JPS58111938A - Radiosensitive emulsion - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of the Invention Jin's invention is useful in the field of photography.
This invention relates to a radiation-sensitive emulsion commonly used to form i111I.

(b) A photograph l which, by prior art exposure, yields an image with an optical density directly related to the radiation received! The original is called Negatipu Working (Nega!!I). - wrinkle photo 1iii1
1I is obtained by forming a negative photographic image and then forming a second photographic Im image which is a first negative or l di-image. Direct positive type - I is understood to be an image that is formed without first forming a negative image in photography - Direct I type photography is a type of positive photography - I am understood to be an image that is formed without first forming a negative image in photography. It is advantageous for islands that get a direct approach.

The usual approach to directly forming four-dimensional particles is to use photographic elements with internal fII-forming cylinization-particles. After exposure, the silver halide grains are developed with a surface developer.The surface developer is a solution that leaves the latent image areas within the silver halide grains substantially free from obvious K. Depending on the example of simultaneous exposure, uniform exposure, or the use of nucleating agents, the dihalonated particles are subjected to existing conditions that do not cause fogging of the surface f11-forming photographic element. Under these conditions, the internal latent image-forming halo/silver halide grains that accept actinic radiation during imagewise exposure are exposed at a slower rate compared to the internal latent image-forming silver halide grains that are not imagewise exposed. Become a current servant. Result 11 In a 0 color photograph that is a direct 4-di ffi silver image, the oxidized developer obtained during W14 development is used to form the corresponding positive-working, direct-positive dye image. Multicolor direct/digital photography has been extensively studied in connection with IiIjg11 transfer photography.

The direct tenon type internal 1111gI forming emulsion takes the form of a Helog/compound conversion type emulsion. Such an emulsion is
U.S. Patents 2,456,943 and 2,592,250
It is explained by.

Very recently it has been found advantageous to use core-shell emulsions. Early teachings on core-shell emulsions were provided by US %TF3,206,313, #
In one patent, a coarse grain monodisperse chemically sensitized emulsion is mixed with a finer grain emulsion. The mixed pi#a1 particles are Ostwald ripened onto chemically sensitized larger particle surfaces. As a result, a shell is formed around the coarse particles O. The chemical sensitization of the coarse particles is "embedded" by the shell within the resulting core-shell particles.Due to the imagewise exposure, latent image sites are formed at internal sensitization sites, so that they are also located internally. The main function of the shell structure is that the surface f
The purpose is to prevent the As liquid from approaching the internal latent image area, thereby making it possible to achieve a minimum temperature of 9 degrees.

Chemical sensitization of the core emulsion can take an O-shape. One technique is to sensitize the surface of the core with conventional sensitizers, such as sulfur and gold. US Pat. No. 4,035,185 teaches the following. That is, controlling the ratio of intermediate chalcodan to the noble metal sensitizer used for core sensitization can control the contrast obtained by the core shell. Another technique that can be employed is to incorporate metal particles such as iridium, bismuth or lead into the core particles as they are formed.

The shell of the core-shell particle is U.S. Patent No. 3.206,31
1 need not be formed by Ostwald ripening as taught by US Pat. No. 3,761,27, but can alternatively be formed by direct precipitation on the sensitized core particles.
6.3,850,637 and 3,923,513 teach the following: That is, after the core-shell particles are formed, it is possible to further increase photographic speed if they are surface chemically sensitized. However, surface chemical sensitization is limited in order to maintain a balance of surface and internal sensitization that favors the formation of internal latent image sites.

The use of mixtures of negative working emulsions to control the shape and position of the characteristic curves of photographic elements is generally well known in the photographic art. Regarding this kind of implementation, Z*likm
9, “Photographic Emulsion O1&il Preparation and Coating” (Focal Publishing, 1964, 23'4-
(p. 238) Discussed in K. Mixing of superficially coupled direct positive emulsions also yields 1fI1%tf3,61
5,573, conventional negative working emulsions and superficially coupled direct positive working emulsions are generally prepared as monodisperse or heterogeneous emulsions, and these emulsions However, these preparations are carried out as monodisperse emulsions depending on the percentage of the core-shell emulsion. In contrast, the Ostwald ripening process of US Pat. No. 3,206,313 mentioned above requires that both the core and shell emulsions be monodisperse. Additionally, the above U.S. Pat. No. 3,761,276.3,8
50,637 and 3,923,513, monodisperse core emulsions control shell formation and make it nonuniform even when precipitation occurs directly on the core emulsion. .

Mixing of core-shell emulsions has been taught prior to this invention only when core-shell grains having similar average grain sizes are mixed. For example, the above-mentioned US patent 4,0
In No. 35,185, monodisperse core-shell emulsions with different proportions of sulfur to total internal sensitization are successfully mixed. Other recently, semidisperse core-shell emulsions with different degrees of surface chemical sensitization but with the same average grain size have been successfully mixed.

Black-and-white photography relies on traditionally developed silver to form the visualized image.Moths are not contaminated with the final image - although they are often recovered, they can be used in many applications such as silver image transfer. Silver is rarely recovered.

The chimes that form the images are sometimes recovered, and are exposed to radiation 11
Although recovered from the base, even in this case the silver remaining in the imaging island base is not available for multi-year recycling. Because of the cost of silver, it is highly desirable to make effective use of the silver in silver. The most important measure of efficiency for silver mail is the covering power. In the present invention, the covering power is quantitatively determined as the ratio of the maximum density to the developed chain multiplied by 100, and is expressed in Durhams to the square of the decimega. high covering)
4W has been recognized as an advantageous element in favor of black and white photography. The covering tools and conditions that influence it are James's ``Theory of the Photographic Process'' (Th@o
ry of th@Photographic Pro
c@m5) (4th edition + Macmillamt 197
7 years 404, 489, and 490 pages), and Firx
＋＊11 and 8o1oman “4-hour Coverings of Photographic Silver Deposit”, Journal Op Photographic Science (Th@Journal o
f Photography@5science), 1
8, 1970, pp. 94-101.

(c) DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a radiation-sensitive emulsion particularly adapted for forming direct positive-working images consisting of a dispersant and halodized grains, the emulsion having enhanced The purpose of the present invention is to provide a silver covering power of 4%.
is achieved by an emulsion having a halodanized grain and a dispersion medium in which a first core-shell silver halide grain population has a coefficient of variation of less than 20% and a second halodanized silver halide grain population has a variation coefficient of less than 20%. It is possible for the particle population to internally supplement the photolytically generated electrons, and the first particle population ([/
) that the second particle population is unable to form a surface latent image within the exposure latitude;
[having an average diameter of no more than 70 mm and further characterized by the presence of said silver particle bands in a weight ratio of 5:1 to 1:5. The emulsion of the present invention Fi% (particularly adapted for forming direct I photographic images) emulsion comprises a dispersion medium and at least two different populations of halogenated grains. The population consists of monodisperse core-shell halodanized particles, i.e. core-shell halodanized particles 11t.
It has a coefficient of variation of less than 20-. For applications requiring high contrast (typically at least S The variation coefficient is defined as 100 times the standard deviation of the grain diameter divided by the average grain diameter.The second halog/silveride grain population is mixed with the first grain population.The second halodane grain population is mixed with the first grain population. The grain population cannot attract photolytically generated electrons therein and cannot form a surface latent image within the direct positive exposure layer of the emulsion.

The second population of particles has an average diameter that is less than 65 times the average diameter of the first population of particles, preferably less than 50 times the average diameter of the population of particles. have less than 40% of The orchestra of the first and second particles is 5 to 1 to 1
:5, preferably in the emulsion in the range of 2:1 to 1:30 electron dow ratio.

Silver Halide Grain Mixtures The emulsions of this invention can be prepared by pre-mixing the emulsions independently by methods known in the art. The first particle band is a normal core-shell emulsion, if kept in US Patent 3,2
06,313.3,761,276.3,850,6di, 3.923,513, and 4,035,185K obtained by any one of the emulsions described. Therefore, the following discussion is limited to certain core-shell emulsion characteristics that are particularly preferred and which differ from the teachings of the above literature.
limited to signs.

Useful core-shell emulsions can be created by first forming a sensitized core emulsion. The core emulsion may be comprised of silver bromide, silver chloride, silver chlorobromide, silver chloroiodide, bromo-dide, or chlorobromide-grain. It can take minute size and (10
0), (111) or (110) crystal planes. The crystal grains may be high aspect ratio tabular grains. The variation coefficient of the 0 core grain is the desired 0 variation coefficient of the completed core-shell particle. Yoshi shouldn't be higher either.

The simplest technique for forming islands of sensitized core particles is
Probably by incorporating a metal donut into the core particles when they are formed. The metal donut can be charged into a reaction vessel, where the silver salt is introduced. Core particle formation occurs before. Separately, metal dopants can be used at any stage of precipitation without interfering with the introduction of silver and/or halide salts.
Iridium, which can be introduced during the growth of silver y'nide grains, is particularly preferred as a metal dopant. It is preferably incorporated into the halogenated particles in a composition of about 10-8 to 10-4 mole to -1 mole. Iridium can be conveniently incorporated into the reaction vessel as a water-soluble salt, such as an alkali metal salt of a rhodan-iridium coordination complex, preferably a sodium or potassium hexachloride or hexapromoiridate. An example of the incorporation of iridium (47) is shown in U.S. Pat. No. 3,367,778.

Lead is also a particularly preferred metal dopant for core particle sensitization. Lead is a common dopant in direct baking and baking emulsions and can be used in the practice of this invention in similar molar ranges. A concentration of up to about 5 x 10-2, preferably 2 x 10-'' per mole of O-1 is generally preferred.
Iridium salts can also be introduced as iridium salts in the form of water-soluble salts such as lead acetate, lead nitrate, and cyanide, as described in U.S. Pat. No. 3,287.
, 136 and 3,531,291, another method of sensitizing core particles is to stop the precipitation of the particles after the core particles have been produced, and then to sensitize the surface of the core particles. It is chemically sensitized. After that, hello l'
Further precipitation of the silver oxide forms a shell surrounding the core. Particularly advantageous chemical sensitizers for this purpose are intermediate chalcodans, ie sulfur, selenium and/or tellurium sensitizers.

The intermediate chalcogen sensitizer is 11m! Approximately 0 per mole,
Preferably used in concentrations ranging from 0.05 to 151 v, preferably from about 0.1 to 10 to 11 moles. It is further advantageous to use it in combination with a gold sensitizer.
．． It is preferably used in a concentration range of 5 to 5 times. The preferred a degree of the gold sensitizer is 0.01 to 40 Wv per mole of silver.
Controlling the contrast depends on controlling the ratio of intermediate chalcodan to gold sensitizer, which is typically about 0.1 to 20 M9 per mole of silver. U.S. Pat. No. 4,035,185
specifically taught by. U.S. Patent 3,76 mentioned above
1,276.3,850,637 and 3,923,51
No. 3 provides specific examples of intermediate chalcone core particle sensitizers.

Although it is preferred that the core particles be sensitized to islands to form complete core-shell particles prior to shell formation, it is not necessary. It is necessary for $ to have the ability to form internal S* image sites when the core-shell particle is formed. Internal sensitization sites obtained by shell formation of the sensitized core particle, i.e. within the core-shell particle. to another (
(i.e., other than silver and halodane), the substance 01  is hereafter referred to as the internal chemical sensitizing site, which is the island that distinguishes it from the internal physical sensitizing site. It is possible to incorporate internal physical sensitizing sites by creating irregularities in the crystal lattice of core-shell particles61.
It is Noh. Such internal irregularities are caused by heronization and precipitation! i
By making the core-shell particles discontinuous or
This can be achieved by suddenly changing the proboscis 111iilf. For example, the following has been observed: That is, precipitation of the silver bromide core, followed by shell formation with more than 5 moles of bromide, is a direct process that does not require internal chemical sensitization to form islands that form III-III images. Although the sensitized core emulsion may be shelled by the Ostwald ripening technique described in U.S. Pat. precipitate directly onto the core particles. D'Aprouge, Tosei, ``Research Disclosure J (vol. 176, December 1978,
17643, Section I)K, which are well known to those skilled in the art. "Research Disclosure" and its previous publications, Product Licensing Index,
The product is manufactured by Industrial OIT, Niti Co., Ltd. (Hom@w
@11+Havant, Hampshlre+PO9I
This is a publication of EFt English #iA). The octaronide device in the shell portion of the grain is
Machi Naru Kageline Moto p is obtained. In order to improve developability, the shell portion of the particles contains at least 480 moles of chloride;
The remaining halide is bromide or bromide and 10 mol S
It is preferable to use jin, which is a Japanese monster. Unless otherwise stated, all halide/dacentages are to the corresponding emulsion, grain, or grain within the grain range discussed. When the shell portion of the core-shell particles consists of at least 80 moles of chloride as mentioned above, an improvement in low concentration reciprocity can also be seen.
Because of these advantages of each, silver chloride is particularly preferred. On the other hand, the highest photographic sensitivity that has been achieved is
61,276.3, 850,637 and 3.923,5
As shown by No. 13, it is generally believed that the use of bromide particles provides superior results. Thus, the specific selectivity of the preferred halide to the shell portion of the core-shell particle will depend on the particular photographic application. If the same halide is chosen to form both the core and shell portions of a core-shell grain structure, the introduction of silver and halides in the transfer from the core to the shell formation may be hindered. Both the core and shell parts of the particle are t-
Preference is given to using a precipitate for the production.

The silver halide that forms the shell part of the core-shell particle is
There must be sufficient islands to restrict access of the developer to the sensitized core of the grains. This varies as a function of the ability of the developer to dissolve the shell of the grains during development. will. Although a small shell thickness of a few crystal lattice planes is taught in the prior art for developers with very low halodanization-1M powers, the shell portion of the core-shell particles is Patent 3,206.3
13 and 4,035,185, it is preferred that the molar ratio with respect to the core portion of the particles be between about 1:4 and 8:1.

The amount of filtration exposure that can be withstood by the emulsions of this invention without promoting re-inversion can be increased for this purpose by incorporating core-shell particles into wire mesh donuts. The term "reinversion" as used in the present invention is intended to refer to the negative action properties exhibited by direct overexposed di-type emulsions. (Reinversion is the opposite of solarization, and is an Idityping characteristic exhibited by overexposed negative emulsions). Preferred metals for this purpose which may be used as metals are divalent and trivalent cationic metals such as cadmium, zinc, lead and erbium. These components are less than about 5 x 10-' per mole, preferably 5 x 10
Generally valid once: There should be at least 10, preferably at least 5 x 10-' dots per mole of silver present in the silver halide precipitation medium reactor. is effective even if introduced at some stage of silver halide precipitation. The reinversion-modifying dopant may be incorporated into either or both the core and shell. When the core-shell grains are high aspect ratio tabular grains, it is preferred that the do not be introduced at a later stage of precipitation (eg, confined to the shell).

Metal dopants can be introduced into the reaction vessel as water bathable metal salts or divalent and trivalent metal halides.

U.S. Pat. No. 3,287,136.2,950,972 describes the use of zinc, lead and cadmium additives for silver halides at lW1-like concentrations to obtain a degenerative effect on birds.
．． No. 3,901,711 and No. 4,269,927. Other techniques for re-inverting sound improving islands, discussed below, may be used either independently or in combination with the metal dono arm described.

After the shell portion has precipitated onto the sensitized core grains to complete the formation of the core-shell grains, the emulsion can be washed to remove soluble salts. If normal cleaning techniques fail, the aforementioned ``Research Disclosure'' (Item 1764)
Since the core-shell emulsion is intended to form an internal latent image, conscious sensitization of the surface of the core-shell grains may be used. It's not required. However, Rk? To obtain an achievable reversal speed of #6, the previously mentioned U.S. Patent 3,761,27
6.3,850,637.3,923,513 and 4.
It is preferred that the core-shell particles have their surfaces chemically sensitized as taught by No. 035,185.

As mentioned earlier, [Research Disclosure] (Item 1)
Any type of surface chemical sensitization known for use with silver chloride emulsions to form a corresponding surface latent image can also be used, as described in US Pat. . Intermediate chalcog/and/or noble metal sensitization is preferred, as described by the previously mentioned US Pat. No. 4,035,185. Sulfur, selenium and gold are percent preferred surface sensitizers.

The degree of surface chemical sensitization is limited to the following degree: that is, it increases the reversal speed of the internal latent image forming emulsion. It is 1g degree that shifts to the surface and does not compete with internal sensitizing sites. Thus, a balance between internal and hexahedral sensitization is preferably maintained for maximum speed, with internal sensitization predominating. The iFFFF level of surface chemical sensitization can be readily determined by the following test. Two samples of the high aspect ratio intraplatelet-forming silver halide emulsions of the present invention are deposited on a transparent film support on a 1 square meter surface. Coat with a silver coverage of 4 g per plate. The coated material was then exposed to a SOOW tungsten bulb at a distance of 0.6 m.
．． The exposed coated sample was then exposed for 1 to 6 seconds in the following developer Y (type S in r) developer, note that Vl! fibers are mixed in to access the interior of the particles) for 20 minutes. Develop for 5 minutes at 0C, stop, wash and dry.Repeat the procedure described above for a second similarly coated and exposed sample. The procedure is the same again.
However, for developer Y, the following developer X (r surface type)
Developer solution) is used as a substitute. Island 1 internal S type emulsion gI that satisfies the requirements of the present invention as an effective internal latent image forming emulsion
It must exhibit a maximum density that is at least 5 times greater than the specimen developed in the solution (developer X). This density difference is a positive indication, ie, an indication that the latent image center of the silver halide grain is preferentially formed inside the grain and cannot be reached by most published Type III developers.

The following margin developer X Gram N-Methyl-P
-Amine phenol sulfate 2.5 Ascorbic acid 10.0 Potassium meta#l acid
35.0 beautifying potassium
Add l, 0 water to make 11.

N-methyl-P-aminophenol sulfate 2
．． 0 Sodium sulfite, dry* 90.0 Hydroquinone 8.0 Sodium carbonate, -hydrate 52.5 Beautifying potassium
5.0 potassium iodide
Add 0.5 water to make 11.

In one particularly preferred form of spinning, the core-shell used in the practice of this invention is a high aspect ratio tabular grain core-shell emulsion. The phrase “high 7 spectral ratio” is commonly used for emulsions.
In the present invention, the thickness is less than 0.5 micrometer (preferably 0.3 micrometer) and the thickness of at least 0.
．． Core-shell particles with a diameter M of 6 micrometers have an average aspect ratio that is greater than 8 to 1 and occupy at least 50 S of the total projected area of the core-shell particles. shall mean.

For purposes of this invention, tabular grains are grains having two parallel crystal faces, each of which is substantially larger than any single crystal face of the grain. @The phrase "parallel" used in the present invention means to include surfaces that appear parallel when visually inspected directly or indirectly at a magnification of -10,000 times. ” shall mean the ratio of the particle diameter to the particle thickness. On the other hand, the "lI diameter" of the grain O is defined as the diameter of a circle having an area equal to the projected area of the grain when the emulsion sample is observed with a hazy mirror. The core-shell tabular grains have an average aspect ratio of 8 to 1 and preferably 10 to 1. Originally, average aspect ratios of 50 to 1 or even 100 to 1 are possible.Obviously, the thinner the particles, the thinner the bars, the higher their aspect ratio for a given diameter. Typically, grains of desirable aspect ratios are grains having an average thickness of less than 0.5 micrometers, preferably less than 0.3 micrometers, and even more optimally less than 0.2 micrometers. The tabular grains have an average thickness of at least 0.03 micrometer, preferably at least 0.05 micrometer, but thinner tabular grains have an average thickness of at least 0.03 micrometer, preferably at least 0.05 micrometer.
In principle, it can be used. Preferred of the present invention! I!
In M, the tabular grains occupy at least 70S and more optimally at least 90S of the total projected area of the core-shell halodized stator, and the average diameter of the tabular grains is in all cases less than 30 micrometers. , preferably 15
Less than a micrometer and less than 10 micrometers for T&T.

Emulsion according to the present invention! A second emulsion can be mixed with the core-shell emulsion described above. The purpose of mixing the second emulsion is to obtain a densely mixed first core-shell grain population with a low coefficient of variation. When forming an emulsion into a core-shell emulsion, the following (1) to (3) must be coupled. : (1) relative proportions of the first and second grain populations, (2) relative grain sizes of the first and second grain populations, and (3) silver halide grains forming the second grain population tW. specific properties of.

Although mixing the emulsions is preferred, island techniques that bring a second population of grains into close proximity to a first population are within the scope of this invention.

The relative proportions of the first and second particle populations mentioned in (1) above may vary; as mentioned above, from 5 to 1 to 1
A coulometric ratio of the first and second particle populations in the range of 5 to 5 is generally preferred, with 2 to 1 to 1 to 30 coulometric ratios being preferred for most applications. The advantages of the present invention may not be fully realized if the second particle system is less than the above-mentioned minimum proportion. If it were higher, the reform of the silver debt amount would not be sufficiently refreshing. However, the photography fee book is the best in the settlement! The broader ranges indicated for the weight ratios of the first and second particle populations cannot be excluded, as they constitute a striking balance that overcomes the need to satisfy the convenience of membership. Can not.

The correlation between the average particle sizes of the first and second particle populations in (2) mentioned above is such that the second particle population is less than 70 inches, preferably less than 50 inches, of the average diameter of the core-shell particle population of g. Optimally, a particle system of o'#IJ2 is formed in such a relationship that it has an average diameter of less than 40.

Groups can be of either a different ratio or a ratio. It is generally preferred that the coefficient of variation of the second population of particles is less than about 30%. However, the smaller average particle size makes it more cylindrical! The first core-shell particle population can be easily accepted with a factor of 4. The choice of % is dependent on the particular photographic custom and the size of the grain. The preferred photographic feel L (which generally increases with increasing grain size), the covering power (
The average grain diameter for a tabular grain core-shell emulsion is given above, including grain size (which generally decreases with grain size) and granularity (which generally increases with grain size). Average diameters of less than about 3.0 micrometers, preferably less than about 2.0 micrometers, are usually possible for non-tabular core-shell particles. It is generally advantageous to obtain an average particle diameter.

This varies as a function of the composition and structure of the second particle population. In addition, the specific characteristics of the halogenated particles constituting the second particle population (37g) are the following (1) and (b) = (Otori) The second population particles are optically generated. It is possible to supplement the electrons inside and (
b) The second particle population is directly exposed to the surface of the first particle population up to the critical S-slope. 1111vr
What can be formed.

When photons are stimulated by silver halide upon exposure, electron and hole pairs are generated within the grain's crystal structure 411. Halodanization - internal IW particles forming particles attract photolytically generated electrons into the interior. Thus, the second grain population can be selected from among silver halide grains capable of forming an intrasa image. However, the second particle population does not limit the internal am forming particles. Although optically generated electrons can be effectively internally stimulated by internally coupled particles, they cannot form a latent image due to the coupled particle Fi dust light. It is generally preferred to use a conventional internal latent image forming the grains of this wing which are internally coupled by exposure to the halide grains or islands forming the second population of grains. The point to consider is (b) that it is not possible to form a latent image directly within the first particle population. , when a photographic element containing the first and second particle populations according to the invention is imaged and then processed in a surface developer to give a direct positive tone-ms.
'Due to the presence of the second particle population, it is not possible to increase the minimum density to more than 20 - of the maximum image density. Preferably the minimum density is less than 10 times the maximum density, and optimally less than Fiss. The minimum acceptable density varies considerably for certain photographic applications, e.g. projection films can tolerate a larger minimum density than reflection prints.@If the first particle population is omitted, the second particle population is 0.
．． A density difference in exposed and unexposed areas (greater discrimination) of less than 2, optimally less than 0.05 is preferably produced. The illustrated photographic element is realized under exposure and processing conditions that form a direct four-dimensional image in the photographic element containing a second population of particles. The fact that T- can be manufactured to obtain higher minimum densities or higher density differences at various exposure levels or processing conditions is immaterial.
For example, it is possible to use a core-shell emulsion as the second grain population, which incurs extended development times compared to the photographic element in which it is incorporated, in order to obtain substantial separation.

IK, the first core-shell emulsion, and the nine considerations listed above.
A second grain population t-m can be formed by mixing with conventional latent image-forming emulsions or such emulsions that are internally coupled. It is possible to use halodide-type emulsions to obtain the second grain population. It is explained accordingly. Depends on the person skilled in the art! As noted above, a halide-conversion emulsion can be prepared by contacting a silver chloride emulsion with bromide and, optionally, an iodide salt. Displaces chloride ions within the silver chloride crystal lattice, providing internal crystallites GL that act as internal electron recruitment sites. Generally, the converted halide particles will consist of at least 50 moles of bromide, preferably at least 80 moles of bromide, based on total halide. The balance of halides present is in combination with chloride, optionally chloride. Iodide is usually present in concentrations of less than 10 moles based on total halides.

In a particularly preferred form mK of the invention, the second population of particles is also core-shell particles. In view of the considerations mentioned above, they may be identical to the core-shell particles of the first population of particles. In general, other considerations are also satisfied if the second core-shell particle population satisfies the relative size condition of the two particle ensembles, where the first and second particle populations have the same halide bride composition. It is also internally sensitized.

It is also possible to maintain the second grain band collectively in the absence of internal surface chemical sensitization, direct positive aII1 of the mixed emulsion.
It is advantageous both to reduce the surface latent image forming ability of the second grain population and to increase the reversal sensitivity of the mixed emulsion within one photon. 3,761,27 mentioned above to form the first particle population.
6.3,850,637.3,923.513 and 4,
Similar core-shell emulsions with surface chemical sensitization of the type disclosed by No. 035,185 having an average grain size and without or with reduced surface chemical sensitization forming a second grain population Particularly preferred is the grain mixed with the core-shell grains.The mixed emulsion of the present invention can be spectrally sensitized if desired. Only the first particle population has a spectrally sensitizing dye adsorbed on their surface, but if the spectrally sensitized is subsequently mixed, the dye is adsorbed to both particle ensembles. obtain.

For multicolor photographic applications, core-shell particles are intended to be recorded in red, red,
A spectrum 1 sensitizing dye is used that is either marginal or, if desired, blue in color. For black and white image formation applications, orthochromatic,
Although chromatic or panchromatic sensitization is usually preferred, spectral sensitivity is not required. In general, spectrally sensitized colors*,
For iL<, combination with negative action silver halide emulsion is effective 1! Dyes known to be dyes can be used with the mixed emulsions of this invention. The spectrally sensitizing dyes in question are those disclosed in the aforementioned Research Disclosure (Item 17643, Section 4). The 20 spectral sensitized color IA preferred for % is “Research Disclosure J (151
Vol., November 1976, Item 15162) Although the emulsion can be spectrally sensitized with a variety of 1 kSm dyes, the preferred spectrally sensitizing dye is the I rimetelene dye69, which contains cyanine, merocyanine, cyani/and merocyanine complex (
(i.e. tri-, tri-, tetra-, and tetramonocyanine and merocyanine), oxonol, he2-oxonol, styryl, merosteryl, and streptocyanine dyes. Cyanine and merocyanine dyes are preferred.

Spectral sensitizing dyes that sensitize surface-to-surface direct-to-dimension emulsions generally sensitize both negative chiller-acting emulsions and the core-shell emulsions of this invention, and therefore are not normally intended for use in the practice of this invention. Spectral sensitization can be carried out at any stage of emulsion manufacture that has been known to be effective. Most commonly, spectral sensitization is carried out in the industry following completion of chemical sensitization. In particular, the following points are covered: That is, spectral sensitization can alternatively be carried out simultaneously with chemical sensitization, or it can completely precede surface chemical sensitization. can be enhanced by phi adjustment, including:

It has been found to be advantageous to use a nucleating agent rather than a nucleating agent during the nucleating agent treatment. The ``nucleating agent'' (i.e. ``nucleating agent'')
Silver heronide grains f having an internal # image formed by the intensifying light in the six directions for the technically recognized use in the present invention: It is used to represent a capri agent that can selectively structure silver halide grains that do not have internal latent flaws.

The formulated emulsions of this invention preferably incorporate a nucleating agent into the islands which promotes the formation of Form I di-m* directly upon processing.

Although the nucleating agent can be incorporated into the emulsion during processing, the nucleating agent is preferably incorporated during production of the photographic element, usually prior to coating. This ◆ is 11-Decrease of the required nucleating agent. This can be reduced by restricting the mobility of the nucleating agent in the matrix. ballmsting funation
) are commonly used. Nucleating agents containing islands or more groups that promote surface adsorption of silver halide grains have been found to be effective at surprisingly low concentrations. A class of nucleating agents are aromatic hydrazines. Particularly preferred aromatic hydrazines are those in which the aromatic nucleus is substituted with one or more groups to limit mobility and, preferably, to promote adsorption of hydrazine to the surface of the silver halide grains. It is such a hydrazide.

More specifically, preferred hydrazides are those represented by the following formula (1): H D-N-N-φ-M (1) (wherein DII'i is an acyl group; φ is phenyl/or [For example, a halo, an alkyl, or an alkoxy-filtrate is used as a phenylene crystal; and hereafter, the margin M is a moiety that can limit mobility, such as an adsorption-promoting moiety).

Particularly preferable phenyl hydrazide is represented by the following formula (1
1) where R is hydrogen or an alkyl, cycloalkyl, haloalkyl, alkoxyalkyl, phenylalkyl substituent, or more than -0,30 R is a phenyl nucleus with positive Hammett's sigma value induced electron guiding property; R is phenylene or haalkyl, halo, 41 or alkoxy-[ltf!l!L phenylene group;
To water TC1:, yzyl, alkoxypencyl, halopennor J or alkylbenzyl, s, 6: RUC, ~, 8
an alkyl, haloalkyl, alkoxyalkyl or phenylalkyl substituent of cycloalkyl moiety &, which has a positive Hammett's sigma value less than +0.50 and is a phenyl nucleus or naphthyl; R4 are independently selected from the same all substituents as hydrogen or BS; or R3 and R4 are taken together to form a heterocyclic nucleus forming a 5- or 6-membered ring, in which a kII-like atom is selected from hydrogen, hydrogen, carbon, oxygen, sulfur and selenium atoms; provided that at least one of R2 and R4 must be hydrogen and, unless specifically mentioned, the alkyl moiety in each case is from 1 to 6. carbon atoms and the cycloalkyl moiety has 3 to 10 carbon atoms).

As shown by 8 in formula (II), preferred acyl hydrazinophyl thioureas for use in the practice of the present invention include, for example, formic acid, acetic acid, propionic acid,
Butyric acid, higher homologs of these acids with up to 7 R atoms, contain acyl groups which are car/acid residues, and halogens, alkoxy, phenyl and their O-corresponding substituted derivatives.

In a preferred embodiment, the acyl group is formed by a non-containing aliphatic carbon atom bound to 1 to 5 t-benzene atoms. Preferred acyl groups for the axis are formi and acetyl. Regarding compounds that differ in proportion from the point of view of having formyl or acetyl groups, formyl Mi
Compounds having a higher nucleating agent function exhibit higher nucleating agent action. In the wt group for carunic acids, the alkyl moiety has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. In addition to acyclic aliphatic carunic acids, carunic acids have R For example, cyclo-10vir, cyclodecyl, cyclopentyl, cyclohexyl, methylcyclohexyl,
cyclooctyl, cyclodecyl efJ3 to 10
Lateral aliphatic radicals having 5 carbon atoms and, for example, delnyl and iso a11! of lunyl radicals! Selected ginseng species are recognized as being a tachibana-fuyō variant. Cyclohexyl is a sometimes preferred cycloalkyl l111 substituent. The use of alkoxy, cyano, halogen, and corresponding direct cycloalkyl moieties is a matter of course.

Preferred acylhydrazinophenylthioureas used in the practice of the present invention, K as denoted by R' in formula (1), contain a phenylene or substituted phenylene group.

Particularly favorable IL phenylene groups are m- and p-phenylene groups. Examples of preferred phenylene substituents are alkoxy substituents on C, 1 to 6 alkyl substituents on % C, ~6, fluorine-, chloro-1 bromine-1 and sulfur-do substituents. Unsubstituted p-phenylene groups are preferred in %-4
! Preferred alkyl moieties are those having 1 to 4 carbon atoms. Although phenylene and substituted phenylene groups are preferred linking groups, other similarly acting divalent acyl groups such as naphthalene groups can also be used.

In one embodiment R represents unsubstituted benzyl or substituted equivalents thereof such as alkyl, halo or haalkoxy substituted benzyl groups, in a preferred embodiment 6
No more than 4 and most preferably no more than 4 carbon atoms contribute to the substituents of the benzyl group. The substituent for the benzyl group is preferably at the /4 position. Preferred benzyl groups for 4I are unsubstituted, 4-halo-substituted, 4-methoxy-substituted and 4-position.
-Methyl-formed by a substituted benzyl group. In another particularly preferred form R represents a hydrogen atom.

Referring again to formula (1), it is clear that R and R can independently take various forms. One possible form is an alkyl group or a substituted alkyl group, for example a total of 18
a haloalkyl group, an alkoxyalkyl group, a phenylalkyl group, or a corresponding group having up to 12 carbon atoms, preferably up to 12 carbon atoms. Especially R and/or
or R4 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl or higher homologous groups having up to 18 carbon atoms in total; fluoro-, chloro-, promo-, or sulfur-
Do-substituted derivatives; may take the form of alkoxy-substituted derivatives of methoxy, ethoxy, proyl, butoxy or higher homologs thereof, ζ in which the total number of carbon atoms is necessarily at least -2 to 181. ; and can take the form of their phenyl-substituted derivatives, where the total number of carbon atoms is necessarily at least 7 and T
o) at about 181 as in the case of benzyl.

In a particularly preferred form, R and/or R can take the form of an alkyl or phenylalkyl substituent, and in ζ the alkyl moiety is in each case 1
Consisting of 6 to 6 carbon atoms.

In addition to the previously extended acyclic aliphatic and aromatic forms H
I and/or R4 are cycloaliphatic substituents, such as Cs-
cyclodecyl, cyclobutyl, which can take the form of a cycloaliphatic substituent such as a cycloalkyl substituent having
It is also possible to use cyclo(entyl, cyclohexyl, methylcyclohexyl, cyclooctyl, cyclodecyl and bridged ring variants such as lunyl and iso&ni3). Cycloexyl is the preferred cycloalkyl substituent.Alkoxy , cyano, )-logon and the corresponding substituted cycloalkyl substituents are preferably used.

VtS and/or R4 are aromatic substituents, such as phenyl or naphthyl (i.e. 1-naphthyl or 2-
naphthyl) or a corresponding aromatic group, 9 e.g. 1-. 2-
, or 9-anthryl.As shown in formula (If), R and/or R4 can take the form of a phenyl nucleus that is either electron donating or electron withdrawing, but
The highly electron-withdrawing phenyl nucleus makes an inferior nucleating agent.

The electron-withdrawing or electron-donating properties of a particular phenyl nucleus can be evaluated by reference to Hammett's sigma value. For the phenyl nucleus, the Hammett sigma value of its substituents (
That is, the Hammett sigma-value induced electron-withdrawing property can be established, which is the algebraic sum of the substituents, if any, for the phenyl group. For example, the Hammett sigma values of the substituents for the 7-enyl ring of the phenyl nucleus can be determined by determining the Hammett sigma values known from the literature for each substituent and obtaining their algebraic sum. Yes, it can be easily calculated algebraically. Positive fern for electron-withdrawing substituents! − value], while the electron-withdrawing substituent is set with a negative sigma value.

A few examples of meta- and/or meta-sigmer and procedures for their measurement are given in J. PhysrealOrg.
ami@Ck@m1mtry J 2nd edition, page 87,
Published in 1962) H, Pankven, p, g, Pelkado and B, M, Webster, R@e, Tray.
, Chim, J. (78 volumes, 815-t-/, 1959
), P, R, Wells r Ch@w, Ray
s, J (63 volumes, 171 pages, published in 1963)
, H.H., Jaffee r Ch@w, Rays, J.
(53 volumes, 191 pages, published in 19153), M
- J, S, Dewar and P, J.

Darisdell r J, Am@r, Ch@w, 8@@
, J (Volume 84, Page 3S48, Published 1962) and Perrin and Perrin R Quart, Rays.
For the purpose of the present invention, the ortho-substituent to the phenyl ring can be set to a published nine-four sigmer value, as described in J (vol. 20, p. 75 et seq., 1966).

Preferably, the phenyl nucleus has a positive Hammett sigma-value induced electron-withdrawing characteristic as small as +0.50.

R2 and/or R6 are phenyl ring substituents, including field, fluoro-, chloro-, fwa-mo, eye-do, C1
It is possible to choose among phenyl nuclei with alkyl groups having ~6 and alkoxy groups having 01-4.

Preferably, the phenyl ring substituent is present at the normal or 4-ring position.

Rather, RF and R together, together with the nitrogen atom in the 3-position of the thiourea, are chosen independently.
- or a 6-membered ring. The ring atoms can be selected from nitrogen, carbon, oxygen, sulfur and selenium atoms. The ring always contains at least one nitrogen atom. Examples of such rings include morpholino, piperidino, pyrrolidinyl, pyrrolinyl, thiomorpholino, thiazolidinyl, 4-thiazolinyl, selenacylinyl, 4-selenacylinyl, iodazolidinyl, iζdacilinyl, oxazolidinyl and 0% preferred where the 4-oxazolinyl ring is opened. The lower ring is saturated or otherwise to avoid electron withdrawing from the 3-position nitrogen atom!
It has been completed.

Acylhydrazinophenylthiourea nucleating agents and their synthesis are described in U.S. Pat. Nos. 4,030,925 and 4,27
6.364. Variants of the acylhydrazinophenylthiourea nucleating agents described above are described in U.S. Pat. No. 4,139,387 and British Patent Application No. 2,012.
It is disclosed in 443mu.

Another preferred class of phenylhydrazide nucleating agents is %
N-(acylhydrazinophenyl)-thioand nucleating agent, for example as shown below: where R and R1 are ; M is +N, -8- or -0-: q' represents the atoms necessary to complete the heterocyclic nucleus; R'Fi hydrogen, phenyl, alkyl, alkylphenyl independently selected from phenylalkyl; and in each case the alkyl moiety Fil to 6 carbon atoms).

These compounds include compounds having a heterocyclic thio-enzyme nucleus, such as 4-thiazoline-2-thione, thiazolidine-2-thione, 4-oxinacillin-2-thione,
Includes compounds such as oxazolidine-2-thione, 2-pyrazoline-5-thione, pyrazolidine-5-thione, indoline-2-thione, and 4-izoline-2-thione.

A particularly preferred heterocyclic thioary nucleus of the sucrose is %Q
is represented by the formula (■): (wherein , inrodanine, and a 2-thio-2,4-oxazolidinedione nucleus. Some hexa-eukaryotic acids, such as thiobarbic acid, are believed to correspond to the medicinal ring contained within formulas (to).

Another @-preferred subclass of heterocyclic thioado nuclei is formed when Q' is of the formula: where L is a methine group; L is a xy substituent; 2 represents a nonmetallic atom necessary to complete the basic heterocyclic nucleus present in the cyanine dye; n and dFi integers 1 and 2; R and R are hydrogen, alkyl, alkylphenyl,
and phenylalkyl are independently selected; and in each case the alkyl moiety contains 1 to 6 carbon atoms).

The meaning of (to) for Ql gives Ql a heterocyclic thioamide nucleus corresponding to the nuclear Omethine substitution form shown above in the meaning of formula (I). In a particularly preferred form, the heterocyclic thioodo nucleus is preferably methine-substituted 2-
Thiohydantoin, rhodanine, isodanine, or 2-
It is a thio-2,4-oquinasiridine-dione nucleus. The heterocyclic thioamide nucleus represented by . 2 is necessary to complete a basic 5- or 6-membered heterocyclic nucleus of the type found in cyanine dyes with ring-forming atoms selected from the class consisting of carbon, nitrogen, oxygen, sulfur and selenium. represents a nonmetallic atom.

N-(acylhyto2dinophenyl)thioamide nucleating agents and their synthesis are disclosed in more detail in US Pat. No. 4,080,207.

Yet another preferred class of phenyl-hydracite nucleating agents are triazole-substituted phenylhydracite nucleating agents. More specifically, preferred triazole-substituted phenylhydrazide nucleating agents are those represented by the following 2V: JHH R-C-N-NR-Moum-A M
and R1 (denoted by I and having nine meanings; A is alkylene or oxaalkylene; Al is triazolyl or benzotriazolyl nucleus); the alkyl and alkylene moieties in each case are 1 to 6; carbon atoms).

Yet another percentage of preferred triazole-substituted phenylhydrazide nucleating agents are those represented by the following formulas: where R is hydrogen or methyl; n is from 1 to 4; must be an integer; and E is C1-4 alkyl).

Triazole-substituted phenylhydrazide nucleating agents and their synthesis are disclosed in US Pat. No. 4,278,748. Comparable nucleating agents with a somewhat wider range of adsorption-promoting groups are described in corresponding British Patent Application No. 2,011,3.
91A.

The aromatic hydrazides represented by formulas (II), @ and (to) each contain an adsorption-promoting substituent. In many cases, along with these aromatic, family hydrazides,
It is preferred, however, to further use hydrazides or hydrazones that do not contain substituents specifically intended to promote adsorption to the silver halide grain surfaces, although such hydrazides or hydrazones may be incorporated into the photographic element. These hydrazides or hydrazones can be used as the sole nucleating agent if desired.Such hydrazides and hydrazones are represented by the formula ( II) and (Foundation)
1, including that represented by 'r-N-N=T'
010 (in both formulas, T is an aryl group, including a substituted aryl group, %T is an acyl group, and T
includes alkylidene groups and substituted alkylidene groups. ).

A typical aryl group for the substituent TK has the formula M-T'-
in which T is an aryl group (e.g. phenyl, 1-
7 methyl, 2-naphthyl), yt is hydrogen, human o
4, amino, alkyl, alkylidene group, aryl group, heterocyclic amino (ani)-containing heterocyclic moiety), alkoxy, aryloxy, acyloxy, aryl carbon amide, alkyl caldenide, heterocyclic Cal?
A variety of substituents can be used for alkyl sulfonamides (heterocyclic moieties containing carbon atoms), arylsulfonamides, alkylsulfonamides, and heterocyclic sulfonamides (heterocyclic moieties containing sulfonamides).

Typical acyl groups for substituent T1 have the formula To form a group, it has the formula: %Formula%, where A represents an alkyl or a group having a heterocyclic group.A typical alkylidene group for substituent T2 has the formula: =CH-D, where D can be a hydrogen atom or groups such as alkyl, aryl and monocyclic groups.

Typical aryl substituents for the hydrazine and hydrazone mentioned above include phenyl, naphthyl and diphenyl. Typical heterocyclic substituents for the hydrazine and hydrazine mentioned above include azole, azine,
Includes furan, thiophene, quinoline and pyrazole. Typical alkyl (or alkylidene) substituents for the hydrazine and hydrazo mentioned above are methyl, ethyl, isoprobyl,! -Provil, isobutyl,! −
Butyl, 1-butyl, amyl! -Octyl! having from 1 to 22 carbon atoms, including -decyl, needocodyl, tan-octadecyl, tan-eicosyl, and neatcodyl.

The hydrazides and hydrazines represented by Nibi) and Co. and their syntheses are disclosed in U.S. Pat. No. 3,227,5
52.

A second preferred general class of nucleating agents for use in the practice of this invention are N-substituted cycloammonium quaternary salts. Particularly preferred species of such nucleating agents are of the formula: Represents the atoms necessary to complete the entire heterocyclic ring containing a 5- to 6-atom heterocyclic ring containing a quaternary nitrogen atom; j represents a positive integer of 1 to 2; a represents 2 to 2; represents a positive integer of 6;
and L2, when used together, represent atoms necessary to complete a cyclic group selected from cyclic oxyacetals and cyclic thioacetals having 5 to 6 atoms in the heterocyclic cyclic acetal ring, and (,) 1 - represents a member selected from the group hydrazinoalkyl; and El represents a hydrogen atom, an alkyl group, an aralkyl group, an alkylthio group, or an aryl group including, for example, phenyl or 7-tyl and substituted aryl groups. expressed.

N-substituted cycloammonium quaternary salt nucleating agents represented by formula (3) and their synthesis are described in U.S. Pat.
．． 61! No. S and No. 7,759,901. In a variation, E' is a divalent alkylene group of 2 to 4 carbon atoms linking two substituted heterocyclic nuclei as shown in formula 00. Such nucleating agents and their synthesis are disclosed in US Pat. No. 3,734,738.

A substituent for a quaternized nitrogen atom of a heterocyclic ring may itself in other variations form a fused ring with the heterocyclic ring. Such nucleating agents include 1.2-
Illustrated by dihydroheterocyclic quaternary salts comprising a dihydroaromatic heterocyclic nucleus. Particularly preferred are the 1,2-dihydroheterocyclic nuclei Kti, such as the 1,2-dihydropyridinium nucleus. Particularly preferred dihydroaromatic quaternary ring nucleating agents include those represented by the following formulas: (wherein 2 is carbon, nitrogen, oxygen, sulfur, or selenium) together with another atom of the selected heterocyclic ring, represents a nonmetallic atom necessary to complete a heterocyclic nucleus containing a quaternary nitrogen atom and containing 65 to 6 heterocyclic rings; n is l; represents a positive integer having a value of 2 to 2; when n is 1, 8 represents a member selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and a carbamide group; 2, R represents a C1-4 alkylene group; each of R and R2 represents a member selected from the group consisting of a hydrogen atom, an alkyl group and an aryl group; and X'''' represents an anion. .). Dihydro-tetraaromatic quaternary salt nucleating agents and their synthesis are disclosed in US Pat. No. 3,719,494.

Particularly preferred h-class N-substituted cycloammonium quaternary salt nucleating agents are those containing - or more alkyl substituents. Such nucleating agents include compounds represented by the general structural formulas illustrated by the following formulas: where 2 is for forming a 5- or 6-membered heterocyclic nucleation. R represents an aromatic group necessary for At least one of R, R and R is a propargyl group, a butynyl group, or a substituent containing a propargyl group or a butynyl group, and X- represents an anion. where n is 1 or 2, and n is 1 when the compound forms an internal complex salt.

Such alkynyl-substituted cycloammobiquaternary salt nucleating agents and their synthesis are described in U.S. Pat.
22.

The particular choice of nucleating agent will be influenced by a variety of factors. The nucleating agents of the aforementioned US Pat. No. 4,080,207 are particularly preferred for many applications because they are effective at very low concentrations. A minimum concentration of nucleating agent of 0.1 slv per mole of silver, preferably at least o, slv per mole of silver, and optimally at least 1 slv per mole of silver is disclosed in U.S. Pat. No. 4,080,207. Disclosed. The nucleating agents of U.S. Pat. No. 4,080,207 are particularly advantageous in reducing sensitivity loss and, in some cases, allowing sensitivity to be gained while increasing processing temperatures.

The nucleating agent of U.S. Pat. No. 4,080,207 is
．． When used with a 227.552O nucleating agent, sensitivity changes as a function of processing temperature can be minimized.

Aromatic hydrazide nucleating agents have relatively high levels of voice,
Alkynyl-substituted cycloammonium quaternary salt nucleating agents, which are generally preferred when used in photographic elements typically intended to be processed with Fi 13 or higher, are generally preferred when processed with Fi less than 13. Particularly useful. UK patent application 2
, 012,443 teaches nucleating agents that are effective when treating the 10 to 13 vocal range, preferably the 11 to 12.5 range.

N-substituted cycloammonium quaternary salt nucleating agents containing, in addition to the previously mentioned nucleating agents, another nucleating agent treated at a level in the range of about 10 to 13; is exemplified by one class of nucleating agents that are effective when Such a nucleating agent is described by the following formula (Xllll): where 2 represents an atom completing an aromatic carbocyclic nucleus of 6 to 10 carbon atoms; z2 is cyanine. represents the atoms completing the heterocyclic nucleus of the type found in the color chart; m is the adsorption-promoting moiety; m and n are 1 or...2; and R'sR2 and R3 are independently selected from the group consisting of hydrogen, alkyl, aryl, alkaryl, and aralkyl, R1 and R5 are independently selected from acyl, alkenyl, and alkynyl, and the aliphatic moiety contains up to 5 carbon atoms. and the aromatic moiety has from 6 to 10 carbon atoms.When these nucleating agents are used, the preferred treatment is in the range of 1O12 to 12.0.

201) Nucleating agents of the type represented by K and their synthesis are disclosed in US Pat. No. 4,306,016.

Another class of nucleating agents that are effective in the 10-13, preferably 10.2-12 vocal range are dihydrospiropyran bis-condensation products of salicylaldehyde and at least one heterocyclic ammonium salt. In a preferred form, such a nucleating agent is represented by the following formula 0: where X and Y each independently represent a sulfur atom, a selenium atom or a -〇(RR)- group. , R1 and R2 independently represent C1-5 lower alkyl or together represent C4 or C, alkylene group, R, R, R and R each represent hydrogen, hydroxy group or C
represents a lower alkyl or C3-, alkoxy group, zl and 2 each represent a non-metallic atom completing a nitrogen-containing heterocyclic nucleus of the type found in cyanine dyes, and R and R each represent Represents a ring nitrogen substituent of the type found in cyanine dyes.

In a preferred form, 2 and 2 each contain a carbon atom, -nitrogen atoms and optionally sulfur or selenium atoms in the ring structure, preferably fused to at least one benzene ring, 5- Or complete a 6-membered ring.

Nucleating agents of the type represented by the formula and their synthesis are disclosed in US Pat. No. 4,306,017.

Yet another class of nucleating agents useful in the 10-13, preferably 10.2-12 vocal range are diphenylmethane nucleating agents. Such a nucleating agent has the following formula (XV)
K is represented by: where 2 and 2 represent nitrogen atoms completing the phenyl nucleus; R1 is hydrogen or C7-6 alkyl; and R2#R
s1 and R are hydrogen, halogeno, alkyl, hydroxy,
``Independently selected from alkoxy, aryl, alkaryl, and aralkyl, or 1h.

R'' and R together are a covalent bond, the divalent alkyl moiety contains 1 to 6 carbon atoms, and each aryl moiety contains 6 to 10 carbon atoms.

Nucleating agents of the type represented by formula (XV) and their synthesis are disclosed in US Pat. No. 4,315,986.

Instead of being incorporated into the photographic element during manufacture, nucleating agents may alternatively or additionally be incorporated into the developer solution.Hydrazine (
H2N-NH2) is an effective nucleating agent that can be incorporated into the developer solution. As an alternative to the use of hydrazine, a variety of water-soluble hydrazine derivatives can be added to the developer. Preferred hydrazine derivatives that can be used in the developer include the following organic hydrazine compounds: where R1 is an organic group and each of R2, R1 and R4 is a water X atom or an organic group. be. The organic groups KFi represented by R', 1-aM and R4 include hydrocarbyl groups such as alkyl groups, aryl groups, aralkyl groups, alkaryl groups and alicyclic groups, and include, for example, alkoxy groups, Included are hydrocarbyl groups in which car is substituted with a substituent such as an xyl group, a sulfonate group, and an atom.

Particularly preferred hydrazine derivatives to be incorporated into the developer solution include alkylsulfonic arylhydrazines, such as p-(methylsulfonatomyl)phenylhydrazine, and alkyl hydrazine, such as p-(methylsulfonatrimethyl)phenylhydrazine. Contains sulfonaodoalkylarylhydrazine.

The previously mentioned hydrazine and hydrazine derivatives are described in U.S. Pat.
892.715KI! It is shown. Preferred hydrazine incorporated into the developer is disclosed in U.S. Pat. No. 4,269,92.
9. Another preferred class of nucleating agents that can be incorporated into the 1A imaging solution corresponds to formula (1) above, but in which there is no moiety M capable of limiting mobility, this type of nucleating agent is described in US Pat. , 221,857 and 4.224
, 401.

Once the silver imaging core-shell emulsions have been generated by precipitation procedures as described above, washed, and then sensitized, their preparations are treated with nucleating agents as described above and conventional photographic additives. They can be perfected by incorporating agents as desired, and they can be usefully applied in photographic applications requiring the silver images to be produced, such as conventional black and white photography.

The core-shell emulsion consists of a dispersion medium], and this dispersion medium 1 [inside,
The core-shell particles are dispersed. The dispersion medium of the core-shell emulsion layer and other layers of a photographic element can contain various colloids alone or jointly as a vehicle (which includes both binder and peptizer). Preferred peptizers can be used alone or 1E can be used in combination with hydrophobic substances.

Preferred peptizers are gelatin, such as alkali-processed gelatin, (cow bone or leather gelatin) and acid-processed gelatin (pork skin gelatin), and gelatin derivatives, such as acetylated gelatin, phthalated gelatin, etc.2 (some useful vehicles are , “Research Disclosure” (Item 17)
6643, cited above, Section 9). The layers of the photographic element containing crosslinkable colloids, gelatin-containing layers at 41, are described in "Research Disclosure" (Item 17643, cited above at 1).
It can be cured with a variety of organic and inorganic curing agents, as described by Sekison 10) K.

By incorporating stabilizers, antifoggants, antikinks, latent image stabilizers, and similar additives prior to coating, instabilities that reduce maximum density in direct positive emulsion coatings can be avoided. . A wide variety of such additives are described in Research Disclosure, 1
Volume 76, December 1978, Item 17643, Sector 1 - @C, E, Maze (M・■)
, De theory op de photography, re process, Iris 2nd edition, Macmillan, 1954, 677-68
As described on page 0, many of the antifoggants that are effective in emulsions can also be incorporated into developers and can be classified under the general headings of Sections 2 and 3.

Improved results may be obtained in some applications when direct pour emulsions are processed in the presence of certain antifoggants such as those disclosed in U.S. Pat. No. 2,497,917. I can do it. Typically useful antifoggants of this type include benzotriazoles such as benzotriazole, 5-methylbenzotriazole, and 5-ethylbenzotriazole; benzotriazoles such as 5-nitrobenzimidazole; - pendithiazoles such as nitrobenzothiazole and 5-methylbenzothiazole; heterocyclic thiones such as 1-methyl-2-tetrazoline-5-thione; 2,4-dimethylamine-6-chloro-5- Included are thiazines such as triazine; benzoxazoles such as tribenzoxazole; and pyrroles such as 2#5-dimethylpyrrole.

In some embodiments, good results are obtained when the element is processed in the presence of high levels of the anti-brittle agents described above. When using a high fogging agent such as benzotriazole, the processing solution is 1! Right! Up to 5II, preferably 1! Good results can be obtained when they contain 1 to 3 II; when they are incorporated into photographic elements, concentrations of 1.000 M9''* per mole of silver and preferably per mole of silver are used. In addition to sensitizers, hardeners, and antifoggants and stabilizers, various other commonly used photographic additives may be present. The specific selection of agents will depend on the particularities of the photographic application and can be readily accomplished by one skilled in the art. Useful additives are described in Research Disclosure, Item 17643 (cited above). Fluorescent brighteners may be incorporated as described in Patent Document Item 17643.

Absorbing and scattering materials can be used in separate layers of emulsions and photographic elements according to the present invention, as described in the same article previously published in Ibid. 9. Coating aids and coating materials as described in Section 9.
Flexibilizers and lubricants may be present as described. An antistatic layer may be present as described in the patent application. The method of adding additives is described in Sexy Adventures. A matting agent can be incorporated as described in Sexy Sone XM. If desired, developers and development modifiers may be incorporated as described in Seksin Bean and Seksin Carbon XM. Emulsion layers, interlayers, overcoats, and subbing layers, if present, are listed in Item 17643, Sector m.
:/XV.

The layers of the photographic element can be formed by coating on various supports. Typical photographic supports include polymeric films, wood fibers (e.g. paper), metal sheets and foils,
There are glass and ceramic support elements that improve the adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, friction properties, antihalation properties and/or other properties of the support surface. For this purpose, one or more subbing layers can be formed. A suitable photographic support is item 1
7643% Sexy Encyclopedia 1.

The emulsion layer or layers are usually coated as a continuous layer on a support having opposing planar major surfaces, but this need not be the case.

The emulsion layer can be coated as a plurality of laterally displaced layer segments onto a flat support surface. When segmenting one or more emulsion layers, it is desirable to use a microporous support; useful microporous supports are described in PCT Application Publication No. WO 30101614 (August 1980).
Published on March 7th; Belgian Patent No. 881,513, 198
(August 1, 2013) and U.S. Patent No. 4,307,
No. 165. The size of the micropores is 1 to 2 in width.
00 micrometers and a depth of 1000 micrometers or less. Generally, in the field of normal black and white photography, when enlarging photographic images to %, the size of the micropores is preferably at least 4 micrometers wide and less than 200 micrometers deep, and the best size is the width and depth. Both are about 10 to 100 micrometers.

The photosensitive silver chloride contained in the photographic element can be processed according to conventional methods.

Although development is preferably carried out in the presence of a nucleating agent to provide a photographic element as described above, overall exposure can alternatively be carried out immediately before or preferably during development. . When an O/D-all flash exposure is used, the exposure can be of high intensity and short duration, or alternatively can be of long duration and low intensity.

The Haloda developing silver developer used in the process is a surface developer.The term "surface development" forms a surface latent image center on the silver heronide grains, but it develops the surface silver halide emulsion. A zero-surface developer is generally understood to include a developer that does not form substantial internal latent image centers in the internal latent image-forming emulsion under the conditions normally used to develop the internal latent image. A silver halide developer or a ring agent can be used, but
The developer solution or composition generally contains a small amount of substantially non-oxidizing solvents (e.g., water-soluble thiocyanates, water-soluble thioethers, thiosulfates, and ammonia) that disrupt or dissolve the particles to form the surface carbonate. Excess chloride is sometimes removed in the developer solution or
Although preferred when incorporated into the emulsion as an iodide-releasing compound, large amounts of iodide or iodide-releasing compounds are generally avoided to prevent substantial grain collapse.

Typical silver halide developers that can be used in the developing compositions of the present invention include hydroquinone, catechol,
Aranophenol, 3-pyrazolidinone, ascorbic acid and its derivatives, reductone, phenylenedi7one,
or a combination thereof. Developers can be incorporated into the photographic element in which they are contacted with the silver halide after in-plane exposure; however, in some embodiments they are incorporated into the photographic element. It is preferably used in

Once a silver image has been formed in a photographic element, it is common practice to fix the undeveloped silver halide. The high-aquid ratio tabular grain emulsions of the present invention are particularly capable of completing fixing in a shorter period of time. This is advantageous in that it makes it possible. This speeds up the process and allows nine processes to be performed.

The photographic elements and techniques described above for producing dye-imaged silver images can be easily applied to produce color images using dyes. In perhaps the simplest technique for obtaining a projectable color image, conventional dyes can be incorporated into a photographic support and formation of a silver image can be carried out as described above. In the areas where the silver image is formed, the photographic element becomes substantially opaque to light, and in other areas, corresponding to the color of the support, it transmits light. Color images can be easily formed in this way. This same effect can also be achieved by using a separate dye filter layer or an element with a dye filter element and a transparent support element.Silver halide photographic elements can be It can be used to form dye images by formation.

The photographic element is a silver-dye-
Dye images can be formed by selective destruction of dyes or dye precursors, such as by bleaching methods. Photographic elements for forming silver images can be used to form dye images by developing a developer containing a dye image forming agent such as a color coupler. In such form m, the developer comprises a color developer (eg, an aromatic primary aone) capable of reacting (coupling) with the coupler in oxidized round form to form a dye image.

Dye-forming couplers are preferably incorporated into photographic elements; dye-forming couplers can be incorporated in different amounts to achieve different photographic effects. British Patent 923,
No. 045 and U.S. Pat. No. 3,843,369 teach limiting the concentration of coupler with respect to rounding and silver coverage to lower amounts than those normally used in fast and intermediate speed emulsion layers.

The dye-forming couplers incorporated are selected to form subtractive primary color (i.e. yellow, magenta and cyan) image dyes, and these couplers are non-diffusive colorless couplers;
For example, two- and four-equivalent couplers of the open-chain ketomethylene, pyrazolone, pyrazolotriazole, birazolopenzimidal, phenol and naphthol types, which are incorporated into high-boiling organic (coupler) solvents.

Dye-forming couplers with different reaction rates in single or multiple separate layers can be used to achieve the desired effect in a particular photographic application.

Dye-forming couplers can be used, by coupling, as development inhibitors or accelerators, bleach accelerators, developers, silver halide solvents, toners, hardeners, fogging agents, anti-capri agents, competitive graphics, chemical or spectral sensitization. releases photographically useful fragments such as agents and desensitizers. Development inhibitor releasing (DIR) couplers can be implemented. Silver halide emulsions with relatively poor photosensitivity, such as Ridgeman emulsions, are
It was utilized as an interlayer and an overcoat layer to prevent and inhibit the migration of development inhibitor fragments as disclosed in U.S. Pat. No. 3,892,572.

Various couplers and image dye stabilizers are well known to those skilled in the art and are described in the various patents cited in Research Disclosure, Item 17643, supra, supra.

Dye images can be formed or amplified by employing methods that employ oxidizing agents in the form of inert transition metal iosium complexes and/or peroxide oxidizing agents in combination with dye image-forming reducing agents. Photographic elements are particularly suited for forming dye images by such methods.

Removal of developed silver by bleaching is common practice in the art of forming dye images in silver halide photographic elements. Removal of such silver may be achieved by incorporating a bleach accelerator or its precursor into certain layers of the photographic element in a processing solution.
It can be promoted well. In some cases, especially when amplifying dye images as described above, the amount of silver formed by development is small compared to the amount of dye produced, so that there is no substantial visible shadow. silver bleaching is omitted.

In still other applications, a silver image is retained and a dye image is utilized to enhance or supplement the density provided by the silver image. When increasing the density of a silver image with a dye, it is usually desirable to use a single neutral dye or a combination of dyes capable of producing an overall neutral image.

Application to Margin Multicolor Photography The product of the present invention can be used to produce multicolor photographic images. Any conventional multicolor image direct positive photographic element, generally containing at least one core-shell silver halide emulsion layer, can be improved simply by substituting the core-shell emulsion of the present invention with the emulsion. 0 The present invention is applicable to both additive and subtractive polychromatic images.

Application of the emulsions of this invention in multicolor photographic elements in which multicolor images are produced by the subtractive dye combination K provides particular advantages.

Such photographic elements typically consist of a support and at least three sets of silver halide emulsion layers in overlapping layers that record blue, green, and red light exposures separately as yellow, magenta, and cyan dye images, respectively. Unless otherwise specified, multicolor photos i! ! The element can have/behave the characteristics of the photographic element described above.

Multicolor photographic elements often contain two or more color-forming layers.

will be explained. The most common multicolor photographic elements contain three overlapping color-forming layers, each color-forming layer unit capable of recording a different third of the spectrum and complementary subtractive al1. at least one silver emulsion layer capable of producing dye images, i.e., blue, green and red color-forming layers capable of producing yellow, magenta and cyan dye images, respectively; The zero dye forming material used does not necessarily need to be present in any color forming layer unit and can be supplied entirely from the processing solution.When the dye forming material is provided in a photographic element, it may be present in certain emulsion layers. or in a layer positioned to receive an oxidizing or electron transfer agent from an adjacent emulsion layer of the same color-forming layer unit.

A scavenger is generally used to prevent the electron transfer agent from oxidizing between the color-forming layer units from migrating and degrading the color.

Scavenger U.S. Patent No. 2,937,086-IK
The emulsion layer itself can be located within the emulsion layer as taught and/or the scavenger-containing interlayer can be placed within the adjacent color-forming layer 22, as described in U.S. Pat. No. 2,336,317. It can also be placed in between.

Although each color-forming layer unit can include a single emulsion layer, there are often two, three or more emulsion layers of different photographic speed within a single color-forming layer unit. If the desired layer configuration does not permit multiple multicolor emulsion layers of differing sensitivities to be disposed in a single color-forming layer, multiple (usually two or three) emulsion layers may be used in a single photographic element.
) It is common to provide blue, green and/or red recording color forming layer units.

A multicolor photographic element using an emulsion according to the present invention may be in any commonly used form as long as it meets the above requirements!
Gorokhovskll *Spectral Studies of Photography, Re-Process, Focal Press. two.

-Yoke, p, 211 Any of the six possible layer arrangements listed in Table 27m can be employed. Simple and 1
jliiiKIf I were to explain it, it would be the commonly used multicolored 10r.
In the process of preparing silveride photographic elements, such photographic elements are provided with two or more emulsion layers according to the invention that are sensitive to the negative blue portion of the spectrum and are exposed to radiation prior to other emulsion layers. can be provided. However, in most cases, it is possible to modify the layer arrangement as necessary and replace the conventional negative blue recording emulsion layer with the one according to the present invention.
It is desirable that the third layer be replaced with two or more negative blue recording emulsion layers.

The present invention may be better understood with reference to the following preferred illustrative figures.

Layer structure 1 Exposure ↓ Layer structure Exposure ↓ Layer structure Exposure ↓ Layer structure ■ Exposure ↓ G Layer structure V Exposure ↓ R In the above layer structure, 1, G and 8 respectively represent the back of the normal type;
Indicates green and red recording color forming layer unit; color forming layer unit) F appearing before B, G or R indicates that the color forming layer unit records the same third exposure of the spectrum in the same layer configuration. Indicates that the photographic sensitivity is higher than that of at least one other coloring layer;
shows that the color-forming layer unit has lower photographic sensitivity than at least one other color-forming layer with the same third exposure in the same layer configuration9; If necessary to protect the edges and/or red recording emulsion from pre-exposure, an intermediate layer containing a yellow filter material is provided. Providing the green and/or red recording emulsion layers in close proximity to the exposing radiation source as well as the previous recording emulsion layer (1) silver chloride and silver chlorobromide core grains (see U.S. Pat. No. 2,344,084); Or (
2) Requires that green/or red recording emulsion layers, such as emulsion layers containing high aspect ratio tabular grains, be relatively insensitive to blue. Each of the high-speed or low-speed color layer units records the same third exposure of the spectrum as a result of its arrangement in the layer configuration, its photographic speed, its unique photographic speed, or both. They can differ in terms of their combinations.

In layer configurations 1 to V, the position of the support is not shown (1); in accordance with conventional practice, the support is usually placed furthest from the exposing radiation source, ie below the nine layers shown.

If the support is colorless and slightly reflectively transmissive, ie, transparent, a transparent support can be provided between the exposure source and the displayed layer. More generally, the support can be placed between the exposure source and any color-forming layer unit intended to record the light to which the support is transparent.

Dye Image Transfer A single dye-forming layer consisting of a core-shell halodanized chain emulsion layer as previously described and at least one dye-image-forming substance in the emulsion layer itself or in an adjacent layer of the layer unit. It is possible to construct a dye image transfer film unit according to the present invention which is capable of producing a monochromatic transferred dye image by arranging the dye image on a support. In addition, the dye image transfer film unit comprises a dye-receiving layer that can mordant or otherwise immobilize dyes transferred thereto. To obtain a transferred nine-dye image 9, the core-shell emulsion is imagewise exposed and then contacted with an alkaline processing composition having juxtaposed dye-receiving and emulsion layers. To obtain the transferred dye image, the core-shell emulsion is exposed to light,
The dye-receiving layer and emulsion layer are then juxtaposed and contacted with an alkaline processing composition. In a particularly advantageous application for monochromatic transferred dye images, a dye-im-donor material is used to obtain a neutral transferred dye image. Monochromatic transferred dye images of any hue can be produced, depending on what is desired.

The monochromatic dye image transfer film of the present invention employs three dye-forming layer units: (1) consisting of a red-sensitive silver heronide emulsion associated with a cyan-dye image-forming material;
A cyan-dye-forming layer consisting of a green-sensitive silver halide emulsion associated with (2) a magenta-dye-image-forming substance! Zenter pigments - forming layers, and (3) yellow - pigments associated with one stroke and one forming substance -
Yellow-dye-forming layer unit consisting of a sensitive silver halide emulsion.

Each dye-forming layer unit includes one, two, three or more separate silver halide emulsion layers and one or more separate silver halide emulsion layers forming part of the emulsion layer or dye-forming layer unit. The dye-image-forming material may be included in the layer. One or a combination of emulsion layers can be formed with the core-shell silver halide emulsion layers described above.

Depending on the dye-forming substance used, it can be incorporated into the silver halide emulsion layer or into a separate layer associated with the emulsion layer. Any of those known to those skilled in the art, such as pigments, dye inhibitors, and redox dyes, may be used, and the particular agent employed will depend on the nature of the element or film unit and the uniformity desired. Depends on the type of. Materials useful in diffusion transfer films include a dye component and a monitor component. In the presence of the alkaline processing composition and as a function of silver halide development, the monitor component is sensitive to changes in the mobility of the dye component. These dye-forming substances are initially mobile and U.S. Pat.
, 606, it can be immobile as a function of the current state of silver rodanide. Alternatively, they may be initially immobile and, in the presence of the alkaline treatment composition, become mobile as a function of the oxidation composition.

This latter class of materials includes redox color tag-emitting compounds, in which the monitor group is a carrier from which the dye is released as a direct function of the silver oxide present or the ion rodan. It is released as an inverse function of silver oxide. Compounds that release dye as a direct function of non-rhodanized development are referred to as negative release compounds, while compounds that release dye as an inverse function of non-rhodanized development are referred to as positive release compounds. Since the internal latent image-forming emulsions of the present invention are developed in the unexposed areas in the presence of a forming agent and a surface developing agent, a positive transfer dye image is formed using a negative-working release compound, so that the latter preferable.

A preferred class of negative-release compounds is disclosed in U.S. Pat.
54,312.4,055,428 and '4,076,
ortho or ortho-sulfonamidophenols and naphthols disclosed in US Pat. In these compounds, the dye moiety is bonded to the sulfonate group, and the sulfonamide group is ortho or/to the phenolic hydroxyl group.
Similarly, during development, the sulfonamide compound is oxidized and then released depending on hydrolysis.

Another preferred class of negative release compounds is a stabilized dye that has a labile dye attached to the coupling-off site.
It is either a forming (color-forming) or a non-pigment-forming (non-color forming) fogger. For example, para-phenylenediamine,
When combined with an oxidized color developer, the mobile dye is positioned such that it can be transferred to a receiver. The use of compounds that form such negative color bulk images is described in U.S. Pat.
27,550 and 3,227,552 and English 1ii1%
No. 1,445,797.

Since the silver halide emulsions used in the image transfer films of the present invention are of the 4-dye type, the use of positive-working release compounds will give negative transferred dye images; useful positive-working release compounds are , nitrobenzene and quinone compounds as disclosed in U.S. Pat. No. 4,139,379, hydroquinone as disclosed in U.S. Pat. be.

Details regarding the above-mentioned release compounds, their method of action, and methods of their manufacture are described in the above-mentioned patents.

Any material can be used as the dye-receiving layer in the film unit of the present invention, so long as it mordantes or otherwise immobilizes the dye that diffuses into the dye-receiving layer. The optimal material selected will of course depend on the particular dye or dyes to be mordanted; the dye-receiving layer may contain UV absorbers, brighteners and colorants to protect the dye from UV-induced degradation. It may contain similar substances to protect or enhance the vote image. The polyvalent metal, which is preferably immobilized in association with / shear, is disclosed in U.S. Pat.
239,849 and U.S. Pat. No. 4,241,163 to chelate one transferred image dye. Dye-receiving layers and materials useful for their manufacture are described in Research Disclosure (Item 15).
162, cited above) and US Pat. No. 4,258,117.

The alkaline processing composition used in the dye transfer film may contain alkaline substances such as alkali metal hydroxides or carbonates (e.g. sodium hydroxide or sodium carbonate) or anhydride (e.g. diethylamine). You can get it with 11 liters of water. Preferably the alkaline composition has a pH of greater than 11. Preferred materials for use in such compositions are disclosed in the Research Disclosure (Item 15162, cited above).

Although the developer may be contained in a separate solution or process sheet, or the developer may be incorporated into any processing composition-permeable layer of the film unit, the developer is preferably in an alkaline processing composition. Contained in When the developer is separated from the alkaline processing composition, the alkaline composition serves to activate the developer and then provide a medium with which the developing agent contacts and develops the silver halide. Silver heronide developing agents can be used when processing the Film Enix F of the present invention. Selection of the optimum developer depends on the type of film unit used with it and the particular dye image formation used. Depends on the substance. Suitable developers include, for example, hydroquinone, a-denophenol (e.g. N-methyla-denophenol), 1-phenyl-3
-pyrazolidinone, 1-phenyl-4,4-dimethyl-
3-pyrazolidinone, l-phenyl-4-methyl-4-
hydroxymethyl-3-pyrazolidinone, and N, N,
It can be selected from compounds such as N', N'-tetramethyl-p-ph, dilene diamine. Non-chromogenic agents in this list are preferably used in dye transfer films. This is because they have little tendency to contaminate the dye image-receiving layer. Image transfer film units useful in the practice of the present invention and their characteristics are further described in the "Research Disclosure".
(Item 15162, cited above).

Margin below (d) Embodiment Example 1 Control Coating - A 6, o, s micrometer octahedral core-shell silver bromide emulsion was prepared by the Mudapluzier precipitation technique. Octahedral odor of 0.55 micrometer diameter Core particles consisting of silver oxide particles are mixed with 0.789 Na2820 per mole of silver.
3”5H20 and 1.18■ KAu per mole of silver
Chemically sensitized using C14 at 85°C for 30 minutes.

Silver 1%kJl (1.0■Na2820g"5H2
The core-shell emulsion was chemically sensitized using C.0 for 30 minutes at 74.degree. 4! Silver 6.4 emulsion on reprocessed support
The emulsion was coated with 61/m-rich and gelatin 4841/m''. The emulsion layer also contained the spectral sensitizing dye anhydro-3,3'-
Bis(3-sul-gakujipropyl)-4゜5-benzothiacyanine hydroxide, sodium salt (chromium) and anhydro-5,5'-dichloro-3,9-diethyl-3'-sul-7oglobiloxasi Ani/-Hide Ω oxide (color chart B) each at 200W per mole of silver
v and nucleating agent: formyl-4-[2-(2,4-no-thialuphenoxy)-butanide]phenylhydrone, and formyl-4-(3-!l-hexylureido)phenyl A photographic element containing 1,001,119 hydrazine per mole of silver, respectively, is coated with 1 part by weight of bis(vinylsulfonylmethyl)ether to the total gel concentration to form a coating according to the present invention. A cubic core-shell silver bromide emulsion with a diameter of 0.25 micrometers was prepared according to the Dapluzier precipitation technique. A core consisting of cubic silver bromide with a diameter of 0.20 micrometers was heated to 12 da Nm2820s'5H2 per mole of silver.
Chemically sensitized using KAuCl4 at 0 and 1011p to 1 mole of silver at 75°C for 40 minutes. The core-shell emulsions were not chemically sensitized internally or under various conditions (see Table 5). , a larger (0.8 micrometer) core-shell emulsion and a smaller (0.25 micrometer) core-shell emulsion) are blended with isoelectric silver and then deposited on an ester film support. , 1m” total silver coverage 4.all
and 3.23 J' for a total gelatin coverage of 1 m''. The emulsion layer also contained spectral sensitizing dyes, Dye A and Dye B, each 20011p per mole of silver, and a nucleating agent: Holzuru 4. -(2-(2,4-di-t-acylphenoxy)butanide) phenylhydrazine, p and 4-(3-n-hexylphenoxy)-phenylhydrazine with silver 1 The coating film contained iooNg per mole of xenon lamp K for 10 seconds.
Exposure was performed through a density step/tablet, a 0-3.0 (0.15 density step) and a 0.86 neutral density filter as well as a filter to rate the film emitting at a maximum wavelength of 465. In an automatically vibrating, temperature-controlled chamber, the coating was incubated in Developer I for 90 seconds at 38°C.
℃ treatment to optimize the level of drag preservative for each coating. The results are shown in Table 1 below. As is evident from the results, there is good discrimination resulting in high Dwax and low Dmtn, both for the control at higher silver laydowns and for the coatings according to the invention at much lower silver laydowns. can get. Furthermore, the 111th edition related to the present invention is
4 compared to the control, albeit at a lower silver laydown.
Gives a higher Dm&x value. The coatings according to the invention also show a common feature and are much more sensitive than the control, even in the absence of surface sensitization of the smaller core particles with sulfur or gold.
The results also show the following contents. That is, the coatings of the present invention work well when small faciel emulsions are not internally surface sensitized and when sulfur is used to change the sulfur and total surface sensitization levels.

Comparative Example 2 A cubic silver bromide emulsion with a diameter of 0.2 micrometers was prepared according to the Dapruget precipitation technique, and per 1 mole of silver,
61M1ONa2S20. “5H20 and 5 to 1 mole of silver”? Netfff using 0KAu C14
The emulsion was surface sensitized for 40 minutes at 70° C. This was co-coated with a 1:1 blend with a 0.8 micrometer diameter octahedral core-shell emulsion as in Example IK, exposed and processed as in Example 1. The development time for sample 9 was 75 seconds. The results are shown in Table 1, and the results show the following: That is, if the small emulsion is not an internally sensitized core-shell emulsion, but only the surface is sensitized and the nine emulsions are sensitized. If so, we obtain inferior nine-image discrimination ability, that is, a high Dmin.

Margin below Table ■ [A 6.46 0.05 0.08 3.65 0
．． 16 289 vs. II B 4.31 0.05 0
．． 08 5.0 4.8 Example 3 Control coating film This coating film is similar to #1m film, and 9 is color 1.
1A 3 , 3'-cisulfate propylbenzo-1゜2
-Spectral sensitizer 5# in place of naphthothiazole cyanine
5'-dimethoxy-3,31-bis(3-sulfoprobyl) selenacyanine was used as a combination nucleating agent (nucleating agent 1) for Lareta, control coatings, or 3-provinyl-quinaldinium trifluoromethylsulfonate nuclei. Either of the forming agents (Nucleating Agent I) was used at 50 μm per mole of silver.

Coatings according to the invention were prepared using a cubic core-shell silver bromide emulsion with an E diameter of 0.25 micrometers by double-shed precipitation technique. A core of cubic silver bromide with a diameter of 0.20 micrometers was prepared using 70% of Na28203.5H20 at 12 to 1 mole of silver and 10 drops of KA11C14 per mole of silver.
Chemically sensitized for 40 minutes at °C. The core-shell emulsion was not internally chemically sensitized and mixed and then prepared as in Example 1, except that the same dyes and nucleating agents as previously described in the control coatings were substituted. Coat quality with larger grain core shell emulsion (0.89 micrometers).

The coatings were exposed and processed as in Example 1, but the coatings containing nucleating agent (1) were also developed for 60 seconds in an amino-free developer (see appendix). The results are shown in Table M and demonstrate the usefulness of nine different forming agents, developers and spectral sensitizing dyes.

Margin Example 4: The emulsions, dyes and coating procedures for the control and inventive coatings were similar to those in Example 3, except that no nucleating agent was present in the emulsion layer and the coating procedure was similar to that in Example 3. .

The coating was exposed and then processed in the same manner as in Example 3, except that developers M and ■ (see appendix, both of which contain forming agents) were used. Development time was 60 seconds. The results are shown in Table 3, which show the following fact: good image separation power and sensitivity not only depend on the nucleating agent mixed into the coating, but also the coating does not contain any nucleating agent. It can also be obtained by treating the coating film in a developer containing hydrazine or a hydrazide nucleating agent.

EXAMPLE 5 Control Coating - Same as Example 3 An octahedral core-shell silver bromide emulsion having a coating diameter of 0.21 micrometers according to the invention was prepared by double jet precipitation technique. A core made of octahedral silver bromide with a diameter of 0.14 micrometers was mixed with 7 to 7 Na2S2O3'5H20 per mole of scissors.
and chemically sensitized using 4M KAuCl4 at 10.5M9 per mole of silver at 80°C for 30 minutes. The core-shell particles were not internally chemically sensitized. The emulsion layers and coating procedure were similar to those of Example 3, except that a smaller grain population of Bc, o, zi micrometer core-shell grains was used.

The coatings were exposed and processed as in Example 3. 7th result
Shown in the table. The results show the following fact: small grain octahedral, core shell emulsions and small grain cubic core shell emulsions give good sorting power and sensitivity.

γ Margin Table V pair # 6.460.050.084,050.0430
1 wA 4.31 0.0!5 0.0?
4.7 0.06 277 Note developer! Ingredients' I/1 Tap water 850.0 (ethylene dinitrile) 1 taste 1 臥2 sodium 4 (EDT
A) 1.0 potassium hydroxide, 45 tatami
22.05-1fsyl) Lifsol s (MBT) 0.05-0.151-Phenyl-2-tet2zoline-5-thione (PMT) SOD4
~0.16 Sodium Sulfite, Anhydrous
75.04.4'-Dimethyl-1-phenyl-3-virazolizonone 0.4 Sodium bromide 8.0 Sodium hydrogen carbonate 7,02-ethylaminoethanol 58.6
3.3-Diaminodiprobylamine
4.0 Hydroquinone
40.0 potassium hydroxide, 45 excellent
7. o! 1. Add each component in the order shown and then allow to dissolve before adding the next.Adjust the pH to 10.70 at 280'F (32°C) enough to optimize the response for Sensitobary for each individual membrane. Level developer adjusted for ■ Ingredients 1/l Na25o, 65. lNaBr
4.31 Elon@(N-methyl-p-inophenol sulphate) 10. Jl Hydroquinone
40.145% KOH59
,7+' (Ethylenedinitrilo)I11iEa tetrasodium salt 5. 15-Methylbenzotriazole 2-1.-100011 in water
7 and 'pH11,0't? 2. The developer solution was adjusted to optimize the sensitometric response for each coating. same.

Developer ■ 4-Cf1-1 tansulfonamidoethyl) phenylhydrazine hydrochloride 2.011/l is used as the developer!
The advantage of the present invention is that an increase in silver covering II (depending on the mixed grain collective emulsion) can be achieved.

This was completely unexpected from the prior art use of core-shell emulsions. In one preferred form 11, described in more detail below, increased sensitivity for photographic elements is realized even when silver coverage is reduced.

Incorporation of polyvalent metal ions as a shield additive into the emulsions of the present invention reduces reinversion of the emulsion. Reinversion can also be reduced by increasing the concentration of iodide forming the shell portion of the core-shell particle. In cases where the shell portion of the particles contains chloride, low intensity--reduced reciprocity failure and a) continuous processing can also be achieved.

patent applicant Eastman Kodak Kanno 4 Knee Patent Application Agent Patent attorney Akira Iku Patent Attorney Kazuyuki Nishitate Patent attorney 1) Yukio Patent attorney Akira Yamaguchi

Claims (1)

[Claims] 1. consisting of silver halide grains and a dispersion medium, the first silver halide grain population has a variation coefficient of less than 20, and the second silver halide grain population has a photolytic It is possible to collect the generated electrons internally, and it is impossible to form surface latent scratches within the direct positive exposure layer of the first particle group, and the second particle group is the corresponding number
having an average diameter less than 70 − of the average diameter of the particle population of
Furthermore, the 1st and 20th/% rondized particle populations are 5
Radiation-sensitive emulsions which are particularly applicable for forming direct II/DIT images, with % rut being present in the weight ratio range of =1 to l:5.