin ・ ・ ・ 0.6 Sensitizing dye I ・ ・ ・ 1 × 10 ^-4 Sensitizing dye II ・ ・ ・ 3 × 10 ^-4 Sensitizing Dye III ・ ・ ・ 1 × 10 ^-5 Coupler C-3 ・ ・ ・ 0.24 Coupler C-4 ・ ・ ・ 0.24 Coupler C-8 ・ ・ ・ 0.04 Coupler C-2 ・ ・ ・ 0.04 Dispersion Oil Oil-1 ・・ ・ 0.15 Same as above Oil-3 ・ ・ ・ 0.02 Fifth layer (third red-sensitive emulsion layer) Silver iodobromide emulsion (Silver iodide 10 mol%, average grain size 0.7μ) ・ ・ ・ Silver 1.0 gelatin ・ ・・ 1.0 Sensitizing dye I ・ ・ ・ 1 × 10 ^-4 Sensitizing dye II ・ ・ ・ 3 × 10 ^-4 Sensitizing dye III ・ ・ ・ 1 × 10 ^-5 Coupler C-5 ・ ・ ・ 0.05 Coupler C-7・ ・ ・ 0.1 Dispersed oil Oil-1 ・ ・ ・ 0.01 Same as above Oil-2 ・ ・ ・ 0.05 Sixth layer (intermediate layer) Gelatin ・ ・ ・ 1.0 Compound Cpd-A ・ ・ ・ 0.03 Dispersed oil Oil-1 ・ ・ ・0.05 Seventh layer (first green-sensitive emulsion layer) Silver iodobromide emulsion (iodine 4 mol% silver halide, average particle size 0.3 μ) ・ ・ ・ 0.30 Sensitizing dye IV ・ ・ ・ 5 × 10 ^-4 Sensitizing dye VI ・ ・ ・ 0.3 × 10 ^-4 Sensitizing dye V ・ ・ ・ 2 × 10 ^-4 Gelatin ・ ・ ・ 1.0 Coupler C-9 ・ ・ ・ 0.2 Coupler C-5 ・ ・ ・ 0.03 Coupler C-1 ・ ・ ・ 0.03 Dispersion oil Oil-1 ・ ・ ・ 0.5 Eighth layer (second green emulsion layer) ) Silver iodobromide emulsion (5 mol% silver iodide, average grain size 0.5 μ) ・ ・ ・ 0.4 Sensitizing dye IV ・ ・ ・ 5 × 10 ^-4 Sensitizing dye V ・ ・ ・ 2 × 10 ^-4 sensitizing Dye VI ・ ・ ・ 0.3 × 10 ^-4 Coupler C-9 ・ ・ ・ 0.25 Coupler C-1 ・ ・ ・ 0.03 Coupler C-10 ・ ・ ・ 0.015 Coupler C-5 ・ ・ ・ 0.01 Dispersion Oil Oil-1 ・ ・ ・0.2 ninth layer (third green-sensitive emulsion layer) emulsion G emulsion (silver iodide 5 mol%, average particle size 0.7 .mu.m) ... silver 0.85 gelatin ... 1.0 sensitizing dye VII ... 4.0 × 10 ^{- 4} sensitizing dye VIII ··· 1.4 × 10 ^-4 coupler C-11 ··· 0.01 coupler −12 ・ ・ ・ 0.03 Coupler C-13 ・ ・ ・ 0.20 Coupler C-1 ・ ・ ・ 0.02 Coupler C-15 ・ ・ ・ 0.02 Dispersed oil Oil-1 ・ ・ ・ 0.20 Same as above Oil-2 ・ ・ ・ 0.05 10th Layer (yellow filter layer) Gelatin ・ ・ ・ 1.2 Yellow colloidal silver ・ ・ ・ 0.08 Compound Cpd-B ・ ・ ・ 0.1 Dispersion oil Oil-1 ・ ・ ・ 0.3 Eleventh layer (first blue-sensitive emulsion layer) Monodisperse odor Silver halide emulsion (4 mol% silver iodide, average grain size 0.3 μ) ・ ・ ・ Silver 0.4 Gelatin ・ ・ ・ 1.0 Sensitizing dye IX ・ ・ ・ 2 × 10 ^-4 Coupler C-14 ・ ・ ・ 0.9 Coupler C- 5 ・ ・ ・ 0.07 Dispersion oil Oil-1 ・ ・ ・ 0.2 12th layer (second blue sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 10 mol%, average grain size 1.5 μ) ・ ・ ・ Silver 0.5 gelatin・ ・ ・ 0.6 Sensitizing dye IX Coupler C-14 ・ ・ ・ 0.25 Dispersion oil Oil-1 ・ ・ ・ 0.07 13th layer (first protective layer) Gelatin ・ ・ ・ 0.8 UV absorber UV-1 ・ ・ ・ 0. 1 Same as above UV-2 ・ ・ ・ 0.2 Dispersion oil Oil-1 ・ ・ ・ 0.01 Dispersion oil Oil-2 ・ ・ ・ 0.01 14th layer (second protective layer) Fine silver bromide (average particle size 0.07μ) ・ ・・ 0.5 Gelatin ・ ・ ・ 0.45 Polymethylmethacrylate particles (diameter 1.5μ) ・ ・ ・ 0.2 Hardener H-1 ・ ・ ・ 0.4 Formaldehyde scavenger S-1 ・ ・ ・ 0.5 Formaldehyde scavenger S-2 ・ ・ ・0.5 In addition to the above components, a surfactant was added to each layer as a coating aid.

The chemical structural formulas or names of the compounds used in the present invention are shown below: Oil-1 Tricresyl phosphate Oil-2 Dibutyl phthalate Oil-3 Bis (2-ethylhexyl) phthalate

[Brief description of drawings]

FIG. 1 is an electron micrograph of the crystal structure of silver halide grains in the silver halide emulsion of Sample-5 of Example-3,
The magnification is 15,600 times.

Claims (1)

[Claims] 1. In a photographic light-sensitive material having at least one silver halide emulsion layer on a support, 50% or more of the total projected area of all silver halide grains in the silver halide emulsion layer is 50% or more. A silver halide photographic light-sensitive material, which is a normal crystal grain satisfying the following conditions, and 70% or more (number) of the normal crystal grains are grains satisfying the following conditions. 60% of the surface of the silver bromide or silver iodobromide grains which are substantially normal crystals of (111) and (100) faces.
The above is the (100) plane. It is chemically sensitized in the presence of a sensitizing dye that is more selectively adsorbed to the (100) plane than the (111) plane, and a latent image is preferentially formed on the (111) plane.