JP3333518B2 - Dye image-forming photographic element - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a color photographic element comprising a radiation-sensitive tabular grain silver halide emulsion layer.

BACKGROUND OF THE INVENTION In the 1980's, improved speed sensitivity-granularity relationships in both single and multiple emulsion layer formats, increased covering power, both on an absolute basis and as a function of binder cure, faster A wide range of photographic advantages such as developability, increased thermal stability, increased separation of native and spectral sensitization to provide imaging sensitivity and improved image sharpness are achieved by using tabular grain emulsions. Based on the findings obtained, there have been significant advances in the field of silver halide photography.

An emulsion is generally understood to be a "tabular grain emulsion" when the tabular grains account for at least 50% of the total grain projected area. Its thickness (t) of its equivalent circular diameter (ECD)
When the ratio to is at least 2, the grains are generally considered to be tabular grains. The equivalent circular diameter of a grain is the diameter of a circle having an area equal to the projected area of the grain. The term "medium aspect ratio tabular grain emulsion" is
Emulsion having an average tabular grain aspect ratio in the range of 8. The term "high aspect ratio tabular grain emulsion"
Refers to emulsions having an average tabular grain aspect ratio greater than 8. The term `` thin tabular grains '' is generally 0.2
It is understood to be tabular grains having a thickness of less than μm. The term "ultrathin tabular grains" is generally 0.06 µm
It is understood to be tabular grains having the following thickness. The term "high chloride" refers to particles containing at least 50 mole percent chloride, based on silver. For mixed halide containing grains, the halides are named in order of increasing molarity. For example, silver iodochloride has a higher chloride molarity than iodide.

The overwhelming main component of the tabular grain emulsion contains tabular grains, which are irregular octahedral grains. An octahedral particle contains eight identical crystal planes, each of which is present in a different {111} crystallographic plane. A tabular disordered octahedron contains two or more parallel twin planes that separate two principal crystal planes that lie within a {111} crystallographic plane. The {111} major faces of the tabular grains exhibit a triangular or hexagonal triple symmetry. The tabular shape of the grains indicates that after the inclusion of parallel twin planes, the twins have edge sites that are favorable for silver halide precipitation, with the result that the grains grow on the sides with a slight increase in thickness, if any. It is generally accepted that it is the result of making.

Although tabular grain emulsions are advantageously used in a variety of photographic and radiographic applications, the need for parallel twin plane formation and {111} crystal planes places limitations on both emulsion production and use. These disadvantages are most pronounced when tabular grains containing high chloride concentrations are considered. It is generally accepted that silver chloride grains are likely to form cubic grains, ie, grains bound by six identical {100} crystal faces. Tabular grains bound by {111} planes in silver chloride emulsions often return to nontabular shapes if not morphologically stabilized.

Although tabular grain silver bromide emulsions were known in the art long before the 1980s, Wey U.S. Pat. No. 4,399,215 made the first tabular grain silver chloride emulsions. The tabular grains were of the twin type showing the principal plane of triple symmetry existing on the {111} crystallographic plane. An ammoniacal double jet precipitation method was used. Since the ammonia ripener thickens the tabular grains, the thickness of the tabular grains was greater than that of contemporary silver bromide and silver bromoiodide tabular grain emulsions. In order to effect ammonia ripening, it was also necessary to precipitate the emulsion at a relatively high pH, which was known to produce elevated minimum concentrations (fog) in high chloride emulsions. Further, the tabular grains, for which both bromide and iodide ions were determined to prevent deterioration, were removed from the tabular grains at the beginning of their formation.

In Wey U.S. Pat. No. 4,414,306, a twinning method was developed to produce a silver chlorobromide emulsion containing less than 40 mole percent chloride, based on total silver. This process has not been successfully extended to high chloride emulsions. The highest average aspect ratio reported in the examples was 11.

Maskasky U.S. Patent No. 4,400,463 (hereinafter Maskasky
I)) to produce high chloride emulsions containing tabular grains having parallel twin planes and {111} major crystal planes with significant advantages allowing significant internal content of other halides. Evolved policy. The strategy was to use a specially selected synthetic polymeric deflocculant in combination with a grain growth modifier that has the function of promoting the formation of {111} crystal faces. It has been disclosed that adsorbed aminoazaindenes, preferably adenine and iodide ions, are useful grain growth modifiers.

Maskasky US Patent No. 4,713,323 (hereinafter Maskasky)
II) contains tabular grains having parallel twin planes and {111} major crystal planes using an aminoazaindene growth modifier and a gelatino-peptizer containing up to 30 micromol / g methionine. The production of high chloride emulsions has significantly advanced the state of the art. If the methionine content of the gelatino-peptizer is undesirably high, a strong oxidizing agent (or
Maskasky II can be readily reduced by treatment with an alkylating agent, King et al., U.S. Pat. No. 4,942,120) so that a large amount of bromide and iodide prepared starting with conventional and conventional peptizers High chloride tabular grain emulsions containing ions were within the reach of the art.

Maskasky I and II stimulated further studies of grain growth modifiers that could produce high chloride emulsions of similar tabular grain content. U.S. Pat.No. 4,804,62 to Tufano et al.
No. 1, di (hydroamino) azines are used as particle growth modifiers, and Takada et al., U.S. Pat.
U.S. Pat.No. 4,952,491 to Shikawa et al. uses spectral sensitizers and divalent sulfur atom containing heterocycles and acrylic compounds, and U.S. Pat.No. 4,983,508 to Ishiguro et al. Is used.

Bogg U.S. Pat. No. 4,063,951 reports the first tabular grain emulsions in which the tabular grains have parallel {100} major crystal faces. Bogg's tabular grains exhibited square or rectangular main crystal faces, so there was no triple symmetry of conventional tabular grains {111} main crystal faces. In the only example, Bogg
Used an ammonia ripening method to produce silver bromoiodide tabular grains having an aspect ratio in the range of 4: 1 to 1: 1. The average aspect ratio of this emulsion was 2, and the highest aspect ratio grains (Grain A in FIG. 3) were reported to be only 4. Bogg states that this emulsion can contain up to 1% iodide and shows only a 99.5% bromide 0.5% iodide emulsion. Attempts to produce tabular grain emulsions by the Bogg method have been unsuccessful.

U.S. Pat. No. 4,386,156 to Mignot shows an improvement over Bogg that avoids the disadvantages of ammonia ripening in making silver bromide emulsions containing tabular grains having square and rectangular major crystal faces. Mignot specifically requires ripening in the absence of silver halide ripening agents other than bromide ions (eg, thiocyanates, thioethers or ammonia).

Endo and Okaj, "Empirical rules for modifying the crystal habit of silver chloride to form tabular grains in emulsions (An Empiric
al Rule to Modify the Habit of Silver Chloride to
form Tabular Grains in an Emulsion) ", The Journa
l of Photographic Science, 36, 182-188, 1988, discloses a silver chloride emulsion prepared in the presence of a thiocyanate ripening agent. Emulsion preparation by the disclosed method produced emulsions containing few tabular grains within the general grain population exhibiting mixed {111} and {100} crystal faces.

Mumaw and Haugh, "Silver halide precipitation coagulation method (Silv
er Halide Precipitation Coalescence Processes),
Journal of Imaging Science, Vol. 30, No. 5, September / October, 1986
Years, pages 198-299, are essentially repetitions of Endo and Okaji, with particular reference to Section IV-B.

Symposium: Torino 1963, photographic Science,
Ed. C. Semerano and U. Mazzucato, Focal Press, pp. 52-55, discloses the ripening of cubic grain silver chloride emulsions at 77 ° C. for several hours. During ripening, tabular grains appeared and the original cubic grains were reduced by Ostwald ripening. Manufacturing below
As indicated by II, after 3 hours of ripening, the tabular grains occupied only a small portion of the total grain projected area, and only a small portion of the tabular grains were less than 0.3 μm thick. In further research that went beyond the actual teachings given,
Extended ripening removed many smaller cubic grains, but also degraded many tabular grains to a thicker form.

JP-A-2-024643, published Jan. 26, 1990, was cited in the PCT search report as relating to the tabular grain structure claimed in the claims, but in the opinion of the present inventor, I haven't. The present invention relates to hydrazide derivatives and 0.6-0.2
It is directed to negative emulsions containing tabular grains having an equivalent circular diameter of μm. It only discloses conventional tabular grain production and only exemplifies silver bromide and silver bromoiodide emulsions.

U.S. Pat. No. 4,952,491 to Nishikawa et al., Cited above, discloses the use of tabular silver halide emulsions having a high chloride content in color photographic elements. The tabular grains described in this patent are linked by {111} major crystal planes as illustrated in FIGS. 1 and 2 of that patent.

The use of imageable compounds in color photographic elements has been known for many years. Typically, these compounds are used in reactive association with the silver halide emulsion layers in such elements. During the development process, the dye-forming compound reacts with an oxidized developing agent (hereinafter referred to as an oxidized developing agent) to form a dye. The dye density that can be obtained for a particular amount of developed silver is higher, and silver halide grains with higher sensitivity tend to give smaller dye density than grains with lower sensitivity. It is greatly affected by the morphology of the silver halide grains in the layer. Accordingly, there remains a need for a combination of a silver halide emulsion and an image dye-forming compound that can provide both high sensitivity and high dye density formation. This need is due to the fact that high chloride content allows for faster and easier development processability, including faster and easier development, bleaching and fixing, so silver halides with higher chloride content This is particularly evident in emulsions.
Unfortunately, silver halide emulsions having a high chloride content that also exhibit high photographic speed are difficult to prepare.

It is also known that advantageous effects can be obtained when a silver halide emulsion layer is used in a color photographic element consisting of a compound containing a photographically useful group released in reaction with an oxidized developing agent. Such compounds may be intercalated (interl
Used to obtain a desired effect, such as an ayer effect or an interimage effect or an image accutance effect. These compounds are referred to simply as "photographically useful substrate release compounds" as described more fully below, and are described in U.S. Pat.
Nos. 962, 4,409,323 and 4,861,701 and European Patent Application 354,532. Examples of such photographically useful group releasing compounds are development inhibitor releasing (DIR) compounds known in the photographic art. DIR compounds release development inhibitors during photographic processing, such development inhibitors can be used to provide various photographic effects such as reducing gamma, and are used to control curve shapes can do. Unfortunately, development inhibitor releasing compounds have limited utility in cubic silver halide emulsions having a high chloride content. This is because such compounds tend to have a small effect on latitude or gamma when used with such emulsions. In addition, DIR compounds often cause loss of sensitivity in such emulsions.

In the art, tabular silver halide grains in combination with image-forming compounds and photographically useful group-releasing compounds such as the non- disadvantageous DIR compounds described above,
In particular, it is apparent that it is highly desirable to have a color photographic element that includes a radiation-sensitive tabular grain emulsion layer consisting of grains having a high chloride content. It is an object of the present invention to provide such a color photographic element.

Related Patent Application A continuation-in-part of U.S. Patent Application No. 764,868 filed on September 24, 1991, and a continuation-in-part of U.S. Patent Application No. 955,010 filed on October 1, 1992, filed on the same date as the present application Applied Maskasky U.S. Pat.No. 5,292,632, entitled `` High Tabularity High Chloride Emulsions with I
"Nherently Stable Grain Faces" (commonly transferred, hereinafter referred to as Maskasky III) has a high aspect ratio tabular grain height that contains no internal iodide and contains {100} major tabular grains. Chloride emulsions are disclosed. In a preferred embodiment, Maskasky III uses an organic compound containing a nitrogen atom having a resonance-stabilized π-electron pair to facilitate the formation of the {100} major surface.

Filed on the same date as the present application as a continuation-in-part of U.S. Patent Application No. 940,404 filed on September 3, 1992, which is a continuation-in-part of U.S. Patent Application No. 826,338 filed on January 27, 1992 House, Brust, Hartsell and Black U.S. patent application Ser.No. 08/034060, entitled `` High Aspect Ratio Tab
“ular Grain Emulsions” (each commonly transferred) includes all remaining tabular grains selected based on criteria of adjacent major surface edge ratios less than 10 and thicknesses less than 0.3 μm and meeting these criteria. All-grain projections having a higher aspect ratio than (1) having an average aspect ratio greater than 8 and (2) internally containing iodide and at least 50 mole percent chloride at its nucleation site 50% of area
Emulsions containing tabular grains bound by {100} major faces occupying the same are disclosed.

Brust, filed on the same date as the present application and normally transferred,
House, Hartsell and Black U.S. Patent Application 08/085009
No., title of invention `` Moderate Aspect Ratio Tabular Grai
n Emulsions and Processes Their Preparation "discloses a radiation-sensitive emulsion comprising a dispersion medium and silver halide grains. At least the total grain projected area
50% are joined by {100} major surfaces having an adjacent edge ratio of less than 10, each having an aspect ratio of at least 2 and an average aspect ratio of 8 or less, and internally having iodide and at least Occupied by tabular grains containing 50 mol% chloride. A method for producing this emulsion is also disclosed.

Filed on the same date as the present application as a continuation-in-part of US Patent Application No. 940,404 filed on September 3, 1992, which is a continuation-in-part of U.S. Patent Application No. 826,338 filed on January 27, 1992 House, Brust, Hartsell, Black, Antoniades, Tsau
r and Chang U.S. Patent Application No. 08/033738, entitled `` Processes of Preparing Tabular Grain Emulsions ''
(Each commonly transferred) are selected on the basis of an adjacent principal surface edge ratio of less than 10 and a thickness of less than 0.3 μm, internally having iodide and at least 50 mol% chloride at their nucleation sites. 50% of the total grain projected area
A process for producing an emulsion containing tabular grains bound by {100} major faces, comprising: (1) introducing silver and a halide salt into the dispersion medium, Nucleation of tabular grains in the presence of iodide with chlorides, which make up at least 50 mol% of the iodides,
And (2) maintaining the {100} principal plane of the tabular grains until the tabular grains exhibit an average aspect ratio greater than 8 following nucleation, and A method comprising the step of completing grain growth under conditions is disclosed.

Pucket filed on the same date as the present application and normally transferred
t, U.S. Patent Application No. 08/033739, entitled "Origomer
"Modified Tabular Grain Emulsions" discloses a radiation-sensitive emulsion and a method for producing the same. At least 50% of the total grain projected area is bounded by {100} major surfaces having adjacent edge ratios less than 10, each having an aspect ratio of at least 2, and on average at least one pair of Group VIII, periods 5 and 6 A metal ion selected from
It is occupied by high chloride tabular grains contained at adjacent cation sites in its crystal lattice.

Filed on the same date as the present application as a continuation-in-part of U.S. Patent Application No. 940,404 filed on September 3, 1992, which is a continuation-in-part of U.S. Patent Application No. 826,338 filed on January 27, 1992 Brust, House, Hartsell, Black and Marchetti U.S. Patent Application No. 08/034982, entitled `` Coordinatio
n Complex Ligand Modified Tabular Grain Emulsion
s "(each commonly transferred) includes a selection of adjacent major surface edge ratios of less than 10 and a thickness of less than 0.3 μm, which is greater than any remaining tabular grains meeting these criteria. Having a high aspect ratio, (1) having an average aspect ratio greater than 8, and (2) internally containing iodide and at least 50 mole% chloride at its nucleation site. Emulsions containing tabular grains bound by {100} major faces accounting for 50% are disclosed. The tabular grains contain a non-halide coordination complex ligand.

Budz, L filed on the same date as the present application and commonly assigned
igtenberg and Roberts U.S. Patent Application No. 08/034050,
Title of Invention `` Digital Imaging with Tabular Grain Emu
"lsions" disclose a digitally imageable photographic element containing a tabular grain emulsion consisting of a dispersion medium and silver halide grains containing at least 50 mole percent chloride based on silver. At least 50% of total grain projected area
Are occupied by tabular grains having {100} major faces with adjacent edge ratios less than 10, each having an aspect ratio of at least 2.

Szajew filed on the same date as the present application and commonly transferred
ski U.S. Pat.No. 5,310,635, entitled `` Film and C
"amera" discloses a roll film and a roll film camera comprising at least one emulsion layer comprising a tabular grain emulsion consisting of a dispersion medium and silver halide grains containing at least 50 mole percent chloride based on silver. Have been. At least 50% of the total grain projected area is occupied by tabular grains, each having an aspect ratio of at least 2, bound by {100} major faces having adjacent edge ratios of less than 10.

U.S. patent application Ser.No. 08/034317 to Lok and Budz, filed on the same date as the present application and commonly assigned,
ular Grain Emulsions Containing Antifoggants and S
"tabilizers" disclose a tabular grain emulsion comprising a dispersion medium, silver halide grains containing at least 50 mole percent chloride, based on silver, and at least one selected antifoggant or stabilizer. . At least 50% of the total grain projected area has an adjacent edge ratio less than 10
It is occupied by tabular grains each having an aspect ratio of at least 2 bound by 0｝ major faces.

Maskas filed on the same date as the present application and commonly transferred
ky U.S. Pat.No. 5,264,337, entitled `` Moderate As
pect Ratio Tabular Grain High Chloride Emulsions w
ith Inherently Stable Grain Faces contains at least 50 mol%
An emulsion comprising a population of grains consisting of chlorides is disclosed. At least 50% of the grain population projected area is occupied by {100} tabular grains each having an aspect ratio of at least 2 and together having an average aspect ratio of 7.5 or less.

Buchan filed on the same date as the present application and commonly transferred
U.S. Pat.No. 5,443,943 to An and Szajewski, entitled `` Method of Processing Photographic Elements Conta
"Ining Tabular Grain Emulsions" discloses a method for developing and desilvering dye-imageable photographic elements containing high chloride {100} tabular grain emulsions of the type described therein.

SUMMARY OF THE INVENTION According to the present invention, a color comprising a support comprising a dispersing medium and silver halide grains and having at least one radiation-sensitive emulsion layer having image dye-forming compounds in reactive association. A photographic element, wherein (A) at least 50% of the total grain projected area is joined by a {100} major surface having an adjacent edge ratio less than 10;
Each being occupied by tabular grains having an aspect ratio of at least 2, wherein the tabular grains are silver iodochloride grains, and (B) the emulsion layer is also in a reactively related, Having a compound capable of reacting with an oxidized developing agent thereby releasing a photographically useful group;
Color photographic elements are provided wherein the photographically useful group is a development inhibitor, bleach accelerator, development accelerator, competitive coupler, electron transfer agent, bleach inhibitor or dye.

An important feature of the present invention is that the color photographic element can be developed by conventional color developing techniques to provide a developed element that exhibits exceptional image sharpness. Further, as shown in the examples below, the color photographic images of the present invention comprise a photographically useful group such as a development inhibitor group released in reaction with an oxidized developing agent (ie, an oxidized developing agent). The element provides a desirable reduction in gamma with a concomitantly large increase in latitude, which is completely unexpected, in light of the results obtained with prior art silver halide emulsions consisting of comparable cubic silver halide grains. Also, as shown in the examples below, the present invention allows the use of compounds that release a variety of photographically useful groups in the practice of the present invention, so that in selecting the desired specific photographic activity, Provides excellent flexibility. For example, suitable photographically useful groups include:
Includes development inhibitors, development accelerators, bleach inhibitors, bleach accelerators, electron transfer agents or couplers such as competitive couplers.

The present invention has been facilitated by the discovery of a novel approach to forming tabular grains. When producing tabular grains formed to produce tabularity and thereby having {111} major faces, instead of having parallel twin planes within the grains, the chloride in solution within the selected pCl range is The presence of iodide in the dispersing medium during the high chloride nucleation step, in combination with the retention of chloride ions, results in the formation of tabular grain emulsions in which tabular grains are bound by {100} crystal faces. Was found to result in

The above approach of forming tabular grains brings tabular grains bound by {100} crystal faces with grain composition and grain thickness not heretofore realized within the art. For example, an ultrathin tabular grain emulsion in which grains are linked by {100} crystal planes can be obtained. In a preferred form, the methods described herein can be used to provide medium and high aspect ratio tabular grain high chloride emulsions that exhibit high levels of grain stability. Unlike high chloride tabular grain emulsions, in which the tabular grains have {111} major faces, such emulsions have a morphological stability adsorbed to the major faces of the grains to maintain their tabular morphology. No agents are required. Finally, although apparently applicable to high chloride emulsions, the present invention provides a method of preparing silver chloride, each of which can be produced by a variety of precipitation methods that does not require the presence of iodide during grain nucleation. It extends to emulsions and silver bromochloride emulsions.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a shadowed micrograph of a carbon particle replica of a representative emulsion prepared by Illustrative Emulsion Preparation, Preparation I, which is a typical emulsion useful in the color photographic elements of the present invention.

FIG. 2 is a photomicrograph with shadow of a carbon particle replica of a control emulsion prepared by Illustrative Emulsion Production, Production II.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The identification of emulsions that meet the requirements of the invention and the significance of the selection parameters can be better appreciated by considering typical emulsions. FIG. 1 is a photomicrograph with shadow of a carbon particle replica of a representative emulsion of the invention described in detail in Example 1 below. It is immediately apparent that most of the particles have right-angled square (square or rectangular) faces. The rectangular shape of the grain plane indicates that these are {100} crystal faces.

The projected area of a few grains in a sample that does not have a square or rectangular face is noted for inclusion in the calculation of total grain projected area, but these grains are clearly tabular grains with {100} major faces. Not part of a group.

Few particles, which are needle-like or rod-like particles (hereinafter referred to as rods), may be observed. These grains are more than ten times longer in one dimension than all other dimensions and are excluded from the desired tabular grain population based on their high ratio of edge length. The projected area occupied by rods is low,
When rods are present, their projected area is noted to determine the total grain projected area.

All the remaining grains have a square or rectangular major surface exhibiting a {100} crystal plane. To identify tabular grains, the ratio of ECD to thickness (t) for each grain,
That is, it is necessary to determine ECD / t. ECD is determined by measuring the projected area (the product of the edge lengths) of the top surface of each grain. The ECD of the particle is calculated from the projected area of the particle. Particle thickness is usually determined by oblique illumination of a particle population that causes individual particles to cast shadows. From the knowledge of the illumination angle (shadow angle), it is possible to calculate the thickness of the particles by measuring the shadow length. Grains having square or rectangular faces, each having an ECD / t ratio of at least 2, are tabular grains having {100} major faces. ｛100｝
Tabular grain projected area is at least 50 of total grain projected area
When accounted for by percent, the emulsion is a tabular grain emulsion.

In the emulsion of FIG. 1, tabular grains have a total grain projected area of
Accounts for more than 50%. From the above definition of tabular grains, the average aspect ratio of tabular grains is the minimum limit of 2
It is clear that one can only approach
In fact, the tabular grain emulsions of the present invention typically exhibit an average aspect ratio of 5 or greater, with high average aspect ratios (> 8) being preferred. That is, the preferred emulsions according to the present invention are high aspect ratio tabular grain emulsions. In particularly preferred emulsions according to the present invention, the tabular grain population has an average aspect ratio of at least 12, optimally at least 20. Typically, the average aspect ratio of a tabular grain population is
High aspect ratios in the range of 50 or less but 100,200 or greater are feasible. Average aspect ratio is 2
Emulsions within the contemplation of the present invention approaching the minimum average aspect ratio limit of further provide a surface to volume ratio that is 200% of that of the cubic grains.

The tabular grain means may exhibit any grain thickness consistent with the above average aspect ratio. However, especially when the selected tabular grain population exhibits a high average aspect ratio, the grains contained in the selected tabular grain population are reduced to a thickness of less than 0.3 μm, optimally less than 0.2 μm. It is preferable to further restrict. It is recognized that the aspect ratio of a tabular grain can be limited by limiting its equivalent circular diameter or increasing its thickness. That is, when the average aspect ratio of the tabular grain population is in the range of from 2 to 8, tabular grains occupying at least 50% of the total grain projected area are also each 0.1%.
A particle thickness of less than 3 μm or less than 0.2 μm is indicated. Nevertheless, there are certain photographic applications that benefit from higher tabular grain thicknesses, especially within the 2-8 aspect ratio range. For example, it is specifically contemplated that in constructing a blue recording emulsion layer of maximum achievable sensitivity, tabular grain thicknesses that average 1 μm or even greater can be tolerated. This is because the eye is minimally sensitive to the blue record, so higher levels of image granularity (noise) can be tolerated without objection. There are additional incentives to use larger particles in the blue record, which is sometimes difficult to match the highest sensitivity achievable in the green and red records in the blue record. The source of this difficulty lies in the lack of blue photons in sunlight. On an energy basis, sunlight shows equal parts of blue, green and red light, but the shorter the wavelength, the higher the energy of the particles. So sunlight is slightly blue deficient on a photon distribution basis.

The tabular grain population preferably exhibits a major edge length ratio of less than 5, optimally less than 2. As the principal surface edge length ratio approaches 1 (ie, equal edge length),
The probability of significant rod populations present in the emulsion is reduced. In addition, tabular grains having smaller edge ratios will be less susceptible to pressure desensitization.

In one particularly preferred form of the invention, the tabular grain population accounting for at least 50% of the total grain projected area is also provided by tabular grains exhibiting 0.2 μm. In other words, in this example the emulsion is a thin tabular grain emulsion.

Surprisingly, ultrathin tabular grain emulsions have been prepared by satisfying the needs of the present invention. Ultrathin tabular grain emulsions are those in which the selected tabular grain population has been made from tabular grains having a thickness of less than 0.06 μm. Prior to the present invention, the only halide-containing ultrathin tabular grain emulsions exhibiting a cubic crystal lattice structure known in the art include tabular grains connected by {111} major faces. Was. In other words, it was considered essential to form tabular grains by a mechanism containing parallel twin planes in order to obtain ultrathin dimensions. Emulsions according to the invention can be prepared in which the tabular grain population has an average thickness reduced to 0.02 μm, and even down to 0.01 μm. Ultrathin tabular grains have a very high surface to volume ratio. This allows the ultra-thin particles to be processed photographically at an accelerated rate. Furthermore, when spectrally sensitized, the ultrathin tabular grains exhibit a very high sensitivity ratio in the spectral region of sensitization as compared to the spectral region of intrinsic sensitivity. For example, the ultrathin tabular grain emulsions according to the present invention have a completely negligible level of blue sensitivity, thus exhibiting minimal green staining in photographic products when arranged to receive blue light. Or a red record can be given.

The characteristics of tabular grain emulsions that distinguish them from other emulsions are
It is the ratio to the thickness (t) of the ECD. This relationship has been quantitatively expressed in terms of the aspect ratio. Another quantification that is believed to more accurately assess the importance of tabular grain thickness is tabularity.

T = ECD / t ² = AR / t where T is the flatness, AR is the aspect ratio, ECD is the equivalent circular diameter in micrometers (μm), and t is the particle in micrometers. Thickness.

The high chloride tabular grain population accounting for 50% of the total grain projected area preferably exhibits a tabularity greater than 25, most preferably greater than 100. Since this tabular grain population can be ultrathin, it is clear that very high tabularities, up to 1000 and higher, are within the contemplation of the present invention.

The tabular grain population may exhibit an average ECD of any size that is photographically useful. Although the average ECD in most photographic applications is rarely greater than 6 μm, an average ECD of less than 10 μm is contemplated for photographic utility. Within an ultrathin tabular grain emulsion satisfying the requirements of the present invention, 0.10
ECDs of this tabular grain population of μm and smaller can provide intermediate aspect ratios. As generally understood by those skilled in the art, emulsions comprising a selected tabular grain population having a higher ECD are advantageous for obtaining relatively high levels of photographic speed, while lower
Selected tabular grain populations with an ECD are advantageous for obtaining low levels of granularity.

A photographically desirable grain population is available so long as the tabular grain population satisfying the above parameters accounts for at least 50% of the total grain projected area. It is observed that the advantageous properties of the emulsions of the present invention increase as the population of tabular grains having {100} major faces increases. Preferred emulsions according to the present invention are those in which at least 70%, optimally at least 90%, of the total grain projected area is occupied by tabular grains having {100} major faces. It is specifically intended to provide an emulsion that satisfies the above grain description wherein the selection of ordered tabular grains is extended to sufficient tabular grains accounting for up to 70% or even 90% of total grain projected area.

The remainder of the total grain projected area may be occupied by any combination of co-precipitated grains, as long as the tabular grains having the desired properties described above occupy the required ratio of total grain projected area. Of course, blending the emulsions to obtain a particular photographic objective is a common practice in the art. Blend emulsions in which at least one component emulsion satisfies the above tabular grain description are specifically contemplated.

If the tabular grains that do not satisfy the tabular grain population requirements account for 50% of the total grain projected area, the emulsion does not satisfy the requirements of the invention and is generally a poor photographically emulsion. For most applications (especially those requiring spectral sensitization, requiring rapid development and / or requiring minimal silver coverage), many or all of the tabular grains are relatively Thick emulsions, for example, emulsions containing a high proportion of tabular grains having a thickness greater than 0.3 μm, are photographically inferior.

More generally, poor emulsions that do not meet the requirements of the invention have an excess proportion of total grain projected area occupied by cubes, twin non-tabular grains and rods. Such an emulsion is shown in FIG. Most of the grain projected area is occupied by cubic grains. Also, it can be asserted that the number of rod-like objects is much larger than that in FIG. There are a few tabular grains, but these account for only a small portion of the total grain projected area.

The tabular grain emulsion of FIG. 1 and the predominantly cubic grain emulsion of FIG. 2 satisfying the requirements of the present invention were prepared under identical conditions except that iodine was controlled during nucleation. FIG.
Is an silver chloride emulsion, while the emulsion of FIG. 1 contains a smaller amount of iodide.

Obtaining tabular grain emulsions satisfying the requirements of the present invention has been achieved by the discovery of a novel precipitation method. In this method, nucleation occurs in a high chloride environment in the presence of iodide ions under conditions favoring the appearance of {100} crystal faces.
When grain formation occurs, the iodide content in the cubic crystal lattice formed by silver ions and the remaining halide ions is disintegrating due to the larger diameter of iodide ions compared to chloride ions. is there. The contained iodide ions cause crystal irregularities that become tabular rather than regular (cubic) grains during the subsequent grain growth.

It is believed that the inclusion of iodide ions in the crystal structure at the onset of nucleation will result in the formation of cubic grain nuclei with one or more screw dislocations on one or more cubic crystal faces. . A cubic crystal plane containing at least one screw dislocation will then accept silver halide at an accelerated rate as compared to a regular cubic crystal plane (ie, one lacking screw dislocations). When only one of the cubic crystal faces contains a screw dislocation, grain growth on only one face is accelerated and the grain structure obtained by continuous growth is a rod. The same result occurs when only two opposing parallel faces of the cubic crystal structure contain screw dislocations. However, when any two adjacent cubic crystal faces contain screw dislocations, continued growth accelerates growth on both faces,
Make a tabular grain structure. Tabular grains of the emulsion of the present invention are:
It is believed that these nuclei have 2, 3, or 4 faces containing screw dislocations.

At the beginning of the precipitation, a reaction vessel containing a dispersion medium and a conventional silver and reference electrode for monitoring the halide ion concentration in the dispersion medium is provided. At least 50 mol%
Is a chloride, ie at least half of the number of halide ions in the dispersion medium are chloride ions. PCl of the dispersion medium,
Nucleation favors the formation of {100} grain faces, ie
In the range of 0.5-3.5, preferably in the range of 1.0-3.0,
Optimally, it is adjusted in the range of 1.5 to 2.5.

The particle nucleation step is started when the silver jet is open to introduce silver ions into the dispersion medium. The iodide ions are preferably introduced into the dispersion medium simultaneously with or optimally before the opening of the silver jet. Effective tabular grain formation can occur over a wide range of iodide ion concentrations, up to the saturation limit of iodide in silver chloride. The saturation limit of iodide in silver chloride was determined by H. Hirsch in "Photographic Emu
lsion Grains with Cores: Part I. Evidence for the Pr
esence of Cores ", J. of Photog. Science, 10 (1962
Year), pp. 129-134. In a silver halide grain having an equimolar ratio of chloride ion and bromide ion, iodide of 27 mol% or less based on silver can be contained in the grain. It is preferred to carry out grain nucleation and growth below the iodide saturation limit in order to avoid precipitation of the separated silver iodide phase and thereby avoid creating additional types of unwanted grains. The concentration of iodide ions in the dispersing medium should be
It is generally preferred to keep it lower. In fact, only a small amount of iodide is required during nucleation to obtain the desired tabular grain population. Initial iodide ion concentrations down to 0.001 mol% are contemplated. However, it is preferred to maintain an initial iodide concentration of at least 0.01 mol%, optimally at least 0.05 mol%, for reasons of reproducibility of the results.

In a preferred embodiment of the present invention, silver iodochloride grain nuclei are formed during the nucleation step. Small amounts of bromide ions may be present in the dispersion medium during nucleation. During nucleation, any amount of bromide ion compatible with at least 50 mole percent of the halide in the grain nucleus, which is chloride, may be present in the dispersion medium. Preferably, the particle nucleus
At least 70 mol% based on silver, optimally at least 90 mol%
Contains mol% chloride ions.

Grain nucleation occurs immediately upon introduction of silver ions into the dispersion medium. For handling convenience and reproducibility, silver ion introduction during the nucleation step is preferably extended to a convenient time, typically from 5 seconds to less than 1 minute. There is no need to add additional chloride ions into the dispersion medium during the nucleation step, as long as the pCl is maintained within the above range. However, it is preferred to introduce both the silver salt and the halide salt simultaneously during the nucleation step. The advantage of adding the halide salt at the same time as the silver salt through the nucleation step is that all grain nuclei formed after the start of silver ion addition have essentially the same halide content as the initially formed grain nuclei. It is guaranteed to be of quantity.
Iodide ion addition during the nucleation step is particularly preferred. Unless replenished, iodide will be lost from the dispersing medium since the rate of deposition of iodide ions is much greater than the rate of deposition of other halides.

During the nucleation step any convenient conventional source of silver and halide ions can also be used. The silver ions are preferably introduced as an aqueous silver salt solution such as a silver nitrate solution. The halide ion is preferably lithium,
Sodium and / or potassium chlorides, bromides and / or
Alternatively, it is introduced as an alkali halide such as iodide or an alkaline earth halide.

During the nucleation step, silver chloride or silver iodochloride Lippmann grains can be introduced into the dispersion medium, but are not preferred. In this case, particle nucleation has already taken place, and what is shown above as the nucleation step is actually a step of introducing irregularities in the particle surface. The disadvantage of slowing the introduction of grain-plane irregularities is that it makes tabular grains thicker than would otherwise be obtained.

Before the nucleation step, the dispersion medium contained in the reaction vessel consists of water, the dissolved halide ions and the deflocculant. The dispersing medium may exhibit a pH within any convenient conventional range for silver halide precipitation, typically a pH of from 2 to 8. It is preferred, but not necessary, to maintain the pH of the dispersion medium on the neutral acidic side (ie, <7.0). The preferred pH range for precipitation is 2.0 to minimize fog.
5.0. Mineral acids such as nitric acid or hydrochloric acid and bases such as alkali hydroxides can be used to adjust the pH of the dispersion medium. It is also possible to include a pH buffer.

The peptizers may take any convenient conventional form known to be useful in the precipitation of photographic silver halide emulsions, especially tabular grain silver halide emulsions. For an overview of conventional peptizers, see Research Disclosure, Volume 308, December 1989.
Month, Item 308119, Section IX. Research
Disclosure is from Kenneth Mason Publications, Ltd., Emsw
orth, Hampshire P010 7DD, published from the UK.
Synthetic polymeric deflocculants of the type disclosed in Maskasky I, cited above and incorporated herein by reference, can be used, but use of gelatin deflocculants (eg, gelatin and gelatin derivatives) Is preferred. It is a known method to use deionized gelatin deflocculants when made and used in photography, but gelatin deflocculants typically contain significant concentrations of calcium ions. . In the former example, it is preferred to compensate for calcium ion removal by adding alkaline earth or earth metal ions, preferably divalent or trivalent metal ions such as magnesium, calcium, barium or aluminum ions. . Particularly preferred deflocculants are low methionine gelatin deflocculants (ie, those containing less than 30 micromoles of methionine per gram of deflocculant), optimally having less than 12 micromoles of methionine per gram of deflocculant. These peptizers and their manufacture are described in Maskasky II and King et al., Cited above and whose disclosure is incorporated herein by reference. However, grain growth modifiers of the type taught to be included in the Maskasky I and II emulsions (e.g., adenine) are those which have twinning and {111}
It should be noted that it promotes the formation of tabular grains having major faces and is not suitable for inclusion in the dispersion medium of the present invention. Generally, at least about 10%, typically 20-80%, of the dispersion medium forming the finished emulsion will be present in the reaction vessel at the beginning of the nucleation step. Relatively low levels of peptizer, typically 10-20% of the peptizer present in the finished emulsion
Is maintained in the reaction vessel at the beginning of the precipitation. In order to increase the proportion of thin tabular grains having {100} faces generated during nucleation, the concentration of the deflocculant in the dispersing medium is between 0.5 and 0.5% of the total weight of the dispersing medium at the start of the nucleation step. Preferably it is in the range of 6% by weight. It is conventional practice to add gelatin, gelatin derivatives and other vehicles and vehicle extenders to produce coating emulsions after precipitation. Any naturally occurring levels of methionine may be present in the gelatin and gelatin derivatives added after precipitation is complete.

The nucleation step can be performed at any convenient conventional temperature for precipitation of silver halide emulsions. Temperatures near the ambient temperature, for example, in the range of 30 ° C. to about 90 ° C. are contemplated, with temperatures in the range of 35-70 ° C. being preferred.

Since grain nucleation occurs almost instantaneously, only a very small proportion of the total silver needs to be introduced into the reaction vessel during the nucleation step. Typically, about 0.1 to 10 mole% of total silver is introduced during the nucleation step.

The grain growth step in which grain nuclei grow until a tabular grain having a {100} major surface of the desired average ECD is obtained is continued to the nucleation step. The purpose of the nucleation step is to form a population of particles having the desired contained crystal structure disorder,
The purpose of the growth step is to deposit additional silver halide over the (growing) existing grain population while avoiding or minimizing the growth of additional grains. If additional grains are formed during the growing step, the polydispersity of the emulsion will increase and the additional steps generated in the growing step unless the conditions in the reaction vessel are maintained as described above for the nucleation step. Will not have the desired tabular grain properties described above.

In its simplest form, the process for producing an emulsion according to the invention can be carried out as a single jet precipitation without interruption of silver ion introduction from start to finish. As is generally recognized by those skilled in the art, as the size of the grain nuclei increases, the grain nuclei reach the point at which they receive silver and halide ions at a rate fast enough that no new grains can be formed. Increases the rate at which silver ions and halide ions are received from the dispersion medium, so that a spontaneous transition from grain formation to grain growth occurs even at a constant rate of silver ion introduction. It's a simple operation,
Single jet precipitation limits the halide content and profile and generally results in a more polydisperse population of particles.

It is generally preferred to produce a photographic emulsion having the most geometrically uniform grain population achievable. This is because this allows a higher percentage of the total grain population to be optimally sensitized for photographic applications and otherwise produced optimally. Furthermore, it is generally more common to blend relatively monodisperse emulsions to obtain the desired sensitometric profile than to precipitate a single polydisperse emulsion that matches the desired sensitometric profile. More convenient.

In the preparation of the emulsions according to the invention, it is preferred to interrupt the introduction of silver salts and halide salts at the completion of the nucleation step and before proceeding with the growth step to bring the emulsion to its desired final size and shape. . The emulsion is held in the above temperature range for nucleation for a period of time sufficient to reduce grain dispersity. Retention periods can range from one minute to several hours, with typical retention periods ranging from five minutes to one hour. During the holding period, the smaller particle nuclei are Ostwald ripened over the remaining larger particle nuclei, the overall result is a reduction in particle dispersity.

If desired, the rate of ripening can be increased by the presence of a ripening agent in the emulsion during the retention period. The traditional simple approach to accelerating ripening is
The purpose is to increase the halide ion concentration in the dispersion medium. This forms a complex of silver ions with multiple halide ions that accelerate ripening. When using this approach, it is preferable to increase the chloride ion concentration in the dispersion medium. That is, it is preferable to reduce the pCl in the dispersion medium to a range where increased silver chloride solubility is observed.
Also, by using conventional ripening agents, ripening can be accelerated and the percentage of total grain projected area occupied by {100} tabular grains can be increased. Preferred ripening agents are sulfur-containing ripening agents such as thioethers and thioisocyanates. Typical thioisocyanates are described in U.S. Pat.
No. 64, Lowe et al. U.S. Pat.No. 2,448,534 and Illingswort
h, U.S. Pat. No. 3,320,069, the disclosures of which are incorporated herein by reference. Typical thioether ripening agents are described in McBride U.S. Pat.No. 3,271,157, Jo
Nes. U.S. Pat. No. 3,574,628 and Rosencrantz et al. U.S. Pat. No. 3,737,313, the disclosures of which are incorporated herein by reference. More recently, the use of crown thioethers as ripening agents has been suggested. Ripening agents containing primary or secondary amino units such as imidazole, glycine or substituted derivatives are also effective. Sodium sulfite has also been shown to be effective in increasing the percentage of total grain projected area occupied by {100} tabular grains.

Once the desired population of grain nuclei has been formed, grain growth to obtain the emulsions of the present invention may be performed by any convenient conventional precipitation method for precipitating silver halide grains bound by {100} grain faces. May proceed. Iodide and chloride ions need to be included in the grains during nucleation and are therefore present in grains completed at internal nucleation sites, but are known to form cubic crystal lattice structures. Any halide or combination of halides that can be used during the growth step can be used. Once introduced, the irregular grain nuclei that result in tabular grain growth,
Irrespective of the halide that precipitates during subsequent grain growth, any iodide or chloride ions will remain in the grains during the growth process because the halide or combination of halides will remain as long as they form a cubic crystal lattice. It is not necessary to contain them. This is 13 mol% when silver iodochloride is precipitated.
(Preferably 6 mol%) higher iodide-only levels,
Levels of iodide higher than 40 mole% (preferably 30 mole%) in precipitating silver iodobromide, and proportionate intermediate of iodide in precipitating silver iodohalide containing bromide and chloride. Exclude levels. When depositing silver bromide or silver iodobromide during the growth step, the pBr in the dispersion
It is preferred to keep it in the range of 4.2, preferably 1.6-3.4. When depositing silver chloride, silver iodochloride, silver bromochloride or silver iodobromochloride during the growth step, it is preferred to maintain the pCl in the dispersion medium within the ranges described above when describing the nucleation step.

It was quite unexpectedly found that by including certain halides during grain growth, less than a 20% reduction in tabular grain thickness could be achieved. Surprisingly, the addition of bromide in the range of 0.05 to 15 mol%, preferably 1 to 10 mol%, based on silver, during the growth step, can be achieved under the same precipitation conditions in the absence of bromide ions. It was observed that relatively thin {100} tabular grains were made. Similarly, 0.00 on a silver basis during the growth process
It has been observed that the addition of iodide in the range of 1 to <1 mol% produces {100} tabular grains that are relatively thinner than can be achieved under the same precipitation conditions in the absence of iodide ions. Was done.

During the growth step, both the silver salt and the halide salt are preferably introduced into the dispersion medium. In other words, double jet precipitation is contemplated, if any, with the remaining halide salt or with the added iodide salt being introduced through a separate jet. The rate at which the silver and halide salts are introduced is adjusted to avoid renucleation-the formation of a new grain population. The addition rate adjustment to avoid renucleation is described in Wilgus German Offenlegungsschrift (OLS) No. 2,1
No. 07,118; Irie U.S. Pat.No. 3,650,757; Kurz U.S. Pat.No. 3,672,900; Saito U.S. Pat.No. 4,242,445; T
eitschied et al. European Patent Application No. 80102242 and Wey
"Growth Mechanism of AgBr Crystals in Gelatin Solution" (“Growth
Mechanism of AgBr Crystals in Gelatin Solutio
n "), Photographic Science and Engineering, Volume 21, 1
No., January / February, 1977, pages 14 et seq., Which are generally well known in the art.

In the simplest form of the invention, the nucleation and growth steps of the particle precipitation occur in the same reaction vessel. However, it is preferred to interrupt the particle precipitation, especially after the nucleation step is completed. Further, it is preferred that two separate reaction vessels be substituted for the single reaction vessel described above. The nucleation step of particle precipitation can be performed in an upstream reaction vessel (hereinafter, also referred to as a nucleation reaction vessel), and the dispersed particle nuclei can be formed in a downstream reaction vessel (hereinafter, also referred to as a growth reaction vessel) in which the step of growing particles precipitates. ).
In one arrangement of this type, U.S. Pat.
No. 3,790,386, U.S. Pat.No. 3,897,935 to Forster et al., Fin
As shown by US Pat. No. 4,147,551 to nicum et al. and US Pat. No. 4,171,224 to Verhille et al. A nucleation vessel can be used. In these arrangements, the contents of the growth reactor are recycled to the nucleation reactor.

Various parameters important for the regulation of particle formation and growth, such as pH, pAg, ripening, temperature and residence time in the present invention, must be independently controlled in separate nucleation and growth reaction vessels. It is intended to be able to. Recirculate some of the contents of the growth reactor to the nucleation reactor so that particle nucleation is completely independent of the particle growth occurring in the growth reactor downstream of the nucleation reactor should not do. A preferred arrangement for separating particle nucleation from the contents of a growth reaction vessel is disclosed in U.S. Pat.
No. 2, which also discloses useful features of ultrafiltration during particle growth, Urabe U.S. Pat. No. 4,879,208 and published European Patent Applications 326,852, 326,853.
Nos. 355,535 and 370,116; Ichizo published European Patent Application 0 368 275; Urabe et al. Published European Patent Application 0 374 954; and Onishi et al.
No. 172817 (1990).

The method of grain nucleation using iodide to create the crystal irregularities required for tabular grain formation is as described above, but another nucleation method has been devised and is described in the examples below. It is shown. This method also eliminates any requirement for the presence of iodide ions during nucleation to make tabular grains. Furthermore, these alternative methods are compatible with using iodide ions during nucleation. That is, these methods can be relied entirely on during nucleation for tabular grain formation or can be relied on with iodide ions during nucleation to make tabular grains. .

Rapid grain nucleation, including so-called dump nucleations, where significant levels of dispersing medium supersaturation with halide and silver ions are present in nucleation, accelerates the introduction of grain irregularities that can accommodate flatness. Was observed. Since nucleation occurs essentially immediately, the immediate departure from initial supersaturation to the preferred pCl range described above is completely constant with this approach.

It has also been observed that keeping the level of peptizer in the dispersion medium below 1% by weight during grain nucleation increases tabular grain formation. It is believed that agglomeration of grain nuclei pairs can be at least partially responsible for introducing crystalline irregularities that induce tabular grain formation. Limited flocculation can be promoted by not including a deflocculant in the dispersion medium or by first limiting the concentration of the deflocculant. U.S. Pat. No. 4,334,012 to Mignot shows particle nucleation in the absence of a peptizer by removing soluble salt reaction products to avoid nucleation. Since limited aggregation of particle nuclei is considered desirable, Mignot's active intervention to eliminate particle nucleation may be eliminated or mitigated. It is also contemplated to increase restricted particle aggregation by using one or more peptizers that exhibit reduced adhesion to the particle surface. For example, it is generally accepted that low methionine gelatins of the type disclosed by Maskasky II adsorb weakly to the particle surface than gelatins containing higher levels of methionine. A more moderate level of particle adsorption can be obtained with so-called "synthetic deflocculants", i.e. deflocculants produced from synthetic polymers. The maximum amount of deflocculant compatible with limited aggregation of particle nuclei is, of course, related to the strength of adsorption on the particle surface. Once grain nucleation is complete, shortly after the introduction of the silver salt, the peptizer levels can be raised to all convenient conventional levels for the remainder of the precipitation step.

The emulsions of the present invention include silver chloride, silver iodochloride emulsion, silver iodobromochloride emulsion and silver iodochlorobromide emulsion. 10 per mole of silver
^The dopant may be present in the grains at a concentration of ^-2 moles or less, typically less than ^10-4 moles per silver mole.
Compounds of metals such as copper, thallium, lead, mercury, bismuth, zinc, cadmium, rhenium and Group VIII metals (eg, iron, ruthenium, rhodium, palladium, osmium, iridium and platinum) may be present during particle precipitation. , Preferably during the growth phase of the precipitate. Modification of photographic properties is related to the level and location of the dopant within the grain. When the metal forms part of a coordination complex, such as a six-coordinate or four-coordinate complex, the ligand may be included within the particle, and the ligand may further affect photographic properties. obtain. Ligands such as halo, aquo, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl ligands are contemplated and may be expected to modify photographic properties.

Dopants and their addition are described in U.S. Pat.
195,432; Hochstetter U.S. Pat.No. 1,951,933; Tri
U.S. Pat.No. 2,448,060 to velli et al., U.S. Pat.No. 2,628,167 to Overman, U.S. Pat.
U.S. Pat.No. 3,287,136 to cBride, U.S. Pat.No. 3,488,709 to Sidebotham, U.S. Pat.
U.S. Pat.No. 3,687,676 to Spence et al., U.S. Pat.No. 3,761,267 to Gilman et al., U.S. Pat.
No. 3,890,154 to Ohkubo et al., U.S. Pat.No. 3,901,711 to Iwaosa et al., U.S. Pat.No. 4,173,483 to Habu et al.
U.S. Patent No. 4,269,927 to Atwell, U.S. Patent No. 4,835,093 to Janusonis et al., U.S. Patent No. 4,933,27 to McDugle et al.
Nos. 4,981,781 and 5,037,732, Keevert et al., U.S. Pat.No. 4,945,035, and Evans et al., U.S. Pat.
No. 024,931, the disclosures of which are incorporated herein by reference. For background on alternatives known in the art, attention has been paid to BHCa.
rroll, “Iridium Sensitization: Literature Review” (“Iridium
Sensitization: A Literature Review "), Photographic
Science and Engineering, Vol. 24, No. 6, November / December, 1980,
265-257, and published European Patent Application 0 264 288 to Grzeskowiak et al.

Conventional high chloride tabular grain emulsions with tabular grains linked by {111} are inherently unstable and the presence of morphological stabilizers to prevent the grains from reverting to nontabular form The present invention is particularly advantageous in providing high chloride (greater than 50 mol% chloride) tabular grain emulsions. Particularly preferred high chloride emulsions according to the invention are those which contain more than 70 mol% (optimally more than 90 mol%) chloride.

Although not essential to the practice of the present invention, another method that can be used to maximize the population of tabular grains having {100} major faces is to provide non- {100}
The purpose is to contain an agent capable of suppressing the appearance of the crystal plane of the particles. When used, the inhibitor may be active during particle nucleation, during particle growth or through precipitation.

Useful inhibitors under the intended conditions of precipitation are organic compounds containing a nitrogen atom with a resonance-stabilized π-pair of electrons. Resonance stabilization prevents protonation of the nitrogen atom under relatively acidic conditions of precipitation.

Aromatic resonance can be expected for the stabilization of the π-electron pair of the nitrogen atom. The nitrogen atom may be contained in an aromatic ring, such as an azole or azine ring, or the nitrogen atom may be a ring substituent on an aromatic ring.

In one preferred form, the inhibitor has the formula: Wherein Z represents the atoms necessary to complete a 5- or 6-membered aromatic ring structure, preferably formed by carbon and nitrogen ring atoms. Preferred aromatic rings are those containing one, two or three nitrogen atoms. Particularly contemplated ring structures include 2H-pyrrole, pyrrole, imidazole, pyrazole, 1,2,3-triazole, 1,2,4-triazole,
Includes 1,3,5-triazole, pyridine, pyrazine, pyrimidine and pyridazine.

When the stabilized nitrogen atom is a ring substituent, preferred compounds have the formula: Wherein Ar is an aromatic ring structure containing 5 to 14 carbon atoms, and R ¹ and R ² are independently hydrogen, Ar or any convenient aliphatic group, or together 5 or 6
To form a membered ring).

Ar is preferably a carbocyclic aromatic ring such as phenyl or naphthyl. Also, any of the above nitrogen and carbon containing aromatic rings may be attached to the nitrogen atom of Formula II via a ring carbon atom. In this example, the compound obtained has the formula I and
II Satisfy both. Any of a wide variety of aliphatic groups can be selected. The simplest intended aliphatic group is an alkyl group, preferably an alkyl group having 1 to 10 carbon atoms, most preferably an alkyl group having 1 to 6 carbon atoms. Any functional substituent of an alkyl group known to be compatible with silver halide precipitation may be present. It is also contemplated to use cycloaliphatic substituents that exhibit 5- or 6-membered rings such as cycloalkanes, cycloalkenes and aliphatic heterocycles such as those containing oxygen and / or nitrogen heteroatoms. Cyclopentyl, cyclohexyl, pyrrolidinyl, piperidinyl, furanyl and similar heterocycles are specifically contemplated.

The following are representative of compounds intended to satisfy Formulas I and / or II.

The selection of a preferred inhibitor and its useful concentration is obtained by the following selection method. The compounds contemplated for use as inhibitors are added to a silver chloride emulsion consisting essentially of cubic grains having an average grain edge length of 0.3 μm. This emulsion is 0.2M in sodium acetate, 2.1 p
It has Cl and has a pH at least one unit greater than the pKa of the compound under consideration. The emulsion is maintained at 75 ° C. for 24 hours with inhibitors present. In a microscopic examination after 24 hours, if the cubic particles have a sharper {100} crystal face edge than the control differing only in the point lacking the considered compound, the compound introduced is It acts as an inhibitor. The meaning of the sharper edge of the {100} crystal plane intersection lies in the fact that the particle edge is the most active site on the particle for ions re-entering the dispersion medium. By retaining sharp edges, the inhibitor acts to suppress the appearance of non- {100} crystal faces, such as those present at rounded edges and corners. In some instances, instead of dissolved silver chloride which deposits exclusively on the edges of cubic grains, a new population of grains bound by {100} crystal faces is formed. Optimum inhibitor activity occurs when the new grain population is a tabular grain population in which tabular grains are bound by {100} major crystal faces.

It is specifically contemplated to deposit the silver salt epitaxically on the tabular grains acting as hosts. Conventional epitaxy deposition on high chloride silver halide grains
asky U.S. Patent No. 4,435,501 (especially Example 24B); Ogawa et al. U.S. Patent Nos. 4,786,588 and 4,791,053;
U.S. Patent Nos. 4,820,624 and 4,865,962; Sugi
moto and Miyake, “Mechanism of Br ^- ion-converted colloidal AgCl microcrystal halides”
Halide conversion Process of Colloidal AgCl Micro
crystals by Br ^- Ions "), Part I and Part II, Journal
of Colloid and Interface Science, Vol. 140, No. 2, 1990
February, pp. 335-361, Houle et al., U.S. Patent No. 5,035,992 and JP-A-3-252649 (priority date:
51165 Japan) and JP-A-3-288143 (priority date 199)
0.04.04-JP 089380 Japan). The disclosures of the aforementioned U.S. patents are incorporated herein by reference.

The emulsion used in the present invention is described in TH James, "Theory of the Photographic Processes".
s) ", 4th edition, Macmillan, 1977, pp. 67-76, or as described in Research Disclosur.
e, Volume 120, April 1974, Item 12008, Research Disclosure,
134, June 1975, Item 13452, U.S. Pat.
No. 1,623,499; Matthies et al., U.S. Pat.No. 1,673,522, Wa
U.S. Pat.No. 2,399,083 to Lller et al., U.S. Pat.No. 2,642,361 to Damschroder et al., U.S. Pat.No. 3,297,447 to McVeigh.
U.S. Patent No. 3,297,446 to Dunn; British Patent No. 1,315,755 to McBride; U.S. Patent No. 3,772,031 to Berry et al., Gil
U.S. Pat.No. 3,761,267 to Man et al .; U.S. Pat.
No. 57,711; Klinger et al., U.S. Pat.No. 3,565,633; Ofteda
hl U.S. Pat.Nos. 3,901,714 and 3,904,415 and
30-80 ° C. at a pAg level of 5-10 and a pH level of 5-8, as shown in Simons UK Patent 1,396,696.
Can be chemically sensitized with sulfur, selenium, tellurium, gold, platinum, palladium, iridium, osmium, rhenium or phosphorus sensitizers or a combination of these sensitizers. U.S. Patent No. to Damschroder
U.S. Pat.No. 2,521,926 to Lowe et al., U.S. Pat.No. 3,021,215 to Williams et al. And U.S. Pat.
Thioether compounds as disclosed in US Pat.
tes U.S. Pat.No. 3,411,914; Kuwabara et al. U.S. Pat.
U.S. Pat.No. 3,565,631 to Oguchi et al. And Of
azaindene, azapyridazine and azapyrimidine as described in tedahl U.S. Pat.No. 3,901,714;
Miyoshi et al. European Patent Application EP 294,149 and Tanak
The reaction is carried out in the presence of elemental sulfur as described in EP 297,804 of EP a, et al., and thiosulfonates as described in EP 293,917 of Nishikawa et al. Additionally or alternatively,
Emulsions can be treated with hydrogen, low pAg (eg, below 5), high pH (eg, above 8) with hydrogen as shown, for example, in Janusonis US Pat. No. 3,891,446 and Babcock et al. US Pat. No. 3,984,249. Or US Patent No.
No. 2,983,609, Oftedahl et al., Research Disclosure, 136
Volume, August 1975, Item 13654, U.S. Patent No. 2,518,6 to Lowe et al.
Nos. 98 and 2,739,060; Roberts et al., U.S. Pat.
U.S. Patent Nos. 3,182 and 2,743,183 to Chambers et al.
Reduction sensitization can be achieved using reducing agents such as stannous chloride, thiourea dioxide, polyamines and amine boranes as shown in 3,026,203 and U.S. Pat. No. 3,361,564 to Bigelow et al.

Chemical sensitization is described in US Pat. No. 3,628,960 to Philippaerts et al.
U.S. Pat.No. 4,439,520 to Kofron et al., U.S. Pat.No. 4,520,098 to Dickerson, U.S. Pat.
No. 4,693,965 to Ihama et al. And US Pat. No. 4,791,053 to Ogawa, in the presence of spectral sensitizing dyes. Chemical sensitization is directed to specific sites or crystallographic planes of the silver halide grains as described in Haugh et al., British Patent Application 2,038,792A and Mifune et al., Published European Patent Application EP 302,528. Good. The sensitivity centers obtained from chemical sensitization are described in Morgan U.S. Pat. No. 3,917,485, Becker U.S. Pat. No. 3,966,476 and Research Disclosure, Vol. 181, May 1979, Item 1815.
Partially or totally by precipitation of an additional layer of silver halide using means such as twin-jet addition or pAg circulation with alternating addition of silver and halide salts, as described in 5. May be occupied by Also, as described in Morgan, cited above, the chemical sensitizer can be added before or simultaneously with the additional silver halide formation. Chemical sensitization may occur during or after halide conversion as described in Hasebe et al., European Patent Application EP 273,404. In many instances, the epitaxy deposition on selected tabular grain sites (eg, edges or corners) is directed to chemical sensitization or to perform functions normally performed by chemical sensitization itself. Can be used for either.

The emulsion can be spectrally sensitized with dyes from various types, including polymethine dye types, which include cyanines, merocyanines, complex cyanines and merocyanines (i.e., tri-, tetra- and Polynuclear cyanines and merocyanines), styryls, merostyryls, streptocyanins, hemocyanins, arylidenes, allopolar cyanins
es) and enamine cyanines.

Cyanine spectral sensitizing dyes include quinolinium, pyridinium, isoquinolinium, 3H-indolium, benzoindolium, oxazolium, thiazolium, selenazolinium, imidazolium, benzoxazolium, benzothiazolium, benzoselenazolium, benzo Derived from terrazolium, benzimidazolium, naphthoxazolium, naphthothiazolium, naphthoselenazolium, naphthotellazolium, thiazolinium, dihydronaphthothiazolium, pyrylium and imidazopyrazinium quaternary salts And two basic heterocyclic nuclei linked by a methine bond.

The merocyanine spectral sensitizing dye includes one cyanine dye type basic heterocyclic nucleus bonded by a methine bond,
Barbituric acid, 2-thiobarbituric acid, rhodanine, hydantoin, 2-thiohydantoin, 4-thiohydantoin, 2-pyrazolin-5-one, 2-isoxazolin-5-one, indan-1,3-dione, cyclohexane -1,3-dione, 1.3-dioxane-4,6-dione, pyrazoline-3,5-dione, pentane-2,4-dione, alkylsulfonylacetonitrile, benzoylacetonitrile, malononitrile, malonamide, isoquinolin-4-one, Chroman-2,4-dione, 5H-furan-2-one, 5H-3-pyrrolin-2-one, 1,1,3-
Acidic nuclei, such as can be derived from tricyanopropene and telluracyclohexanedione.

One or more spectral sensitizing dyes can be used. Dyes are known which have a sensitizing maximum at wavelengths throughout the visible and infrared spectra and have a great variety of spectral sensitization curve shapes. The choice and relative ratio of dyes will depend on the region of the spectrum where photosensitivity is desired and the shape of the desired spectral sensitization curve. Dyes with overlapping spectral sensitization curves
Often the combination will result in a curve in which the sensitivities at each wavelength within the region of overlap are approximately equal to the sum of the sensitivities of the individual dyes. That is, in order to obtain a spectral sensitization curve having an intermediate maximum value with respect to the sensitization maximum value of each dye, it is possible to use a combination of dyes having different maximum values.

Supersensitization-that is, a combination of spectral sensitizing dyes that result in a spectral sensitization that is greater than that resulting from the additional effect of the dye, or from all concentrations of one dye alone in some spectral region. Can be used. Supersensitization is a spectral sensitizing dye, a stabilizer and an antifoggant, a development accelerator or an inhibitor,
It can be achieved in selected combinations with other additives such as coating aids, optical brighteners and antistatic agents. One of several mechanisms and compounds that can cause supersensitization is described by Gilman in Photographic Science and E
ngineering, 18, 1974, pp. 418-430.

Spectral sensitizing dyes can also affect emulsions in other ways. For example, spectral sensitizing dyes can increase photographic sensitivity within the spectral region of intrinsic photosensitivity.
Brooker et al. U.S. Pat.No. 2,131,038; Illingswoth et al. U.S. Pat.No. 3,501,310; Webster et al. U.S. Pat.
As disclosed in U.S. Pat.No. 3,718,470 to Spence et al. And U.S. Pat.No. 3,930,860 to Shiba et al. It can also function as an agent or nucleating agent and a halogen acceptor or electron acceptor.

Particularly useful spectral sensitizing dyes for sensitizing the emulsions described herein are British Patent No. 742,112, Brooker U.S. Patent Nos. 1,846,300, 1,846,301, 1,846,
No. 302, No. 1,846,303, No. 1,846,304, No. 2,07
8,233 and 2,089,729, Brooker et al., U.S. Pat.
No. 2,165,338, No. 2,213,238, No. 2,493,747, No. 2,493,748, No. 2,526,632, No. 2,739,964 (Reissue No. 24,292), No. 2,778,823, No. 2,917,5
No. 16, No. 3,352,857, No. 3,411,916 and No. 3,43
No. 1,111; Sprague U.S. Pat.No. 2,503,776; Nys et al. U.S. Pat.No. 3,282,933; Riester U.S. Pat.
U.S. Pat.No. 3,660,103 to Kampfer et al .; U.S. Pat.Nos. 3,335,010, 3,352,680 and 3,384, Taber et al.
No. 486, Lincoln et al., U.S. Pat.No. 3,397,981, Fumia et al., U.S. Pat.Nos. 3,482,978 and 3,623,881, Spence et al., U.S. Pat.
No. 349 (the disclosures of which are incorporated herein by reference)
It is described in. Examples of useful supersensitizing dye combinations, non-light absorbing additives that function as supersensitizers, or useful dye combinations are described in McFall et al., U.S. Pat.
No. 3,390; Jones et al., U.S. Pat.No. 2,937,089; Motter U.S. Pat.No. 3,506,443; and Schwan et al., U.S. Pat.
No. 2,898, the disclosures of which are incorporated herein by reference.

The spectral sensitizing dye may be added at any stage during emulsion preparation. These are Wall, Photographic Emulsions, Americ
an Photographic Publishing Co., Boston, 1929, p. 65,
Hill U.S. Pat.No. 2,735,766, Philippaerts et al. U.S. Pat.No. 3,628,960, Locker U.S. Pat.No. 4,183,756,
Locker et al., U.S. Pat.No. 4,225,666, Research Disclosu
re, vol. 181, May 1979, Item 18155 and published European patent application EP 301,508 by Tani et al.
It can be added at the beginning or during the precipitation. These are U.S. Pat.No. 4,439,520 to Kofron et al., U.S. Pat.No. 4,520,098 to Dickerson, and U.S. Pat.
Can be added prior to or during chemical sensitization, as described in US Pat. These can be added before or during emulsion washing as described in Asami et al., Published European Patent Application EP 287,100 and Metoki et al., Published European Patent Application EP 291,399. This dye is disclosed in U.S. Pat.No. 2,912,343 to Collins et al.
It can be mixed immediately before application as described in the item. As described by Dickerson cited above, a small amount of iodide can be adsorbed on the emulsion grains to promote aggregation and adsorption of the spectral sensitizing dye. Dicker
As described by son, post-processing dye stain can be reduced by the proximity of fine high iodide grains to the dyed emulsion layer. Depending on their solubility, the spectral sensitizing dyes may be water or methanol, ethanol, acetone or pyridine dissolved in a surfactant solution as described in Sakai et al., U.S. Pat.No. 3,822,135. As a solution in a suitable solvent or in Uwens et al., U.S. Pat.
As described in JP-A-46-24185 and JP-A-46-24185. As described in Mifune et al., Published European Patent Application EP 302,528, this dye selectively adsorbs to specific crystallographic faces of emulsion grains as a means of suppressing chemical sensitization centers to other faces. Can be done. As described in Miyasaka et al., Published European Patent Applications 270,079, 270,082 and 278,510, spectral sensitizing dyes can be used with less adsorbed luminescent dyes.

The following illustrates a particular spectral sensitizing dye selection.

SS-1 Anhydro-5'-chloro-3'-di- (3-sulfopropyl) naphtho [1,2-d] thiazolothiocyanin hydroxide, sodium salt SS-2 Anhydro-5'-chloro-3 ' -Di- (3-sulfopropyl) naphtho [1,2-d] oxazolothiocyanine
Hydroxide, sodium salt SS-3 Anhydro-4,5-benzo-3'-methyl-4'-phenyl-1- (3-sulfopropyl) naphtho [1,2-d]
Thiazolotiathiazocyanine hydroxide SS-4 1,1'-Diethylnaphtho [1,2-d] thiazolo-2'-cyanine bromide SS-5 Anhydro-1,1'-dimethyl-5,5'-di- (Trifluoromethyl) -3- (4-fluphobutyl) -3 ′-(2,
2,2-trifluoroethyl) benzimidazolocarbocyanine hydroxide SS-6 anhydro-3,3 '-(2-methoxyethyl) -5,5'-
Diphenyl-9-ethyloxacarbocyanine, sodium salt SS-7 Anhydro-11-ethyl-1,1'-di- (3-sulfopropyl) naphtho [1,2-d] oxazolocarbocyanine hydroxide, sodium salt SS-8 Anhydro-5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxaselenacarbocyanine hydroxide, sodium salt SS-9 5,6-dichloro-3 ', 3'-dimethyl-1,1 ', 3-triethylbenzimidazolo-3H-indolocarbocyanine
Bromide SS-10 Anhydro-5,6-dichloro-1,1-diethyl-3- (3
-Sulfopropyl) benzimidazolooxacarbocyanine hydroxide SS-11 anhydro-5,5'-dichloro-9-ethyl-3,3'-di- (2-sulfoethylcarbamoylmethyl) thiacarbocyanine hydroxide, sodium Salt SS-12 Anhydro-5 ', 6'-dimethoxy-9-ethyl-5
Phenyl-3- (3-sulfobutyl) -3 '-(3-sulfopropyl) oxathiacarbocyanine hydroxide, sodium salt SS-13 Anhydro-5,5'-dichloro-9-ethyl-3- (3
-Phosphonopropyl) -3 '-(3-sulfopropyl)
Thiacarbocyanine hydroxide SS-14 Anhydro-3,3'-di- (2-carboxyethyl)-
5,5'-Dichloro-9-ethylthiacarbocyanine bromide SS-15 Anhydro-5,5'-dichloro-3- (2-carboxyethyl) -3 '-(3-sulfopropyl) thiacyanine sodium salt SS-16 9- (5-barbituric acid) -3,5-dimethyl-3'-
Ethyl telluria carbocyanine bromide SS-17 anhydro-5,6-methylenedioxy-9-ethyl-3
-Methyl-3 '-(3-sulfopropyl) tellurachiacarbocyanine hydroxide SS-18 3-Ethyl-6,6'-dimethyl-3'-pentyl-9,11
-Neopentylene lentiazicarbocyanine bromide SS-19 anhydro-3-ethyl-9,11-neopenthylene-3 '
-(3-sulfopropyl) thiazicarbocyanine hydroxide SS-20 anhydro-3-ethyl-11,13-neopenthylene-
3 '-(3-Sulfopropyl) oxathiatricarbocyanine hydroxide, sodium salt SS-21 Anhydro-5-chloro-9-ethyl-5'-phenyl-3'-(3-fluphobutyl) -3- (3 -Sulfopropyl) oxacarbocyanine hydroxide, sodium salt SS-22 Anhydro-5,5'-diphenyl-3,3'-di- (3-sulfobutyl) -9-ethyloxacarbocyanine hydroxide, sodium salt SS- 23 Anhydro-5,5'-dichloro-3,3'-di- (3-sulfopropyl) -9-ethylthiacarbocyanine hydroxide, triethylammonium salt SS-24 Anhydro-5,5'-dimethyl-3, 3'-di- (3-sulfopropyl) -9-ethylthiacarbocyanine hydroxide, sodium salt SS-25 anhydro-5,6-dichloro-1-ethyl 3- (3-
Sulfobutyl) -1 '-(3-sulfopropyl) benzimidazolonaphtho [1,2-d] thiazolcarbocyanine hydroxide, triethylammonium salt SS-26 anhydro-11-ethyl-1,1'-di- (3-sulfopropyl) naphtho [1,2-d] oxazolocarbocyanine hydroxide, sodium salt SS-27 anhydro-3,9-diethyl-3'-methylsulfonylcarbamoylmethyl-5-phenyloxathiacarbocyanine p -Toluenesulfonate SS-28 Anhydro-6,6'-dichloro-1,1'-diethyl-3,
3'-di- (3-sulfopropyl) -5,5'-bis (trifluoromethyl) benzimidazolocarbocyanine hydroxide, sodium salt SS-29 anhydro-5'-chloro-5-phenyl-3,3 '-Di- (3-sulfopropyl) oxathiocyanine hydroxide, sodium salt SS-30 Anhydro-5,5'-dichloro-3,3'-di- (3-sulfopropyl) thiocyanine hydroxide, sodium salt SS -31 3-ethyl-5- [1,4-dihydro-1- (4-sulfobutyl) pyridine-4-ylidene] rhodanine, triethylammonium salt SS-32 1-carboxyethyl-5- [2- (3-ethyl Benzoxazoline-2-ylidene) ethylidene] -3-phenylthiohydantoin SS-33 4- [2-((1,4-dihydro-1-dodecylpyridine-ylidene) ethyl) Den] -3-phenyl-2-isoxazolin-5-one SS-34 5- (3-ethylbenzoxazolin-2-ylidene)-
3-phenylrhodanine SS-35 1,3-diethyl-5-{[1-ethyl-3- (3-sulfopropyl) benzimidazoline-2-ylidene] ethylidene} -2-thiobarbituric acid SS-365 -[2- (3-ethylbenzoxazoline-2-ylidene) ethylidene] -1-methyl-2-dimethylamino-
4-oxo-3-phenylimidazolinium-p-toluenesulfonate SS-37 5- [2- (5-carboxy-3-methylbenzoxazoline-2-ylidene) ethylidene] -3-cyano-4-
Phenyl-1- (4-methylsulfonamido-3-pyrrolin-5-one SS-38 2- [4- (hexylsulfonamido) benzoylcyanomethine] -2- {2-} 3- (2-methoxyethyl)
-5-[(2-methoxyethyl) sulfonamido] benzoxazoline-2-ylidene {ethylidene} acetonitrile SS-39 3-methyl-4- [2- (3-ethyl-5,6-dimethylbenzotellrazolin-2- Ilidene) ethylidene] -1
-Phenyl-2-pyrazolin-5-one SS-40 3-heptyl-1-phenyl-5- {4- [3- (3-
Sulfobutyl) -naphtho [1,2-d] thiazoline] -2
-Butenylidene} -2-thiohydantoin SS-41 1,4-phenylene-bis (2-aminovinyl-3-methyl-2-thiazolinium) dichloride SS-42 anhydro-4- {2- [3- (3-sulfo Propyl)
Thiazoline-2-ylidene] ethylidene {-2-} 3-
[3- (3-sulfopropyl) thiazoline-2-ylidene] propenyl-5-oxazolium hydroxide,
Sodium salt SS-43 3-carboxymethyl-5- {3-carboxymethyl-
4-oxo-5-methyl-1,3,4-thiadiazoline-2
-Ylidene) ethylidene] thiazoline-2-ylidene｝
Rhodanin, dipotassium salt SS-44 1,3-Diethyl-5- [1-methyl-2- (3,5-dimethylbenzotellrazolin-2-ylidene) ethylidene]-
2-thiobarbituric acid SS-45 3-methyl-4- [2- (3-ethyl-5,6-dimethylbenzotellrazolin-2-ylidene) -1-methylethylidene] -1-phenyl-2-pyrazoline -5-one SS-46 1,3-diethyl-5- [1-ethyl-2- (3-ethyl-5,6-dimethoxybenzotellrazolin-2-ylidene) ethylidene] -2-thiobarbituric acid SS -47 3-ethyl-5-{[(ethylbenzothiazoline-2-
Ylidene) -methyl]-[(1,5-dimethylnaphtho [1,2
-D] selenazoline-2-ylidene) methyl] methylene} rhodanine SS-48 5- {bis [(3-ethyl-5,6-dimethylbenzothiazoline-2-ylidene) methyl] methylene} -1,3-diethyl- Barbituric acid SS-49 3-Ethyl-5-{[(3-ethyl-5-methylbenzotellrazolin-2-ylidene) methyl] [1-ethylnaphtho [1,2-d] -tellrazolin-2-ylidene) Methyl] methylene｝ rhodanine SS-50 Anhydro-5,5'-diphenyl-3,3'-di- (3-sulfopropyl) thocyanine hydroxide, triethylammonium salt SS-51 Anhydro-5-chloro-5'-phenyl -3,3'-di- (3-sulfopropyl) thiacyanine hydroxide, triethylammonium salt A negative emulsion that does not increase the minimum density (i.e., fog) of the emulsion coating. Qualitative include stabilizers, antifoggants, kink inhibitor (antikinking agent), by incorporating in the emulsion and contiguous layers prior to applying the latent image stabilizers and similar additives,
Can be protected. CEKMees, The Theory of the Photographic Process, 2
As shown in the edition, Macmillan, 1954, pp. 677-680, most of the antifoggants effective in the emulsions used in this invention can also be used in developers, Can be categorized by a general subject.

To avoid such instability in emulsion coatings, halide ions (eg, bromide salts), chloropalladates and chloroparadite as shown in US Pat. No. 2,566,263 to Trivelli et al. (Chloropalladites), water-soluble inorganic salts of magnesium, calcium, cadmium, cobalt, manganese and zinc as shown in Jones U.S. Pat. No. 2,839,405 and Sidebotham U.S. Pat. No. 3,488,709; U.S. Pat. Mercury salt, Bro, as indicated in the issue
selenols and diselenides as shown in UK Patent No. 1,336,570 to Wn et al. and British Patent No. 1,282,303 to Pollet et al .; U.S. Patent No. 2,694,716 to Allen et al., Brooke
et al., U.S. Pat.No. 2,131,038; Graham U.S. Pat.
Quaternary ammonium salts as shown in U.S. Patent 3,954,478 to Arai et al., Azomethine desensitizing dyes as shown in U.S. Patent 3,630,744 to Thiers et al., U.S. Patent No. Isothiourea as shown in U.S. Pat.No. 2,220,839 and U.S. Pat.No. 2,514,650 to Knott et al., Thiazolidine as shown in U.S. Pat.No. 3,565,625 to Scavron, as shown in U.S. Pat. Peptide derivatives, pyrimidine and 3-pyrazolidone, Ba as shown in Welsh U.S. Pat.No. 3,161,515 and Hood et al. U.S. Pat.No. 2,751,297.
Azotriazole and azotetrazole, as shown in U.S. Pat. No. 3,925,086 to ldassarri et al., Heimbach
U.S. Pat.No. 2,444,605; Knott U.S. Pat.
No. 8, Williams U.S. Pat.No. 3,202,512, Research Dis
closure, Volume 134, June 1975, Item 13452 and 148, 1976
August 1980, Item 14851 and UK Patent 1,338,567 to Nepker et al.
Azaindenes, especially tetraazaindene, as shown in U.S. Pat. No. 2,403,927 to Kendall et al., Kennar
d et al., U.S. Pat.No. 3,266,897, Research Disclosure, 11
Volume 6, December 1973, Item 11684, U.S. Pat.
No. 3,987,303 and Mercaptotetrazole, mercaptotriazole and mercaptodiazole as shown in U.S. Pat.No. 3,708,303 to Salesin, U.S. Pat.No. 2,271,229 to Peterson et al. And Research Disclosur cited above.
e, Azole as shown in Item 11684, Sheppard
U.S. Pat.No. 2,319,090; Birr et al. U.S. Pat.
No. 2,460, Research Disclosure, Item 13452 cited above
Purines, as shown in French Patent No. 2,296,204 to Dostes et al .; 1,3-dihydroxy (and / or 1,3-dihydroxy) as shown in US Patent No. 3,926,635 to Saleck et al.
Carbamoxy) -2-methylenepropane polymer, Gu
Tellurazole, tellurazoline, tellrazolinium salts and tellrazolium salts as shown in U.S. Pat.No. 4,661,438 to nther et al. and U.S. Pat.
Stabilizers and antifoggants can be used, such as aromatic oxatellazidinium salts as shown in US Pat. Nos. 4,661,438 and 4,677,202 to Przyklek-Elling et al. High chloride emulsions are disclosed in Miyoshi et al., Published European Patent Application EP 294,149, especially during chemical sensitization.
And the presence of elemental sulfur as described in EP 297,804 of Tanaka et al. And EP 293,917 and thiosulfonates as described in EP 293,917 of Nishikawa et al. Can be done.

A particularly useful stabilizer for gold sensitized emulsions is Yutzy
U.S. Patent No.
Sulfinamide as shown in No. 2.

Particularly useful stabilizers in layers containing poly (alkylene oxide) are described in US Pat. No. 2,716,062 to Carroll et al.
No. 1,466,024 and U.S. Pat.
Tetraazaindene or resorcinol derivatives, especially in combination with Group VIII noble metals, as shown in 29,486, quaternary ammonium salts of the type shown in Piper U.S. Pat.No. 2,886,437, Maffet U.S. Pat. 45
Smith, a water-insoluble hydroxide as shown in No. 5
Phenols as shown in U.S. Pat.Nos. 2,955,037 and 2,955,038; Dersch U.S. Pat.
Ethylenediurea as shown in US Pat. No. 6, Barbituric acid derivatives as shown in U.S. Pat.No. 3,617,290 to Wood; borane as shown in U.S. Pat. 3-pyrazolidinones as shown in patent 1,158,059 and aldoximines, amides, anilides and esters as shown in Butler et al., UK Patent 988,052.

This emulsion is a sulfocatechol type compound, such as Carroll, as shown in US Pat. No. 3,236,652 to Kennard et al.
Aldoximin as shown in British Patent No. 623,448 and additives such as meta- and polyphosphates as shown in U.S. Pat.No. 2,239,284 to Draisbach and British Patent No. The inclusion of ethylenediaminetetraacetic acid as described above can protect against fog and desensitization caused by trace amounts of metals such as copper, lead, tin, iron and the like.

Particularly useful stabilizers in layers containing synthetic polymers of the type used as vehicles and for improving covering power are mono- and polyhydric phenols such as those shown in Forsgard U.S. Pat.No. 3,043,697. , UK Patent 897,
No. 497 and the sugars as shown in Stevens et al., British Patent 1,039,471 and Dersch et al., U.S. Pat.
No. 8 quinoline derivatives.

Particularly useful stabilizers in protecting the emulsion layer against bicolor fog are the salts of nitrones, such as those shown in Barbier et al., U.S. Patent Nos. 3,679,424 and 3,820,998, W
Mercaptocarboxylic acid as shown in U.S. Pat. No. 3,600,178 to Illems et al. and EJBirr, "Stabilization of Photographic Silver Emulsion.
c Silver Halide Emulsion "), Focal Press, London, 1974, pp. 126-218.

Particularly useful stabilizers in protecting the emulsion layer against development fog are Bloom et al., British Patent No. 1,356,142 and U.S. Pat.No. 3,575,699; Rogers, U.S. Pat. Azabenzimidazoles as shown in Brooker et al., U.S. Pat.No. 2,131,038; Land, U.S. Pat.
Substituted benzimidazole, benzothiazole, benzotriazole, etc. as shown in U.S. Pat.
U.S. Pat.No. 3,081,170 to Weyerts et al., U.S. Pat.
U.S. Pat.Nos. 3,674,478 and A.
mercapto-substituted compounds such as those shown in Rond U.S. Pat.No. 3,706,557, such as mercaptotetrazole,
Isothiourea derivatives as shown in U.S. Pat.No. 3,220,839 to Herz et al., And U.S. Pat.
64,028 and von Konig et al., GB 1,186,441.

When an aldehyde-type hardener is used, the emulsion is Shep
Monohydric and polyhydric phenols of the type shown in U.S. Pat.No. 2,165,421 to Pard et al., British Patent 1,269,26 to Rees et al.
Valbusa, a nitro-substituted compound of the type disclosed in No. 8.
Poly (alkylene oxides) as shown in U.S. Pat. No. 1,151,914 to U.S. Pat.
U.S. Pat.Nos. 3,397,064 to Rees et al. In combination with urazole as shown in U.S. Pat.
It can be protected with an antifoggant such as mucohalic acid in combination with maleic hydrazide as shown in US Pat. No. 295,980.

To protect the emulsion layer coated on a linear polyester support, paravanic acid, hydantoic hydrazide and urazole as shown in U.S. Pat.No. 3,287,135 to Anderson et al. And U.S. Pat.
Additives such as piazines containing two symmetrically fused six-membered carbocycles can be used, such as those indicated in US Pat.

The kink desensitization of the emulsion is described in Overman, U.S. Pat.
Thallium nitrate as shown in US Pat. Nos. 2,759,821 and 2,759,822 to Jones et al., Polymer latexes and dispersions, Rese
azole and mercaptotetrazole hydrophilic colloidal dispersions of the type disclosed in arch Disclosure, Vol. 116, December 1973, Item 11684, Milton et al., U.S. Patent No. 3,033,68.
No. 0, a plasticized gelatin composition of the type disclosed in Ree.
emulsion polymerization in the presence of a water-soluble interpolymer of the type disclosed in U.S. Pat. No. 3,536,491 of U.S. Pat. No. 3,536,491, and poly (alkylene oxide) as disclosed in U.S. Pat. No. 3,772,032 of Pearson et al. Latex and Rakoczy U.S. Pat.
It can be reduced by including a gelatin graft copolymer of the type disclosed in U.S. Pat.

If the color photographic elements of the present invention must be processed at elevated bath or drying temperatures, pressure desensitization and / or increased fog may result from Abbott et al., US Pat. No. 3,295,976.
U.S. Pat.No. 3,545,971 to Barnes et al., U.S. Pat.No. 3,708,303 to Salein, U.S. Pat.No. 3,615,619 to Yamamoto et al.
U.S. Pat.No. 3,623,873 to Brown et al., U.S. Pat.No. 3,671,258 to Taber, U.S. Pat.
earch Disclosure, Volume 99, July 1972, Item 9930, Florens
U.S. Pat.No. 3,843,364; Priem et al. U.S. Pat.
No. 7,152, U.S. Pat.No. 3,967,965 to Adachi et al. And Mika
As shown in U.S. Pat. Nos. 3,947,274 and 3,954,474 to Wa et al., they can be controlled by a selected combination of additives, vehicles, hardeners and / or processing conditions.

In addition to raising the pH or lowering the pAg of the emulsion and adding gelatin, which are known to delay latent image regression, Ezekiel GB 1,335,923, U.S. Pat.
Nos. 1,378,354, 1,387,654 and 1,391,672, E
British Patent 1,394,371 to zekiel et al., U.S. Patent 3,843,372 to Jefferson, British Patent 1,412,294 to Jefferson et al.
Amino acids as shown in U.S. Pat.No. 3,343,904 to Thurston and U.S. Pat.
Carbonyl-bisulfite addition product in combination with hydroxybenzene or an aromatic amine developing agent as shown in U.S. Pat.No. 3,447,926 to Beckett et al., US Pat. A catalase-type enzyme as shown in U.S. Pat.No. 3,600,182 to Matejec et al .; a halogen-substituted hardener in combination with certain cyanine dyes as shown in U.S. Pat.No. 3,881,933 to Kumai et al. Hydrazide, as shown in Honig et al., U.S. Pat.
Alkenyl benzothiazolium salts, such as those shown in U.S. Patent No. 954,478, Thurston UK Patent 1,308,777 and Eze
hydroxy-substituted benzylidene derivatives as shown in kiel et al., British Patent Nos. 1,347,544 and 1,353,527; mercapto-substituted compounds of the type disclosed in Sutherns U.S. Pat.No. 3,519,427; Matejec et al. U.S. Pat. Metal-organic complexes of the type disclosed in U.S. Pat. No. 3,389,089 to Ezekiel, penicillin derivatives as shown in U.S. Pat.
U.S. Pat.No. 3,881,939; propynylthio derivatives such as benzimidazole and pyrimidine as shown in U.S. Pat.No. 0,791; combinations of iridium and rhodium compounds as disclosed in U.S. Pat. And thiazolidine derivatives as shown in British Patent No. 1,458,197 to Ezekiel, as well as Research Discl.
osure, Vol. 136, August 1975, Item 13651, may contain a latent image stabilizer such as a thioether substituted imidazole.

Apart from the features particularly described above for tabular grain emulsion making methods and tabular grains made by this method, their further use in the color photographic elements of the present invention may take any convenient conventional form. Good. It is generally contemplated to replace conventional emulsions with the same or similar silver halide compositions in color photographic elements, replacing the silver halide emulsions with different silver halide compositions, especially other tabular grain emulsions. It is also feasible. The low level of native blue sensitivity of high chloride {100} tabular grain emulsions is attributed to U.S. Pat.No. 4,439,520 to Kofron et al. For both layer ordering and other conventional features of photographic elements containing tabular grain emulsions. The emulsion can be used in all desired layer order arrangements of the multicolor photographic element, including all layer order arrangements disclosed in the disclosure of which is incorporated herein by reference. Conventional features are further illustrated by the following disclosure, which is incorporated by reference.

ICBR-1 Research Disclosure, Volume 308, December 1989, I
tem 308, 119; ICBR-2 Research Disclosure, 225, January 1983, I
tem 22,534; ICBR-3 Wey et al., U.S. Patent No. 4,414,306, November 1983.
Issued on March 8; ICBR-4 Solberg et al., U.S. Pat. No. 4,433,048, 1984
Issued February 21, 1998; ICBR-5 Wilgus et al., U.S. Pat. No. 4,434,226, 1984.
Issued February 28, 1980; ICBR-6 Maskasky U.S. Pat. No. 4,435,501, 1984
Issued March 6, 1987; ICBR-7 Maskasky, U.S. Pat. No. 4,643,966, 1987
Issued February 17, 1998; ICBR-8 Daubendiek et al., US Pat. No. 4,672,027, 1
Issued January 9, 987; ICBR-9 Daubendiek et al., U.S. Pat. No. 4,693,964, 1
Published September 15, 987; ICBR-10 Maskasky U.S. Pat. No. 4,713,320, 1987
Published December 15, 2000; ICBR-11 Saitou et al., U.S. Patent No. 4,797,354, 1989.
Issued January 10, 2001; ICBR-12 Ikeda et al., U.S. Patent No. 4,806,461, issued February 21, 1989; ICBR-13 Makino et al., U.S. Patent No. 4,853,322, 1989.
Issued August 1, 1998; and ICBR-14 Daubendiek et al., US Pat. No. 4,914,014, 1
Issued April 3, 990; the following, as used herein, are simply referred to as "PUG releasing compounds", "dye image forming compounds" and "photographically useful group releasing compounds".
seful group-releasing compound) ".

The dye image-forming compound is typically a coupler compound, a dye redox releasing compound, a dye developing agent compound, an oxychrome developing agent compound or a bleaching dye or dye precursor compound. Image transfer processing
Dye redox emitters, dye developing agents and oxychrome developing agent compounds useful in color photographic elements that can be used in the photographic process are described in The Theory o.
f the Photographic Process), 4th edition, THJames
Ed., Macmillan, New York, 1977, Chapter 12, Section V, and
Kenneth Mason Publications, Ltd., Dudley Annex, 12a N
orth Street, Emsworth, Hampshire P010 7DQ, Research Disclosure, published by UK, December 1989, Item 30.
8119, Section XXIII. Dye compounds useful in color photographic elements used in dye bleaching are
It is described in "Theory of Photographic Processing", 4th Edition, Chapter 12, Section IV.

Preferred dye image-forming compounds are coupler compounds which react with oxidative color developing agents to form colored products or dyes. The coupler compound has a coupling unit, CO, which forms a dye structure by coupling with an oxidized developing agent by a coupling reaction.
UP is included. Further, the coupler compound may contain a group called a coupling-off group, which is bonded to the coupler unit by a bond that is cleaved upon reaction between the coupler compound and the oxidized color developing agent. The coupling off group may be a halogen such as chloro, bromo, fluoro and iodo or an organic group linked to the coupler unit by an atom such as oxygen, sulfur, nitrogen, phosphorus and the like.

A PUG releasing compound is a compound that contains a photographically useful group and that can react with an oxidized color developing agent to release the group.
Such PUG releasing compounds consist of a carrier unit and a leaving group, which are linked by a bond that cleaves upon reaction with the oxidized developing agent. Leaving groups include PUGs that may be present as preformed species or as protected species or precursor species that further react after cleavage of the leaving group from the carrier to form a PUG. The reaction of the oxidized developing agent with the PUG releasing compound produces a colored or colorless product.

The carrier unit (CAR) includes hydroquinones, catechols, aminophenols, sulfonamidophenols, sulfonamidonaphthols, hydrazides and the like which are cross-oxidized by an oxidized developing agent. A preferred carrier unit in the PUG-releasing compound is the coupler unit COUP, which can be combined with an oxidized color developing agent to form a colored species or dye in a cleavage reaction. Carrier unit is COUP
When, the leaving group is referred to as a coupling leaving group. As described above generally for leaving groups, coupling-off groups include PUG as a preformed species or as a protected or precursor species. The coupler units may be ballasted or non-ballasted. It may be a monomer, or may be part of a dimer, oligomer or polymer coupler if more than one group containing PUG is included in the coupler, or a PU
G may form part of a bis compound which forms part of the bond between the two coupler units.

The PUG can be any group typically made available in a photographic element in an image-like format. The PUG can be a photographic reagent or a photographic dye. Photographic reagents that further react with the components in the photographic element upon release as described herein include development inhibitors, development accelerators, bleach inhibitors, bleach accelerators, electron transfer agents, couplers (e.g., competitive Couplers, dye-forming couplers or development inhibitor releasing couplers), dye precursors, dyes, developing agents (eg, competing developing agents, dye-forming developing agents or silver halide developing agents), silver complexing agents, fixing agents, Components such as image toners, stabilizers, hardeners, tanning agents, fogging agents, UV absorbers, antifoggants, nucleating agents, chemical or spectral sensitizers or desensitizers.

The PUG may be present as a preformed species in the coupling off group, or may be present in protected form or as a precursor. For example, the PUG may be a preformed development inhibitor, or the development inhibitory function may be protected at the point of attachment to the carbonyl group attached to the PUG in the coupling-off group. Other examples are preformed dyes, dyes protected to shift their absorption, and leuco dyes.

The PUG releasing compound has the formula CAR- (TIME) _n -PUG (wherein
(TIME) is a bond or a time adjusting group, and n is 0, 1 or 2
And CAR reacts with PUG upon reaction with oxidized developing agent.
(When n is 0) or PUG precursor (TIME) ₁ -PUG or (TIME) ₂ -PUG (when n is 1 or 2) is a carrier unit that releases imagewise Can be. (TIME) ₁ -PUG or (TIME) ₂ -PUG
PUG is produced in the next reaction of.

A linking group (TIME), when present, is a group that undergoes base-catalyzed cleavage, including intramolecular nucleophilic substitution, such as an ester, carbamate, etc., thereby releasing PUG. When n is 2, (TIME) may be the same or different. Suitable groups, also known as time adjusting groups, are described in U.S. Pat.
No. 151,343, No. 5,051,345, No. 5,006,448, No.
No. 4,409,323, No. 4,248,962, No. 4,847,185, No. 4,857,440, No. 4,857,447, No. 4,861,701,
Nos. 5,021,322, 5,026,628 and 5,021,555
No. (all of which are incorporated herein by reference). Particularly useful linking groups are described in U.S. Pat.
No. 5,151,343 and 5,006,448, p-hydroxyphenylmethylene units and the o-hydroxyphenyl substituted carbamate groups disclosed in U.S. Pat.Nos. 5,151,343 and 5,021,555, These cyclize intramolecularly upon release of PUG.

When TIME is attached to COUP, it may be attached at any position where a group is released from the coupler by reaction with an oxidized color developing agent. Preferably, TIME is attached at the coupling position of the coupler unit, so that upon reaction of the coupler with the oxidized color developing agent, TIME will be released from the COUP along with the attached group.

The TIME may be at a non-coupling position of the coupler unit that may be displaced therefrom as a result of the reaction of the coupler with the oxidized color developing agent. When TIME is in the non-coupling position of the COUP, other groups, including conventional coupling-off groups, may be in the coupling position. It is also possible to use the same or different inhibitor units as described in the present invention. Further, the COUP may have TIME and PUG at the coupling position and the non-coupling position, respectively. Therefore,
Compounds useful in the present invention can release more than one mole of PUG per mole of coupler.

TIME can be any organic group that binds the CAR to the PUG unit and then cleaves from the CAR and then from the PUG unit. This cleavage is preferably carried out, for example, in U.S. Pat.
By intramolecular nucleophilic substitution reactions of the type described in U.S. Pat. No. 962 or by electron transfer along a conjugated chain as described, for example, in U.S. Pat. No. 4,409,323.

The term “intramolecular nucleophilic substitution reaction” used in the present invention refers to a reaction in which a nucleophilic center of a compound reacts directly or jointly via an intervening molecule with another site of the compound which is an electrophilic center. It refers to a reaction that causes substitution of a group or atom attached to an electron center. Such compounds have both nucleophilic and electrophilic groups that are spatially related and promote reactive proximity by the configuration of the molecule. Preferably, the nucleophilic and electrophilic groups are located in the compound such that the cyclic or transient cyclic organic ring is readily formed by an intramolecular reaction involving the nucleophilic and electrophilic centers. ing.

Useful time regulating groups have the structure: Nu-LINKE, wherein Nu is a nucleophilic group attached to a position on the CAR where it is displaced during the reaction of the CAR with the oxidized developing agent; E is an electrophilic group attached to the inhibitor unit as described above, from which Nu can be replaced by Nu after it has been replaced from CAR, LINK spatially associates Nu and E, N from CAR
is a linking group for performing an intramolecular nucleophilic substitution reaction with the formation of a 3- to 7-membered ring upon the substitution of u, thereby releasing a PUG unit.)

In this specification, a nucleophilic group (Nu) is defined as a group of atoms, one of which is electron-rich. Such an atom is called a nucleophilic center. In the present specification, the electrophilic group (E) is defined as a group of atoms, one of which is electron-deficient. Such an atom is called an electrophilic center.

That is, in the PUG releasing compounds described herein, the time adjusting group may include a nucleophilic group and an electrophilic group, which groups are spatially related to each other by a linking group. Thus, upon release from the CAR, the nucleophilic center and the electrophilic center react to cause displacement of the PUG unit from the timing moiety. The nucleophilic center must be protected from reacting with the electrophilic center until released from the CAR unit, and the electrophilic center must be resistant to external shocks, such as hydrolysis. The premature reaction occurs when the CAR unit is attached to the timing group at the nucleophilic center or atom in association with the nucleophilic center and cleavage of the timing group and the PUG unit from the CAR does not protect the nucleophilic center and the electrophilic center. Or by adjusting the nucleophilic and electrophilic groups to prevent them from being in reactive proximity until release. The time-adjusting group may include additional substituents such as additional photographically useful groups (PUGs) or precursors thereof, which may be released even if they remain attached to the time-adjusting group. You may.

In time-adjusting groups, because of the intramolecular reaction that occurs between the nucleophile and the electrophile, these groups must be spatially related after cleavage from the CAR so that they cannot react with each other. It will be appreciated that it must not. Preferably,
The nucleophile and the electrophile are spatially related within the time adjusting group such that the intramolecular nucleophilic substitution reaction involves the formation of a 3- to 7-membered ring, most preferably a 5- or 6-membered ring. It is.

In addition, due to the intramolecular reactions that occur in alkaline aqueous solutions encountered during photographic processing, thermodynamics suggests that the overall free energy reduction forms a bond between the nucleophilic and electrophilic groups upon ring closure. It will be appreciated that the bond should be such that it breaks the bond between the electrophilic group and the PUG, and the group should be so selected. All possible combinations of nucleophiles, linking groups and electrophiles are compatible with electrophiles and PUs.
It does not create an advantageous thermodynamic relationship to break the bond between the G units. However, it is within the skill of the art to select an appropriate combination taking into account the above energy relationships.

Representative Nu groups include electron-rich oxygen, sulfur and nitrogen atoms. Representative E groups include electron-deficient carbonyls,
It includes thiocarbonyl, phosphonyl and thiophosphonyl units. Other useful Nu and E groups will be apparent to those skilled in the art.

The linking group may be a ring such as an alkylene, for example, an acyclic group such as methylene, ethylene or propylene, or an aromatic group such as phenylene or naphthylene, or a heterocyclic group such as furan, thiophene, pyridine, quinoline or benzoxazine. It may be a formula group. Preferably, LINK is alkylene or arylene. The groups Nu and E are linked to the LINK and provide a favorable spatial relationship for nucleophilic attack of the nucleophilic center in Nu on the electrophilic center in E upon release of Nu from the CAR. When LINK is a cyclic group, Nu and E may be attached to the same ring or different rings. Aromatic groups where Nu and E are attached to adjacent ring positions are particularly preferred LINK groups.

TIME may be unsubstituted or substituted. Substituents include halogen including fluoro, chloro, bromo or iodo, nitro, alkyl having 1 to 20 carbon atoms, acyl such as carboxy, carboxyalkyl, alkoxycarbonyl, alkoxycarbonamide, sulfoalkyl, alkanesulfonamide, alkylsulfonyl May alter the rate of reaction, the rate of diffusion or the rate of substitution, such as solubilizing groups, ballast groups, or the like, or they may be stabilizers, antifoggants, dyes (eg, filter dyes or solubilizing masking dyes). And the like, which are separately useful in photographic elements. For example, solubilizing groups will increase the rate of diffusion, ballast groups will decrease the rate of diffusion, and electron-withdrawing groups will decrease the rate of substitution of PUG.

As used herein, the term "electron transfer down a conjugated chain"
Means electron transfer along a chain of atoms in which single and double bonds alternate. Conjugated chains are understood to have the same meaning as those commonly used in organic chemistry. This also includes TIME groups that can undergo a fragmentation reaction with zero double bonds. Electron transfer down a conjugated chain is described, for example, in US Pat. No. 4,409,323.

As mentioned above, one or more subsequent TIME units can be usefully used. Useful TIME units may have a finite or very short half-life. The half-life can be controlled by the specific structure of the TIME unit and can be selected to best optimize the intended photographic function. TIME half-lives from less than 0.001 seconds to more than 10 minutes are known in the art. It is known in the art to use TIME units with shorter half-lives to make development inhibitor units, but TIME units with half-lives of greater than 0.1 seconds will result in PUGs that yield development inhibitor units. Often preferred for use in release compounds. TIME units are P after being released from CAR
The UG may be released spontaneously, or the PUG may be released only after further reaction with other species present in the developer, or while the photographic element is in contact with the developer. The PUG may be released at the same time.

The following is a list of patents and publications describing representative coupler compounds containing a COUP group useful in the present invention.

Couplers that form cyan dyes by reaction with oxidative color developing agents are described in U.S. Pat.Nos. 2,772,162 and 2,895,826.
No. 3,002,836, No. 3,034,892, No. 2,474,293
No. 2,423,730, No. 2,367,531, No. 3,041,23
No. 6, No. 4,333,999, "Farbkuppler-eine Literaturubersicht", published in Agfa Mitteilungen, Volume III,
156-175 (1961) and Research Disclosure, Item 3
08119, described in representative patents and publications such as Section VII D, December 1989. Preferably such couplers are phenols and naphthols.

Couplers that form magenta dyes upon reaction with oxidized color developing agents are described in U.S. Pat.Nos. 2,600,788 and 2,369,489.
No. 2,343,703, No. 2,311,082, No. 3,152,89
No. 6, No. 3,519,429, No. 3,062,653, No. 2,908,5
No. 73, "Farbkuppler- published in Agfa Mitteilungen
eine Literaturubersicht ", Volume III, pp. 126-156 (1961
And Research Disclosure, Item 308119, December 1989, Section VII D, in representative patents and publications. Preferably such couplers are pyrazolones or pyrazolotriazoles.

Couplers that form yellow dyes upon reaction with oxidative color developing agents are described in U.S. Pat.Nos. 2,875,057 and 2,407,210.
No. 3,265,506, No. 2,298,443, No. 3,048,19
No. 4, No. 3,447, 928, “Farbkuppler-eine Literaturubersicht”, published in Agfa Mitteilungen, Volume III,
112-126 (1961) and Research Disclosure, Item 3
08119, described in representative patents and publications such as Section VII D, December 1989. Preferably such couplers are benzoylacetamides and pivaloylacetamides.

Couplers that form colorless products upon reaction with oxidized color developing agents are disclosed in GB 861,138, U.S. Pat.
No. 45, No. 3,928,041, No. 3,958,993 and No. 3,96
It is described in representative patents such as 1,959. Preferably, such couplers are cyclic carbonyl-containing compounds that react with oxidized color developing agents but do not form dyes.

PUG groups useful in the present invention include, for example:

1. PUG forming a development inhibitor upon release PUG forming a development inhibitor upon release is disclosed in U.S. Pat. No. 3,227,5
No. 54, No. 3,384,657, No. 3,615,506, No. 3,617,
No. 291, 3,733,201 and British Patent 1,450,479. Useful development inhibitors include iodides and mercaptotetrazoles, selenotetrazoles, mercaptobenzothiazoles, selenobenzothiazoles, mercaptobenzoxazoles, selenobenzoxazoles, mercaptobenzimidazoles, selenobenzimidazoles, oxadi Azoles, benzotriazoles, benzodiazoles, oxazoles, thiazoles, diazoles, triazoles, thiadiazoles, oxathiazoles, thiatriazoles, tetrazoles, benzimidazoles, indazoles, isoindazoles, mercapto Oxazoles, mercaptothiadiazoles, mercaptothiazoles, mercaptotriazoles, mercaptooxadiazoles, mercaptodiazoles, Mercaptoethyloleates oxathiazole such a tellurocarbonyl heterocyclic compounds such as tetrazole compound or benzoisothiazole di azoles. The structure of a typical development inhibitor unit is as follows.

In the above formula, G is S, Se or Te, preferably S, and R ^2a , R ^2d , R ^2h , R ²ⁱ , R ^2j , R ^2k , R ^2q and R ^2r are each independently
Hydrogen; methyl, ethyl, propyl, butyl, 1-ethylpentyl, 2-ethoxyethyl, t-butyl or i
-C1-C8 substituted or unsubstituted, linear or branched, saturated or unsaturated alkyl such as propyl; methoxy, ethoxy, propoxy, butoxy, octyloxy, methylthio, ethylthio, propylthio, butylthio Or alkoxy or alkylthio such as octylthio; CO ₂ CH ₃ , CO ₂ C ₂ H ₅ , CO ₂ C ₃ H ₇ , CO ₂ C
₄ H ₉ , CH ₂ CO ₂ CH ₃ , CH ₂ CO ₂ C ₂ H ₅ , CH ₂ CO ₂ C ₃ H ₇ , CH ₂ CO ₂ C ₄ H ₉ , CH ₂
CH ₂ CO ₂ CH ₃ , CH ₂ CH ₂ CO ₂ C ₂ H ₅ , CH ₂ CH ₂ CO ₂ C ₃ H ₇ and CH ₂ CH ₂ CO ₂
Alkyl esters such as _{C 4 H 9; CO 2 R} 2s, CH 2 CO 2 R 2s and C
Aryl esters or heterocyclic esters such as ^{_{H 2 CH 2 CO 2 R 2s}} ( wherein, R ^2s is a substituted or unsubstituted aryl or substituted or unsubstituted heterocyclic group); methoxy - chloro -, nitro Substituted or unsubstituted benzyl,-, hydroxy-, carboalkoxy-, carboaryloxy-, keto-, sulfonyl-, sulfenyl-, sulfinyl-, carbonamido-, sulfonamido-, carbamoyl- or sulfamoyl-substituted benzyl Benzyl; phenyl, naphthyl or chloro-, methoxy-, hydroxy-, nitro-, carboalkoxy-, carboaryloxy-, keto-, sulfonyl-, sulfenyl-, sulfinyl-, carbonamido-, sulfonamido-, carbamoyl- Or sulfamoyl-
A substituted or unsubstituted aryl such as a substituted phenyl. These substituents may be repeated twice or more as a substituent. R ^2a , R ^2d , R ^2h , R ²ⁱ , R ^2j , R ^2k , R ^2q and R ^2r
Is also pyridine, pyrrole, furan, thiophene, pyrazole, thiazole, imidazole, 1,2,4-triazole, oxazole, thiadiazole, indole, benzothiophene, benzimidazole, benzoxazole And a substituted or unsubstituted heterocyclic group selected from groups such as

R ^2b , R ^2c , R ^2e , R ^2f and R ^2g are R ^2a , R ^2d , R ^2h , R ²ⁱ , R ^2j , R
^As described for ^2k , R ^2q and R ^2r , or individually one or more halogens such as chloro, fluoro or bromo, q is 0, 1, 2, 3 or 4.

2.PUGs that are dyes or form dyes upon release Suitable dyes and dye precursors include azo, azomethine,
Azophenol, azonaphthol, azoaniline, azopyrazolone, indoaniline, indophenol, anthraquinone, triarylmethane, alizarin, nitro, quinoline, indigoid and phthalocyanine dyes or leuco dyes, such as the above, such as tetrazolium salts or shifted salts Dye precursors are included. These dyes may be metal complexed or metal complexable. Representative patents describing such dyes include:
U.S. Patent Nos. 3,880,658, 3,931,144, 3,932,
No. 380, No. 3,932,381, No. 3,942,987 and No. 4,8
No. 40,884. Preferred dyes and dye precursors are azo,
Azomethine, azophenol, azonaphthol, azoaniline and indoaniline dyes and dye precursors.
Typical dye and dye precursor structures are as follows:

Suitable azo, azomethine and methine dyes are described in U.S. Pat.
4,840,884, column 8, lines 1 to 70.

Dyes can be selected, for example, from those described in "Light Absorption of Organic Colorants" by J. Fabian and H. Hartmann, published by Springer-Verlag Co. However, the present invention is not limited to these.

A typical dye has the formula: -X-Y-N = NZ (where X is a heteroatom such as an oxygen atom, a nitrogen atom and a sulfur atom, and Y has a conjugation relationship with an azo group. A group of atoms that has at least one unsaturated bond and is bonded to X via an atom constituting the unsaturated bond, and Z contains at least one unsaturated bond that can be conjugated to an azo group. Which is a group of atoms and the number of carbon atoms contained in Y and Z is 10 or more).

Further, Y and Z are each preferably an aromatic group or an unsaturated heterocyclic group. As the aromatic group, a substituted or unsubstituted phenyl group or naphthyl group is preferred. As the unsaturated heterocyclic group, a 4- to 7-membered heterocyclic group containing at least one heteroatom selected from a nitrogen atom, a sulfur atom and an oxygen atom is preferred, which is part of a benzene fused ring system. You may. The heterocyclic group means a group having a ring structure such as pyrrole, thiophene, furan, imidazole, 1,2,4-triazole, oxazole, thiadiazole, pyridine, indole, benzothiophene, benzimidazole or benzoxazole.

Y may be substituted with other groups and X and an azo group. Examples of such other groups include aliphatic or alicyclic hydrocarbon groups, aryl groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acylamino groups, alkylthio groups, arylthio groups, heterocyclic groups, sulfonyl groups. Group, halogen atom, nitro group, nitroso group, cyano group, -COOM (M = H, alkali metal atom or N
H ₄ ), a hydroxyl group, a sulfonamide group, an alkoxy group, an aryloxy group and an acyloxy group.
Further, a carbamoyl group, an amino group, a ureido group, a sulfamoyl group, a carbamoylsulfonyl group and a hydrazino group are included. These groups may be further substituted, for example, once or twice, with groups such as those repeatedly disclosed above.

When Z is a substituted aryl group or a substituted unsaturated heterocyclic group, the groups described as substituents for Y can be used for Z in a similar manner.

When an aliphatic or alicyclic hydrocarbon unit is contained as a substituent in Y and Z, when the aliphatic hydrocarbon unit is 1 to
Any substituted or unsubstituted having 32, preferably 1 to 20 carbon atoms and, in the case of alicyclic hydrocarbon units, 5 to 32, preferably 5 to 20 carbon atoms. It is also possible to use saturated or unsaturated or straight-chain or branched groups. When the substitution is carried out repeatedly, the maximum number of carbon atoms of the substituent thus obtained is preferably 32.

When Y and Z contain an aryl unit as a substituent, the number of carbon atoms in this unit is generally from 6 to 10, preferably this is a substituted or unsubstituted phenyl group. In the present invention, the groups in the formulas before and after are defined as follows.

Acyl group, carbamoyl group, amino group, ureido group,
Sulfamoyl group, carbamoylsulfonyl group, urethane group, sulfonamide group, hydrazino group and the like are substituted with an unsubstituted group and an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aryl group to form mono-, di- Or a substituted group thereof which forms a tri-substituent, and an acylamino group, a sulfonyl group, a sulfonamide group, an acyloxy group and the like represent an aliphatic group, an alicyclic group and an aromatic group, respectively.

Typical examples of this group represented by the formula for the above azo dyes are contained, for example, in U.S. Pat. Nos. 4,424,156 and 4,857,447, column 6, lines 35-70.

3. Coupler PUG The released coupler may be a non-diffusible color-forming coupler, a non-color-forming coupler or a diffusible competing coupler. Representative patents and publications describing competitive couplers are
W. Puschel, “On the Chemistry of White Coupler
s ", Agfa-Gevaert AG Mitteilungen and der Forschungs
−Laboratorium der Agfa−Gevaert AG, Springer Verla
g, 1954, 352-367, U.S. Pat.No. 2,998,314, ibid.
Nos. 2,808,329, 2,689,793, 2,742,832, German Patent 1,168,769 and British Patent 907,274. Useful competing coupler structures are as follows:

Wherein R ^4a is hydrogen or an alkylcarbonyl such as acetyl, and R ^4b and R ^4c are independently hydrogen or a solubilizing group such as sulfo, aminosulfonyl and carboxy.

Wherein R ^4d is R ^4a or R ^{4b as} defined above, and R ^4e
Are development inhibitors such as halogen, aryloxy, arylthio or mercaptotetrazole such as phenylmercaptotetrazole or ethylmercaptotetrazole).

4. PUG forming the developing agent The released developing agent may be a color developing agent, a black and white developing agent or a cross-oxidizing developing agent. These include aminophenols, phenylenediamines, hydroquinones and pyrazolidones. Representative patents are U.S. Pat.Nos. 2,193,015, 2,108,243, and 2,592,364.
No. 3,656,950, No. 3,658,525, No. 2,751,29
No. 7, No. 2,289,367, No. 2,772,282, No. 2,743,2
No. 79, No. 2,753,256 and No. 2,304,953.

 The structure of a suitable developing agent is as follows:

Wherein R ^5a is hydrogen or alkyl having 1 to 4 carbons, and R ^5b is hydrogen or one or more halogens such as chloro or bromo or carbons such as methyl, ethyl or butyl. 1-4 alkyl).

Wherein R ^5b is as defined above.

Wherein R ^5c is hydrogen or alkyl having 1 to 4 carbons, and R ^5d , R ^5e , R ^5f , R ^5g and R ^5h each independently represent a hydrogen having 1 to 4 carbons such as methyl, ethyl or ethyl. An alkyl of 4,
C1-C4 hydroxyalkyl such as hydroxymethyl or hydroxyethyl or C1-C4 sulfoalkyl).

5.PUG which is a bleaching inhibitor Representative patents are U.S. Patent Nos. 3,705,801 and 3,715,2
No. 08 and German Offenlegungsschrift 2,405,279. The structure of a typical bleach inhibitor is as follows:

(Wherein, R ^6a is alkyl or aryl having 6 to 20 carbon atoms).

6.PUG which is a bleaching accelerator Wherein R ^7a is hydrogen or alkyl having, for example, 1 to 6 carbon atoms such as methyl, ethyl and butyl, alkoxy such as ethoxy and butoxy or alkylthio such as ethylthio and butylthio, which are substituted. R ^7b is hydrogen, substituted or unsubstituted alkyl or substituted or unsubstituted aryl such as phenyl, and R ^7c , R ^7d , R ^7e and R ^7f
Is independently hydrogen, straight or branched alkyl having 1 to 6 carbon atoms, for example, substituted or unsubstituted alkyl such as methyl, ethyl and butyl or substituted or unsubstituted aryl, and s is 1 to 6 And R ^7c and R ^7d or R ^7e and R ^7f may together form a 5-, 6- or 7-membered ring).

Structure for R ^7a and R ^7b : (Wherein R ^7c , R ^7d , R ^7e and R ^7f and s are as defined above) are often preferred.

Other PUG representatives of bleach accelerators include, for example, U.S. Pat.
No. 05,021, No. 4,912,024, No. 4,959,299, No. 4,
Nos. 705,021, 5,063,145, columns 21-22, lines 1-70, and EP Patent 0,193,389.

7. PUG, an Electron Transfer Agent (ETA) ETAs useful in the present invention are 1-aryl-3-pyrazolidinone derivatives, which, when released, are the processing conditions used to obtain the desired dye image. It becomes an active electron transfer agent that can accelerate development under the following conditions.

The electron transfer agent pyrazolidinone units which have been found to be useful in providing a development promoting function are disclosed in U.S. Pat.
It is generally derived from compounds of the type described in 4,209,580, 4,463,081, 4,471,045 and 4,481,287 and JP-A-62-123172. Such a compound has a 3-pyrazolidinone structure having an unsubstituted or substituted aryl group at the 1-position. US Patent 4,85
The combinations disclosed in 9,578 are also useful. Preferably, these compounds are in the 4- or 5-position of the pyrazolidinone ring.
It has one or more alkyl groups in the -position.

Electron transfer agents suitable for use in the present invention are represented by the following two formulas:

Wherein R ^8a is hydrogen and R ^8b and R ^8c are each independently hydrogen, substituted or unsubstituted alkyl having 1 to about 8 carbons (such as hydroxyalkyl), carbamoyl or 6 to 6 carbons. Represents about 10 substituted or unsubstituted aryl, and R ^8d and R ^8e are each independently hydrogen, substituted or unsubstituted alkyl having 1 to about 8 carbons or substituted or unsubstituted having 6 to about 10 carbons. Represents an aryl, R ^8f which may be present at the ortho, meta or para position of the benzene ring is halogen, substituted or unsubstituted alkyl having 1 to about 8 carbons or substituted or unsubstituted having 1 to about 8 carbons Wherein t is 1
When greater than, the R ^8f substituents may be the same or different or together may form a carbocyclic or heterocyclic ring, such as a benzene ring or an alkylenedioxy ring, and t is 0 or 1-3. Is).

When the R ^8b and R ^8c groups are alkyl, they preferably have 1 to 3 carbon atoms. When R ^8b and R ^8c represent aryl, they are preferably phenyl.

R ^8d and R ^8e are preferably hydrogen.

When R ^8f represents a sulfonamide, it is, for example,
It may be methanesulfonamide, ethanesulfonamide or toluenesulfonamide.

8. PUG which is a Development Inhibiting Redox Release Agent (DIRR) DIRRs useful in the present invention include hydroquinone, catechol, pyrogallol, 1,4-naphthohydroquinone, 1,2-naphthohydroquinone, sulfonamidophenol, sulfonamidonaphthol and Hydrazide derivatives are included, which, when released, can release a development inhibitor, such as a hydroxide ion, upon reaction with a nucleophile under the processing conditions used to obtain the desired dye image. It becomes an activity inhibitor redox releasing agent. Such redox releasing agents are described in U.S. Pat. No. 4,985,336, formula (II) at column 3, lines 10-25 and formula (III) at column 14, line 54 to column 17, line 11.
And (IV). Other redox releasing agents are described in European Patent Application No. 0,285,176. Typical redox releasing agents include:

Couplers containing other suitable redox releasing agents are described, for example, in U.S. Pat. No. 4,985,336 at columns 17-62.

The following formula represents a 5-, 6- or 7-membered nitrogen-containing unsaturated heterocyclic group having 2 to 6 carbon atoms, which is bonded to a carrier unit via a nitrogen atom, and a sulfonamide group is attached to the ring carbon atom. And a development inhibitor group or a precursor thereof. Z
Contains 5-, 6-
Or DI represents a group of atoms necessary to form a 7-membered nitrogen-containing unsaturated heterocyclic group, DI represents a development inhibitor group, and
R ^9a represents a substituent, and DI is attached to the carbon atom of the heterocycle represented by Z via the heteroatom contained therein, and the sulfonamide group is attached to the carbon atom of the heterocycle represented by Z. ing. However, the nitrogen atom through which the heterocyclic ring is bonded to the carrier unit and the nitrogen atom of the sulfonamide group are described, for example, in "Theory of Photographic Processing", 4th edition, pp. 298-325. It is arranged to satisfy the Kendall-Pelz rule.

The group represented by the above formula is a group that can be oxidized by an oxidation product of the developing agent. More particularly, the sulfonamide groups are oxidized to sulfonylimino groups, from which the development inhibitors are cleaved.

Specific examples of the development inhibiting redox release agents described herein are as follows.

Other examples of development inhibiting redox releasing agents are described, for example, in European Patent Application 0,362,870, page 13, line 25 to line 2.
It can be found in the coupler shown on page 9, line 20.

In a preferred embodiment, the PUG releasing compound is a development inhibitor releasing (DIR) compound. These DIR compounds are
As is all known in the art, it may be contained in the same layer as the emulsions of the invention, in reactive association with this layer, or in other layers of the photographic material.

These DIR compounds are classified as "diffusible", meaning that they allow the release of higher transportable inhibitor units, or mean they can release lower transportable inhibitor units. It may be one of those classified as “non-diffusible”. The DIR compound may consist of a time adjusting or linking group known in the art.

The inhibitor unit of the DIR compound may not change as a result of exposure to the photographic processing solution. However, this suppressor unit was obtained as a result of photographic processing,
No. 9,167, European Patent Application No. 167,168, JP-A-58-
The structure may be altered and affected in the manner disclosed in US Pat. No. 205150 or US Pat. No. 4,782,012.

When the DIR compounds are dye-forming couplers, they may be in reactive association with the complementary sensitized silver halide emulsion, such as, for example, a cyan dye-forming DIR coupler with a red sensitized emulsion, or in a mixed form, e.g., a green sensitizing emulsion. It may be included in a yellow dye-forming DIR coupler with an emulsion-sensitive emulsion, all of which are known in the art.

DIR compounds are also disclosed in U.S. Pat.
Bleach accelerator releasing couplers as described in 135,839, and U.S. Patent Nos. 4,865,956 and 4,923,7
No. 84 may be included in reactive association with the bleach accelerator releasing couplers. All of these patents are incorporated herein by reference.

Certain DIR compounds useful in the practice of the present invention are disclosed in the above-cited references, for commercial use, and in the Examples included herein that demonstrate the practice of the invention.

Dye image-forming compounds and PUG releasing compounds can be incorporated into the photographic elements of the present invention by equipment and methods known in the photographic art. Dye image-forming compound and
The photographic element containing the PUG-releasing compound can be a single color element consisting of a support and a single silver halide emulsion layer, or it can be a multicolor multilayer element consisting of a support and multiple silver halide emulsion layers. May be. The above compounds can be included in at least one of the silver halide emulsion layers and / or in at least one other layer, such as an adjacent layer, wherein the other layers are in reactive association with the silver halide emulsion layers. , Which can react with oxidized developing agents generated by the development of silver halide in the emulsion layer.
Further, the silver halide emulsion layers and other layers of the photographic element may contain additives conventionally contained in such layers.

A typical multicolor multilayer photographic element is a red-sensitive silver halide emulsion unit with a cyan dye image-forming compound associated therewith, and a green-sensitive silver halide emulsion with a magenta dye image-forming compound associated therewith The unit may comprise a support having thereon a blue-sensitive silver halide emulsion unit having a yellow dye image-forming compound. Each silver halide emulsion unit may be composed of one or more layers, as known in the art and as indicated by the layer order format described below, and the various units and layers are related to one another. May be arranged at different positions.

In the element of the present invention, the layer or unit affected by the PUG can be controlled by including, at an appropriate location in the element, a layer that limits the effect of the PUG on the desired layer or unit. That is, at least one layer of the photographic element can be, for example, a scavenger layer, a mordant layer, or a barrier layer. Examples of such layers include, for example, U.S. Patent Nos. 4,055,429, 4,317,892,
Nos. 504,569, 4,865,946 and 5,006,451. The element may also include additional layers such as antihalation layers, filter layers, and the like. This element will typically have a total thickness excluding the support of 5 to 30 μm. Thinner formulations of 5-25 μm are generally preferred, as they are known to provide improved contact with the processing solution. For the same reason, a more swellable film structure is likewise preferred. Furthermore, the present invention
It is particularly useful in magnetic recording layers such as those described in Research Disclosure, Item 34390, November 1992, page 869.

In the following description of materials suitable for use in the elements of the present invention, reference is made to Research Disclosure, 1989, supra.
Dec., Item 308119, the disclosure of which is incorporated herein by reference.

Suitable dispersion media for the emulsion layers and other layers of the element of the present invention are described in Research Disclosure, December 1989, Item
308119, Section IX and the publications therein.

In addition to the compounds described herein, elements of the present invention include Research Disclosure, December 1989, Item 308119, Sect.
ion VII AE and H and additional dye image-forming compounds as described in the publications cited therein; and
Research Disclosure, December 1989, Sectio of Item 308119
n VII F and G and additional PUG releasing compounds as described in the publications cited therein may be included.

All elements of the present invention include Research Disclosure, 1989
In December, Item 308119, an optical brightener (Section
V), antifoggants and stabilizers (Section VI), antistain and image dye stabilizers (Sections VII I and J), light absorption and scattering agents (Section VIII), hardeners (Sectio)
n X), coating aids (Section XI), plasticizers and lubricants (Sec.
XII), an antistatic agent (Section XIII), a matting agent (Section XVI), and a development modifier (Section XXI).

The elements of the present invention are the Research Disclosure Item Section
It can be coated on various supports as described in XVII and the references cited therein.

The elements of the present invention are identified in Research Disclosure Item 308119
Exposure to actinic radiation, typically in the visible region of the spectrum, to form a latent image, as described in Sections XVIII and XIX of A dye image can be formed. Typically, development processing to form a visible dye image includes contacting the element with a color developing agent, reducing developable silver halide, and oxidizing the color developing agent. The oxidized color developing agent then reacts with the coupler to form a dye.

A preferred color developing agent is p-phenylenediamine. 4-amino-3-methyl-N, N-diethylaniline hydrochloride, 4-amino-3-methyl-N-ethyl-N-β
-(Methanesulfonamido) -ethylaniline sulfate hydrate, 4-amino-3-methyl-N-ethyl-N-β-
Hydroxyethylaniline sulfate, 4-amino-3-β
-(Methanesulfonamido) ethyl-N, N-diethylaniline hydrochloride and 4-amino-N-ethyl-N- (2-
(Methoxyethyl) -m-toluidine di-p-toluenesulfonic acid is particularly preferred.

With negative working silver halide, the above processing steps give a negative image. The above elements are preferably, for example, the 1988
Processing is carried out in a known Kodak Flexicolor C-41 color process as described in the British Journal of Photography Annual, pp. 196-198. To provide a positive (or reversal) image, the color development step involves developing the exposed silver halide, but first developing with a non-color developing agent that does not form a dye, and then uniformly fogging the element to form a non-color developing agent. This can be done by making the exposed silver halide developable. The Kodak E-6 process is a typical inversion process.

The development is followed by bleaching, fixing or bleach-fixing to remove silver or silver halide, washing and drying.

 The following table shows compounds useful in the practice of the present invention.

Table 1 contains formulas of typical dye image-forming coupler compounds.

Table 2 includes formulas of typical PUG releasing compounds that release development inhibitor groups or precursors thereof. Table 3 shows formulas of representative examples of other types of PUG releasing compounds.

Table 4 shows the formulas of various typical photographic compounds that can be used in the elements of the present invention.

Of course, the color photographic element of the present invention includes, for example, an undercoat layer,
Optional additional layers and compounds generally known to be useful in color photographic elements, such as overcoat layers, surfactants and plasticizers, some of which are described in detail above. Anything may be included. These are, for example, Industrial Opportunities Ltd., Homewe
ll Havant, Hampshire, R09 published by P09 1EF, UK
esearch Disclosure, December 1989, Item 308117, Section
All suitable methods can be used for coating on a suitable support, including those described in the XV coating and drying methods, the disclosure of which is incorporated herein by reference.

Photographic elements containing radiation-sensitive {100} tabular grain emulsion layers according to this invention can be used in the ultraviolet and visible (e.g., actinic) and infrared regions of the electromagnetic spectrum, as well as electron beam and beta radiation, gamma rays, X-rays. Imaging with various forms of energy, including alpha particles, neutrons and fine particles in either the non-interfering (random phase) or interfering (in-phase) form as produced by lasers and other forms of wavy radiant energy Exposure. The exposure can be monochromatic, orthochromatic or panchromatic. THJames, Theory of Photo Processing, 4
Edition, Macmillan, 1977, chapters 4, 6, 17, 18 and 23, high or low intensity exposure, continuous or intermittent exposure, from minutes to relatively short duration in the millisecond to microsecond range. Exposure time and overexposure (solarizing exposur)
Imagewise exposure of the environment, including e) at high and low temperatures and / or pressures, can be used within the useful response range determined by conventional sensitometric techniques.

Emulsion Preparation Examples Preparation I This preparation illustrates the preparation of an ultrathin tabular grain silver iodochloride emulsion satisfying the requirements used in the color photographic elements of the present invention.

1.75% by weight of low methionine gelatin (gelatin treated with an oxidizing agent to reduce its methionine content to less than 30 μmol / g), 0.011 M sodium chloride and 1.48 × 10 ⁻⁴ M potassium iodide 2030mL containing solution
Was prepared in a stirred reaction vessel. The contents of the reaction vessel were maintained at 40 ° C. and the pCl was 1.95.

While stirring this solution vigorously, 30 mL of 1.0 M silver nitrate solution
And 30 mL of 0.99 M sodium chloride and 0.01 M potassium iodide solutions were added simultaneously at a rate of 30 mL / min each.
As a result, grain nucleation was performed, and crystals having an initial iodide concentration of 2 mol% based on total silver were formed.

The mixture was then held at a temperature that remained at 40 ° C. for 10 minutes. Following this hold, then a 1.0 M silver nitrate solution and 1.0 M
The sodium chloride solution was maintained at 2 mL /
At the same time for 40 minutes.

The resulting emulsion was a tabular grain silver iodochloride emulsion containing 0.5 mole percent iodide, based on silver. Of the total grain projected area
50% was selected based on the aspect ratio ranking of all {100} tabular grains having a thickness of less than 0.3 μm and a major surface edge length ratio of less than 10, with an average ECD of 0.84 μm and 0.037 μm Given by tabular grains having {100} major faces with an average thickness of The selected tabular grain population had an average aspect ratio (ECD / t) of 23 and an average tabularity (ECD / t ² ) of 657. The ratio of the main surface edge length of the selected tabular grains was 1.4. 72% of the total grain projected area was composed of tabular grains having {100} major faces and an aspect ratio of at least 7.5. These tabular grains have an average ECD of 0.75 μm, an average thickness of 0.045 μm, 18.6
And an average tabularity of 488.

 A representative sample of the grains of this emulsion is shown in FIG.

Preparation II This preparation demonstrates the importance of iodide in the precipitation of the initial grain population (nucleation).

This emulsion was precipitated as in Preparation I except that no iodide was intentionally added.

The obtained emulsion mainly has an edge length of about 0.1 to 0.5 μm.
And a rectangular particle having a very small aspect ratio. There were a few large rods and high aspect ratio {100} tabular grains,
It did not constitute a useful amount of the particle population.

 A representative sample of the grains of this emulsion is shown in FIG.

The color photographic elements of the present invention may consist of a single radiation-sensitive emulsion layer on a support. The element may also include a radiation-sensitive layer applied on each side of the support, a so-called duplitized format. However, a particularly useful embodiment comprises a red light sensitizing unit, a green light sensitizing unit and a blue light sensitizing unit, each unit comprising at least one dye-forming compound in reactive association with a radiation-sensitive silver halide emulsion. Is a multicolor multilayer element.

If desired, the color photographic elements of the present invention can be obtained from Kenneth Ma
son Publications, Ltd., Dudley Annex, 12a North Stree
t, Emsworth, Hampshire P010 7DQ, R published from UK
esearch Disclosure, November 1992, Item 34390, can be used with an applied magnetic layer.

Some preferred layer order arrangements for the multicolor element of the present invention are as follows. Antihalation layers applied on either side immediately next to the support are not shown in these formats. Also shown is a protective overcoat layer that includes gelatin, dyes, UV absorbers, polymer beads, etc. and is applied over the top dye imageable unit.

A typical multicolor multilayer format for the elements of the present invention is represented by Structure I.

In the above structure, the red-sensitized cyan dye image-forming silver halide emulsion unit is located closest to the support, the next order being the green-sensitized magenta dye image-forming silver halide emulsion unit; Next is the top blue sensitized yellow dye image-forming silver halide emulsion unit. The imageable units are typically separated from each other by an interlayer as described above.

Each of the imageable units may contain a single radiation-sensitive silver halide emulsion layer. In addition, each unit independently includes two or three layers of different sensitivities of low sensitivity, high sensitivity or low sensitivity, medium sensitivity, and high sensitivity, respectively, in the order of increasing radiation sensitivity. You may. In the practice of the present invention, a tabular silver chloride emulsion containing grains bound by a {100} major surface and in reactive association with a dye image-forming compound and a PUG releasing compound is a blue sensitized silver halide. May be included only in the emulsion unit,
Or it may be included in each of the silver halide emulsion units. If the unit contains more than one radiation-sensitive layer, the tabular silver chloride emulsion may be in the slowest layer (the slower layer), or it may be in the other emulsion layer of the unit or It may be in all emulsion layers.

Another useful multicolor multilayer format for the elements of the present invention is the so-called reverse layer sequence represented by Preparation II.

In the above structure, the blue sensitized yellow dye image-forming silver halide emulsion unit is located closest to the support, followed by a red sensitized cyan dye image-forming unit.
At the top is a green sensitized magenta dye image-forming unit. As noted above, the individual units are typically separated from each other by an intermediate layer.

As described above for Structure I, each of the imageable units may consist of a single radiation-sensitive layer, or may each independently comprise two (low, high) or three of different sensitivities. A single (low, medium, high) silver halide emulsion layer may be included. Also, as described above for Structure I, tabular silver chloride emulsions containing grains linked by {100} major faces may be located only in the blue sensitized silver halide emulsion units, or May be arranged. If the unit consists of more than one radiation-sensitive layer, the tabular silver chloride emulsion may be in the slowest layer, or in other or all layers of the unit.

Other suitable layer order arrangements for practicing the present invention are shown in Structure II.
Described by I.

In the above structure, the slower red-sensitized silver halide emulsion layer of the cyan dye image-forming unit is located closest to the support, and the next order is the slower green of the magenta dye image-forming unit. A sensitized silver halide emulsion layer, a high-sensitivity red-sensitized silver halide emulsion layer of a cyan dye image-forming unit and a high-sensitivity green sensitized silver halide emulsion layer of a magenta dye image-forming unit. The blue-sensitized yellow dye image-forming silver halide emulsion unit, which may consist of one, two or three emulsion layers, is at the top. As with the previous structures, the imageable units are typically separated from each other by an interlayer. The elements of the invention having the layer sequence shown in Structure III include grains bound by {100} major faces in the slow emulsion layer of the yellow dye imageable unit as well as in the more sensitive emulsion layer of this unit. And a tabular silver chloride emulsion having the formula: Tabular silver halide emulsions can also be used in the lowest speed layers of the green- and / or red sensitized emulsion units and in all other radiation-sensitive layers of this element.

Yet another useful format for the color elements of the present invention is represented by Structure IVa.

In the above structure, the lower-sensitivity silver halide emulsion layers of the red sensitized emulsion unit and the green sensitized emulsion unit are one, two, and three from the high-sensitivity silver halide emulsion layer of these units.
Separated by a blue sensitized emulsion unit which may consist of one or three emulsion layers. According to the present invention, an emulsion having silver halide grains bonded by a {100} major surface,
It can be used in the upper sensitive layer in the green- and red-sensitized silver halide emulsion units and in the red-sensitized silver halide emulsion unit, or it can be used in all of the radiation-sensitive layers of the element. can do.

A variant of structure IVa is structure IVb (not shown),
In b, the positions of the lower and higher speed silver halide emulsion layers have been shifted in both the red and green sensitized emulsion units. That is, the positions of the lower speed green sensitized emulsion layer and the higher speed green sensitized emulsion layer are opposite to those positions in the structure IVa, and the position of the red sensitized emulsion layer is also the same. . In Structure IVb, an emulsion having tabular {100} surface silver chloride grains can be located in the lower, lower layer of the green- and red-sensitized silver halide emulsion units, or It can be used for all of the radiation-sensitive layers of the element.

Other suitable layer order arrangements for the multicolor elements of the present invention are described in Research Disclosure, January 1983, Item 22534, 35-3.
It is described on page 7.

The invention can be better appreciated by reference to the following examples. In each of the examples below, the color photographic elements exhibited unexpectedly high levels of image sharpness.
It is sufficiently remarkable that this image sharpness is evident by simple observation of the developed element. Such sharpness appears to be attributable to the unique morphology of tabular {100} silver halide grains that provide refractive index values very close to those of the dispersion medium present in the emulsion layer. .

Example 1 Preparation and Description of a Silver Halide Emulsion A control silver halide emulsion and tabular silver chloride emulsions linked by {100} major faces according to the present invention were prepared and sensitized as follows. A summary of the emulsions and their properties is provided in Table 5.

A cubic silver chloride control emulsion in which the grains have predominantly {100} faces was prepared as described in US Pat. No. 4,952,491 and Research Disclosu.
re, Item 308119, prepared according to the method described in Section I, December 1989. These emulsions were sensitized to green, blue or red light by methods known in the art.

Prepare a cubic silver iodobromide emulsion using Research Disclosure, Item 308
119, manufactured by the method contained in Section I, December 1989. Sensitization was performed by methods known in the art.

U.S. Pat.No.4,439,520, Resear
ch Disclosure, Item 22534, January 1983 and Research Di
Produced and sensitized by the method described in sclosure, Item 308119, December 1989.

An exemplary method of making tabular silver chloride emulsions joined by {100} major faces useful in the practice of this invention is as follows.

A. Preparation of Emulsions EM-4, EM-7 and EM-10 Six types of solutions were prepared as follows.

Solution 1 Gelatin (bone) 105 g NaCl 1.96 g Distilled water 5798 g Solution 2 KI 0.36 g Distilled water 180 g Solution 3 NaCl 199 g Distilled water 6760 mL Solution 4 AgNO ₃ 5.722 Molarity 510 g Distilled water was added to give a total volume of 6300 mL Solution 5 Gelatin (phthalate) 100 g distilled water 1000 g solution 6 gelatin (bone) 80 g distilled water 1000 g solution 1 was placed in a reaction vessel equipped with a stirrer. Solution 2 was added to the reaction vessel. While vigorously stirring the mixture at a pH of 6.0 and a temperature of 40 ° C.,
Added at mL / min for 0.5 minutes. VAg was adjusted to 175 mV and the mixture was held for 10 minutes. Following this hold, Solution 3 and Solution 4 were added simultaneously at 24 mL / min for 40 minutes, then VAg was added to 175 mV
While maintaining this flow from 24 mL / min over 130 minutes.
Accelerated linearly to 48 mL / min. Solution 5 was added and stirred for 5 minutes. The pH was then adjusted to 3.8 and the gelatin was precipitated while lowering the temperature to 15 ° C. The liquid layer was decanted and the reduced volume was reconstituted with distilled water. Adjust the pH to 4.5, hold the mixture at 40 ° C. for 5 minutes, then adjust the pH to 3.8,
The precipitation and decantation steps were repeated. Solution 6 was added and the pH and VAg were adjusted to 5.6 and 130 mV, respectively.

The resulting emulsion contained mainly tabular silver chloride grains having {100} faces, an average equivalent circular diameter (ECD) of 1.2 μm, and an average thickness of 0.12 μm.

The emulsion thus prepared is treated with 1% NaBr and kept for 5 minutes to remove the spectral sensitizing dyes SS-22 and SS-26.
3: was added at 1 ratio, holding for 10 minutes, the _{Na 2 S 2 O 3 5H 2} O to 1.0 mg / mole and KAuCl ₄ was added at 1.3 mg / mole and the green light by heating for 10 minutes at 60 ° C. After sensitization, a green light-sensitized emulsion, EM-4, was prepared. Similarly, spectral sensitizing dye SS
-25 using SS-25 and SS-23 in a 1: 2 ratio.
And a blue light-sensitized emulsion EM- using the spectral sensitizing dye SS-1.
I got 10.

B. Preparation of Emulsions EM-5, EM-8 and EM-11 Eight solutions were prepared as follows.

Solution 1 Gelatin (bone) 211 g NaCl 1.96 g Distilled water 5800 g Solution 2 KI 0.15 g Distilled water 90 g Solution 3 NaCl 207 g Distilled water 7000 mL Solution 4 NaCl 13.1 g Distilled water 108 mL Solution 5 AgNO ₃ 5.722 Molarity 69.8 g Distilled water 5425 g Solution 6 AgNO ₃ 5.722 Molarity 69.8 g Distilled water 73.7 g Solution 7 Gelatin (phthalated) 100 g Distilled water 1000 g Solution 8 Gelatin (bone) 80 g Distilled water 1000 g Solution 1 was placed at 40 ° C. in a reactor equipped with a stirrer.
Solution 2 was added to the reaction vessel and the pH was adjusted to 5.7.
While vigorously stirring this mixture, add solution 4 and solution 6
Added at 180 mL / min for 30 seconds. The reaction mixture was then held for 10 minutes. Following this hold, solution 3 and solution 5 were added simultaneously at 24 mL / min for 40 minutes while maintaining pCl at 1.91. The rate was then accelerated to 48 mL / min over 130 minutes. The mixture was cooled to 40 ° C., solution 7 was added and the mixture was stirred for 5 minutes. The pH was then adjusted to 3.8 and the temperature was adjusted to 1
The gelatin was precipitated while lowering to 5 ° C. The liquid layer was decanted and the reduced volume was reconstituted with distilled water. The pH was adjusted to 4.5 and the mixture was kept at 40 ° C. for 20 minutes, then the pH was adjusted to 3.8
And the precipitation and decantation steps were repeated. Solution 8 was added and the pH and pCl were adjusted to 5.6 and 1.6, respectively.

The resulting emulsion contained mainly tabular silver chloride grains having {100} faces, an average equivalent circular diameter (ECD) of 1.4 μm, and an average thickness of 0.14 μm.

The emulsion thus prepared is treated with 1% NaBr and kept for 5 minutes to remove the spectral sensitizing dyes SS-22 and SS-26.
3: was added at 1 ratio, holding for 10 minutes, the _{Na 2 S 2 O 3 5H 2} O to 1.0 mg / mole and KAuCl ₄ was added at 1.3 mg / mole and the green light by heating for 10 minutes at 60 ° C. On the other hand, it was sensitized to make EM-5. Similarly, the spectral sensitizing dyes SS-25 and SS-23 are added to
Red light sensitized emulsion EM-8 was obtained using two ratios, and spectral sensitizing dye S
Blue light-sensitized emulsion EM-11 was obtained using S-1.

C. Preparation of Large Tabular Silver Chloride Emulsions A typical method of preparing large (> 2 μm ECD) tabular silver halide emulsions is as follows.

Solution 2 containing 1.77% by weight of bone gelatin, 0.056M of sodium chloride, 1.86 × 10 ^-4 M of potassium iodide at 55 ° C. and pH 6.5
In a stirred reaction vessel containing 945 mL, a 4.0 M silver nitrate solution 15 m
L and 15 mL of a 4.0 M sodium chloride solution were added simultaneously at a rate of 30 mL / min.

The mixture was then held for 5 minutes, and 7000 mL of distilled water was added and the temperature was raised to 65 ° C. while adjusting the pCl to 2.15 and the pH to 6.5. Following retention, the dual-zone method (dual-zone p
The size of the particles obtained through growth using a process is increased. In this method, a 0.67 M solution of silver nitrate was premixed with a 0.67 M solution of sodium chloride and a 0.5% by weight solution of bone gelatin at a pH of 6.5 in a well-stirred continuous reactor having a total volume of 30 mL. The effluent from this premix reactor was then added to the original reaction vessel which served as the growth reactor during this step. During the growth process, the microcrystals from the continuous reactor were aged on the original crystals by Ostwald ripening. During this growth step, the total suspension volume in the growth reactor was kept constant at 13.5 L using ultrafiltration.

The flow rates of the 0.67 M silver nitrate solution and the 0.67 M sodium chloride solution were increased from 20 mL / min to 80 mL / min, 150 mL / min and 240 m at 25 minute intervals.
Increased linearly to L / min. The flow rate of the 0.5 wt% gelatin reactant was kept constant at 500 mL / min. A continuous reactor premixed with these reactants was maintained at 30 ° C. and a pCl of 2.45, while the growth reactor was maintained at a temperature of 65 ° C., a pCl of 2.15 and a pH of 6.5.
The pH was maintained.

This operation resulted in 6 moles of a high aspect ratio tabular grain iodochloride emulsion containing 0.01 mole percent iodide. More than 90% of the total projected grain area was provided by tabular grains having {100} major faces, an average ECD of 2.55 μm and an average thickness of 0.165 μm. Thus, the tabular grain population had an average aspect ratio of 15.5 and an average tabularity of 93.7.

The emulsion was treated with 1% NaBr, held for 5 minutes, added with a spectral sensitizing dye (SS-25 and SS-23, 2: 1 ratio), held for 10 minutes, Na ₂ S ₂ O ₃ 5H ₂ O to 1.0 mg / mole and KAuCl
₄ was added at 1.3 mg / mol and sensitized to red light by heating at 60 ° C. for 10 minutes.

Example 2-Preparation and Development of a Photographic Element A. Preparation of the Element Sample 101 was prepared by applying the following layers to the transparent support in the order described. The amounts of the components are given in g / m ² .

Layer 1 (antihalation layer): consists of gray silver and gelatin.

Layer 2 (photosensitive layer): consists of 0.32 g of EM-1c, 0.54 g of image dye-forming coupler C-1 and 1.54 g of gelatin.

Layer 3 (protective layer): consists of 2.15 g of gelatin.

These layers may further comprise α-4-nonylphenyl-ω-hydroxy-poly (oxy- (2-hydroxy-1,3-propanediyl)) and (para-t-
(Octylphenyl) -di (oxy-1,2-ethanediyl) sulfonate.

This film was treated with 2% by weight of bis-
The film was hardened at the time of coating with vinylsulfonylmethane.

Sample 102 was prepared in the same manner as Sample 101, except that emulsion EM-1c was replaced with an equal amount of emulsion EM-2c.

Sample 103 was prepared in the same manner as Sample 101, except that emulsion EM-1c was replaced with an equal amount of emulsion EM-3c.

Sample 104 was prepared in the same manner as Sample 101, except that emulsion EM-1c was replaced with an equal amount of emulsion EM-4.

Sample 105 was prepared in the same manner as Sample 101, except that Emulsion EM-1c was replaced with an equal amount of Emulsion EM-5.

Sample 106 was prepared in the same manner as Sample 105 except that image dye-forming coupler C-1 was replaced with 0.32 g of image dye-forming coupler C-2.

Sample 107 was prepared in the same manner as Sample 101, except that emulsion EM-1c was replaced with an equal amount of emulsion EM-6c.

Sample 108 was prepared in the same manner as sample 101, except that emulsion EM-1c was replaced with an equal amount of emulsion EM-7.

Sample 109 was prepared in the same manner as Sample 101, except that Emulsion EM-1c was replaced with an equal amount of Emulsion EM-8.

Sample 110 was prepared in the same manner as Sample 101 except that emulsion EM-1c was replaced with an equal amount of emulsion EM-9c and image dye-forming coupler C-1 was replaced with 1.08 g of image dye-forming coupler C-3. Manufactured.

Sample 111 was prepared in the same manner as sample 110, except that emulsion EM-9c was replaced with an equal amount of emulsion EM-10.

Sample 112 was prepared in the same manner as sample 110, except that emulsion EM-9c was replaced with an equal amount of emulsion EM-11.

Coupler C-1 is a cyan image dye-forming coupler, C-2 is a magenta dye-forming coupler, and C-3 is a yellow image dye-forming coupler.
These couplers were provided as photographic coupler dispersions as known in the art.

B. Measurement of Relative Photosensitivity and Dye Density Obtained for Developed Elements Samples 101-112 were graduated for graduated density test
d density test object) and developed using Kodak C-41 processing. This treatment was varied in that the bleaching solution consisted of ferric propylenediaminetetraacetate.

Photographic sensitivity was measured as the exposure required to allow a Status M density of 0.15 greater than Dmin after development. Status M density at Dmax value was also measured.

In Table 6 below, for each sample, emulsion name; surface area per grain; color sensitization; dye image-forming coupler; relative sensitivities observed experimentally; The relative sensitivity expected assuming a linear function of: and the Status M dye density formed in Dmax per g / m ² of coated coupler per silver g / m ^{2 in} each sample, ie Normalized dye concentration yield (normalized d
yedensity yield) (DDY).

The results obtained with control samples 101, 102 and 103 show the difficulty in obtaining high photographic speed or high dye density yields with cubic {100} AgCl particles. As the particle size (and surface area) increases, the dye density yield decreases dramatically, but the photographic speed increases little at all. Photographic sensitivity is expected to increase directly as a function of surface area per grain for spectrally sensitized emulsions, but this expectation was not met for control samples. Conversely, Samples 104 and 105 of the present invention exhibited photographic speed well beyond what would be expected based on the relative particle surface area. In addition, the dye density gains obtained with these samples also exceeded those obtained from the smaller, photographically sensitive control samples.

The results from sample 106 of the present invention show that image dye-forming couplers that require a lower stoichiometric amount of oxidized developing agent for dye formation (coupler C-2 is a two-equivalent image coupler and coupler C- 1 is a 4-equivalent image coupler) or by selecting an image coupler that forms a high quenching image dye, both photosensitivity and dye density yield can be further improved.

The results from Samples 107-109 and from Samples 110-112 show that these beneficial effects were also obtained from the inventive samples which were also sensitive to red and blue light, respectively.

As can easily be seen, the photographic samples according to the invention not only give a greatly improved photographic speed compared to the control sample, but also give a surprisingly high dye density formation as compared to the control sample.

The above sample was exposed to white light through a calibrated density test object and developed for 195 seconds using a color photographic paper developer as described in U.S. Pat. No. 4,892,804. Results similar to those shown in Table 1 were obtained.

Exposure and development using the Kodak C-41 process as described above were repeated on samples 101-112 using development times of 1, 2, 3, 4, and 5 minutes. The improved performance of the element of the invention compared to that of the control sample was again observed in all cases.

Varying the contact time between the photographic material and the processing solution is typically used by those skilled in the art to approximate the effect of changes in temperature or concentration of components in the processing solution. Thus, longer treatment times approximate the effect of increased component concentration or increased temperature or both, while shorter treatment times approximate reduced component concentration or decreased temperature or both. These effects are well known to those skilled in the photographic art so that they can select the processing composition and temperature to obtain the desired result for a particular application from the elements of the present invention. .

Example 3-Preparation and processing of a photographic element containing a PUG releasing compound releasing a development inhibitor A. Preparation of the elements Samples 201-205 were prepared by applying the following layers to a transparent support in the order listed. . The amounts of the components are given in g / m ² .

Layer 1 (antihalation layer): consists of gray silver and gelatin.

Layer 2 (photosensitive layer): Consists of 0.54 g of EM-13c, 0.54 g of image dye-forming coupler C-1, 1.54 g of gelatin and various DIR compounds as listed in Table 7.

Layer 3 (protective layer): consists of 2.15 g of gelatin.

These layers may further comprise α-4-nonylphenyl-ω-hydroxy-poly (oxy- (2-hydroxy-1,3-propanediyl)) and (para-t-
(Octylphenyl) -di (oxy-1,2-ethanediyl) sulfonate.

This film was treated with 2% by weight of bis-
The film was hardened at the time of coating with vinylsulfonylmethane.

Control samples 206 to 211 were prepared in the same manner as samples 201 to 205 except that emulsion EM-13c was replaced by an equal weight of emulsion EM-14c.

Control samples 301-303 were prepared in the same manner as samples 201-205 except that emulsion EM-13c was replaced with an equal weight of emulsion EM-6c.

Control samples 304-306 were prepared in the same manner as samples 201-205 except that emulsion EM-13c was replaced with an equal weight of emulsion EM-9c.

Control samples 307-311 were prepared in the same manner as samples 201-205 except that emulsion EM-13c was replaced with an equal weight of emulsion EM-12c.

Control samples 312-315 were prepared in the same manner as samples 201-205 except that emulsion EM-13c was replaced with an equal weight of emulsion EM-3c.

Control samples 316-321 were prepared in the same manner as samples 201-205 except that emulsion EM-13c was replaced with an equal weight of emulsion EM-4.

Samples 322 to 329 were produced in the same manner as Samples 201 to 205, except that Emulsion EM-13c was replaced with Emulsion EM-5 of the same weight.

B. Effect of PUG-releasing compound releasing development inhibitor on developed element Samples 201-329 were exposed to light through a calibrated density test object and then as a color negative film by Kodak C-41 processing. Developed. This treatment was varied in that the bleaching solution consisted of ferric propylenediaminetetraacetate.

Useful latitude for each sample is Dmin for each sample
It was quantified by measuring the exposure required to allow a Status M density greater than 0.10 and the exposure required to allow a Status M density 0.10 less than Dmax. The greater the difference in exposure, the greater the useful latitude of the sample. Particularly useful are combinations of emulsions and development inhibitor releasing (DIR) compounds that allow a large increase in latitude. In addition, the photographic gamma of each sample was quantified as the rate of change in Status M density obtained after processing as a function of log exposure, with the exposure value towards the center of the useful latitude of the sample. Combinations of an emulsion and a DIR compound that allow a significant reduction in gamma are also particularly useful.

Table 7 below shows, for each sample, the emulsion name; DIR compound name and amount (g / m ² ); the relative gamma of the treated element (in each case, normalized to the corresponding control sample prepared without the DIR compound) And the relative latitude of the treated samples (in each case normalized to the corresponding control sample produced without the DIR compound).

Samples 201 to 211 contain either a cubic silver iodobromide emulsion or a tabular silver iodobromide emulsion similar to those typically used in combination with a DIR compound. These results show a large increase in latitude and a large decrease in gamma made possible by these combinations. Thus, combining specific amounts and types of DIR compounds with silver iodobromide emulsions to obtain the various latitude and gamma positions required for a particular application is well within the skill of the photographic artisan. .

Samples 301-315 contain cubic silver chloride emulsions known in the art. These results indicate that the combination of these cubic silver chloride emulsions with various DIR compounds typically leads, at best, to a very small increase in useful latitude and a small decrease in gamma. In some cases the latitude peaked out, while in other cases gamma increased. This property may be related to the overall sensitivity loss encountered with these combinations or to the change in Dmin.

Samples 317-321 and 323-329 show the combination of a plate-like {100} surface AgCl crystal and a DIR compound according to the present invention.

Photosensitive {100} plane tabular silver chloride emulsion and DIR according to the present invention
It will be readily appreciated that samples consisting of a combination with a compound will simultaneously produce a useful decrease in gamma with a large increase in latitude. These results are known
It is very surprising that 0 ° cubic silver chloride emulsions typically show only increased gamma (undesirable effects) and a small increase in latitude when used in combination with DIR compounds. The elements of the present invention simultaneously allow for both greater latitude gain and greater gamma suppression than can be obtained by combining DIR compounds with emulsions that have been optimized over the years by many skilled in the photographic arts. Doing is particularly noteworthy.

Exposure and processing steps using Kodak C-41 processing and analysis of the above data were performed on samples 201-221 and 301-329 using development times of 1 minute, 2 minutes, 3 minutes, 4 minutes, and 5 minutes. Repeated. The improvement in latitude and reduced gamma previously observed for the elements of the present invention compared to the control sample was maintained.

Varying the contact time between the photographic material and the processing solution, as described above in Example 2, is more typical for those skilled in the photographic arts to approximate the effect of changes in temperature or concentration of components in the processing solution. It is used for By such means,
Photographic artisans are able to select processing times and compositions, DIR compounds, dye-forming compounds and sensitized {100} face silver chloride tabular grain emulsions for particular applications in accordance with the present invention. .

Example 4-Preparation and processing of elements containing various image dye-forming coupler compounds and PUG releasing coupler compounds A. Preparation of elements Samples 901-969 were prepared generally as described for Sample 101 of Example 2. did. All of these samples were coated on a transparent support. Samples 970-972 were coated on a reflective support. All of these elements represent another illustration of the practice of the present invention. The type and amount of the silver halide emulsion and the type and amount of the image dye-forming coupler compound and the PUG releasing coupler compound used in each sample are shown in Table 8 below.

B. Dye Density Yield from Developed Elements Samples were exposed to light through a calibrated density test object and developed using the Kodak C-41 process. This treatment was varied in that the bleaching solution consisted of ferric propylenediaminetetraacetate. In each case, the Status M concentration in the red, green or blue band corresponding to the maximum absorption wavelength indicated by the sample was used. The transmission densities of the samples 901 to 969 were measured, and the reflection densities of the samples 970 to 972 were measured.

Table 8 shows the types and amounts of the emulsions and coupler compounds used in each element. The observed normalized dye concentration yield (DDY) and the wavelength band used (R, G or B) for each sample are also shown.

The above results demonstrate that excellent dye concentration yields were obtained with {100} plane silver chloride tabular grain emulsions and a wide variety of dye image-forming coupler compounds in combination with various PUG releasing coupler compounds. Is shown.

Samples 901-969 were exposed to white light through a calibrated density test object, developed for 45 seconds in a color photographic paper developer described in U.S. Pat. No. 4,892,804, then bleached and fixed. Again, good dye density formation from these elements was observed.

Example 5-Preparation and Processing of Elements Containing Various Development Inhibitor Release (DIR) Coupler Compounds A. Preparation of Elements Samples 401-412 were prepared by applying the following layers to the transparent support in the order listed. Manufactured. The amounts of the components are given in g / m ² .

Layer 1 (antihalation layer): consists of gray silver and gelatin.

Layer 2 (photosensitive layer): 0.33 g of EM-5, 1.82 g of gelatin, image dye-forming coupler (0.54 g) and D shown in Table 9 below
Consists of an IR compound.

Layer 3 (protective layer): consists of 2.15 g of gelatin.

These layers may further comprise α-4-nonylphenyl-ω-hydroxy-poly (oxy- (2-hydroxy-1,3-propanediyl)) and (para-t-
(Octylphenyl) -di (oxy-1,2-ethanediyl) sulfonate.

This film was treated with 2% by weight of bis-
The film was hardened at the time of coating with vinylsulfonylmethane.

B. Effect of DIR Coupler Compound on Resolution of Developed Elements Samples 401-412 to measure modulation transfer function (MFT) percent response as a function of in-plane spatial frequency
Was exposed to white light in a sinusoidal pattern. The sample was then developed using the Kodak C-41 process. The bleach used for the treatment was changed to consist of 1,3-propylenediaminetetraacetic acid. The exposed and processed elements were evaluated to determine the MFT percent response as a function of the number of spatial treatments in the plane of the film. The specific details of this exposure-evaluation cycle can be found in the Journal of Applied Photographic Engine
ering, Volume 6, pages 1-8, RLLamberts and FC, February 1980
Eisen, “A System for the Automatic Evaluation of M
odulation Transfer Functions of Photographic Mater
ials ".

The MTF percent response of the photosensitive layer of these samples was monitored at several spatial frequencies. Higher values of the MTF percent response indicate sharper images. In addition, the spatial frequency at which the MTF percent response drops to 70%, a measure of resolution, was measured. Higher spatial frequencies indicate films with excellent resolution. Table 9 also shows the results of this test.
Shown in

As can be seen, the elements of the present invention, including the various DIR compounds, all exhibited improved sharpness and generally improved resolution. Dye image-forming coupler compound and DIR
With the choice of the coupler compound, the specific spatial frequency increased and the extent of the increase are varied. Suitable combinations for a particular application are readily ascertained by one skilled in the art.

Example 6 Preparation and Development of Elements Containing Development Accelerator Release Compounds A. Preparation of Elements Samples 501-504 were prepared by applying the following layers to the transparent support in the order described. The amounts of the components are given in g / m ² .

Layer 1 (antihalation layer): consists of gray silver and gelatin.

Layer 2 (photosensitive layer): 0.43 g EM-10, 1.82 g gelatin, 0.1 g
At 54 g, it consists of image dye-forming coupler C-1 and a development accelerator releasing (DAR) compound described in Table 10 below.

Layer 3 (protective layer): consists of 2.15 g of gelatin.

These layers may further comprise α-4-nonylphenyl-ω-hydroxy-poly (oxy- (2-hydroxy-1,3-propanediyl)) and (para-t-
(Octylphenyl) -di (oxy-1,2-ethanediyl) sulfonate.

This film was treated with 2% by weight of bis-
The film was hardened at the time of coating with vinylsulfonylmethane.

B. Effect of Development Accelerator Release (DAR) Compounds on Element Sensitivity Samples 501-504 are exposed to white light through a calibrated density test object and then developed using Kodak C-41 processing. Processed. The bleach used for the treatment was changed to consist of 1,3-propylenediaminetetraacetic acid. The relative photographic sensitivity of the samples was then evaluated by measuring the exposure required to make a density 0.15 above Dmin with a normalized gamma of 1.0.

 These values are listed in Table 10.

As can be seen, all DAR compounds produced increased photographic speed within the elements of the present invention. Of course, the amount of increased sensitivity depends on the choice and amount of the dye image-forming compound and the DAR compound. Suitable combinations for a particular application are readily ascertained by one skilled in the art. DAR compounds can also be used in combination with other PUG releasing compounds described elsewhere herein.

Example 7-Preparation and Processing of an Element Containing a Bleach Accelerator Release Compound A. Preparation of the Element Except that the amounts and types of bleach accelerator release (BAR) compounds shown in Table 11 were added to the photosensitive layer. In a manner similar to that used to produce sample 501 of Example 6, samples 505-511
Was manufactured. To further illustrate the practice of the present invention, a development inhibitor releasing (DIR) compound was also added to some of the samples.

B. Influence of Bleaching Accelerator Release (BAR) Compounds Samples 501 and 505-511 were exposed to white light through a calibrated density test object for silver removal from the treated element, followed by US Pat. No. 4,892,804. Developed using the method described. The amount of metallic silver (g / m ² ) remaining in the treated element was determined by X-ray fluorescence. These values are listed in Table 11.

As can be seen, the BAR compounds function to facilitate the removal of metallic silver deposits that greatly reduce the color quality of the visualized or printed images from these films. Of particular note is the ability of the BAR compound to remove silver from the elements of the present invention that also contain a DIR compound whose presence typically leaves large amounts of metallic silver in the developed element.

Example 8-Preparation and development of an element containing a competing coupler releasing compound A. Preparation of the element Example 6 except that the amounts and types of competing coupler releasing (CCR) compounds shown in Table 12 were added to the photosensitive layer. Samples 512 and 513 were produced in a manner similar to that used to produce Sample 501.

B. Competitive coupler release type (CC
R) Influence of Compounds Samples 501, 512 and 513 were exposed to white light through a calibrated density test object and then developed using a Kodak C-41 process. The bleach used for the treatment was changed to consist of 1,3-propylenediaminetetraacetic acid. The relative photographic speed, gamma and maximum density of the processed elements were measured.
These values are listed in Table 12.

As can be seen from the above results, the CCR compound reacts competitively with the oxidized developing agent, thereby reducing the photosensitivity, density and gamma of the element of the present invention. Of course, the magnitude of these effects will depend on the choice of image-forming compound and CCR compound and the respective amounts used. Combinations suitable for a particular application are readily ascertained by one skilled in the art. CCR compounds can also be used in combination with other PUG releasing compounds described elsewhere herein.

Example 9-Preparation and Development of Elements Containing Electron Transfer Agent Release Compound A. Preparation of Elements Samples 514 and 515 were prepared by applying the following layers to the transparent support in the order described. The amounts of the components are given in g / m ² .

Layer 1 (antihalation layer): consists of gray silver and gelatin.

Layer 2 (photosensitive layer): 0.538 g of EM-5, 1.82 g of gelatin,
646 g of image dye-forming coupler C-31, 0.054 g of DIR Compound D-3 and 0.054 g of Compound B-1, and in Sample 515 0.032 g of electron transfer agent releasing (ETAR)
Consists of a compound.

Layer 3 (protective layer): consists of 2.15 g of gelatin.

These layers may further comprise α-4-nonylphenyl-ω-hydroxy-poly (oxy- (2-hydroxy-1,3-propanediyl)) and (para-t-
(Octylphenyl) -di (oxy-1,2-ethanediyl) sulfonate.

This film was treated with 2% by weight of bis-
The film was hardened at the time of coating with vinylsulfonylmethane.

B. Effect of Electron Transfer Agent Emitting (ETAR) Compounds on Element Sensitivity, Gamma and Concentration Samples 514 and 515 are exposed to white light through a calibrated density test object and then subjected to Kodak C-41 processing. And developed. The bleach used for the treatment was changed to consist of 1,3-propylenediaminetetraacetic acid. The relative sensitivity, gamma and maximum density of the processed elements were measured. Table 13 shows these values.

As can be seen, the ETAR compound improved the light sensitivity, density and gamma of the elements of the invention containing it. As shown in this example, ETAR compounds can also be used in combination with other PUG releasing compounds described elsewhere herein.

Example 10-Preparation and Development of an Element Containing a Bleach Inhibitor Release Compound A. Preparation of the Element Sample 516 was prepared in a manner similar to that used to manufacture sample 501.

B. Effect of Bleach Inhibitor Release (BIR) Compounds on Treated Elements Samples 501 and 516 are exposed to white light through a calibrated density test object and then described in US Pat. No. 4,892,804. And developed. The infrared concentration and the amount of metallic silver (g / m ² ) in the sample were measured. These values are listed in Table 14.

As can be seen, the BIR compound prevents bleaching of the processed element containing it, thereby making it possible to use the IR for applications such as movie soundtracks
Enables image-like formation of readable density. BIR compounds can also be used in combination with other PUG releasing compounds described herein.

Example 11-Preparation and Testing of a Multicolor Multilayer Photographic Element A. Preparation of the Element A color photographic element, Sample ML-101, was prepared by applying the following layers in the order described to a transparent support of cellulose triacetate. The amount of silver halide is g of silver
/ shown by m ^2. The amounts of other substances are given in g / m ² .

Organic compounds were used as emulsions or solutions containing coupler solvents, surfactants and stabilizers, both as commonly used in the art. The coupler solvents used in this photographic sample include tricresyl phosphate, di-n-butyl phthalate, N, N-di-n-ethyl lauramide, N, N-di-n-butyl lauramide, 4-di-t-amylphenol, N-butyl-N
-Phenylacetamide and 1,4-cyclohexylene dimethylene bis- (2-ethoxyhexanoate) were included. Mixtures of compounds were used as individual dispersions or as co-dispersions as commonly done in the art. This sample further contains sodium hexametaphosphate,
3,5-disulfocatechol disodium, gold sulfide,
It consisted of propargyl-aminobenzoxazole and the like. The silver halide emulsion was stabilized with 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.

Layer 1 (Antihalation layer): DYE-1 at 0.043 g; 0.021 g
DYE-2; C-39 at 0.065 g; DYE-6 at 0.215 g; gelatin at 2.15 g.

Layer 2 (lowest sensitivity red sensitized layer): 0.215 g of red sensitized silver chloride cubic emulsion, average edge length 0.28 μm; 0.592 g of red sensitized silver chloride {100} plane tabular emulsion, average equivalent circular diameter 1.2 μm, average particle thickness 0.14 μm; C-1 at 0.70 g; D-3 at 0.075 g; gelatin at 2.04 g.

Layer 3 (highest sensitivity red sensitized layer): 0.538 g of red sensitized silver chloride ｛1
00-plane tabular emulsion, average equivalent circular diameter 1.4 μm, average grain thickness 0.14 μm; C-1 at 0.129 g; D-15 at 0.032 g; gelatin at 2.15 g.

Layer 4 {Intermediate layer}: 1.29 g of gelatin.

Layer 5 (lowest sensitivity green sensitized layer): 0.215 g of green sensitized silver chloride cubic emulsion, average edge length 0.28 μm; 0.592 g of green sensitized silver chloride {100} plane tabular emulsion, average equivalent circular diameter 1.2 μm, average particle thickness 0.14 μm; C-2 at 0.323 g; D-17 at 0.022 g; 1.72 g
In gelatin.

Layer 6 (Green sensitized green sensitized layer): 0.538 g, green sensitized silver chloride
00｝ plane tabular emulsion average equivalent circular diameter 1.4 μm, average grain thickness 0.14 μm; C-2 at 0.086 g; D-16 at 0.011 g; gelatin at 1.72 g.

Layer 7 {intermediate layer}: gelatin 1.29 g.

Layer 8 (lowest sensitivity blue sensitized layer): 0.215 g of blue sensitized silver chloride cubic emulsion, average edge length 0.28 μm; 0.215 g of blue sensitized silver chloride {100} plane tabular emulsion, average equivalent circular diameter 1.2 μm, average particle thickness 0.12 μm; C-3 at 1.08 g; D-18 at 0.065 g; 1.72 g
In gelatin.

Layer 9 (highest sensitivity blue sensitized layer): 0.323 g of blue sensitized silver chloride ｛1
00｝ plane tabular emulsion, average equivalent circular diameter 1.4 μm, average grain thickness 0.14 μm; C-3 at 0.129 g; D-18 at 0.043 g; gelatin at 1.72 g.

Layer 10 {Protective layer}: DYE-8 at 0.108 g; unsensitized silver bromide Lippmann emulsion at 0.108 g; silicone lubricant at 0.026 g; tetraethylammonium perfluorooctanesulfonate; t-
Octylphenoxyethoxyethyl sulfonic acid sodium salt; 0.0538 g with anti-matte polymethyl methacrylate beads; 1.61 g with gelatin.

This film was treated with 2% by weight of bis-
The film was hardened at the time of coating with vinylsulfonylmethane. Surfactants, coating aids, scavengers, soluble sorbent dyes and stabilizers were added to the various layers of this sample, as is commonly done in the art. The total dry thickness of the photosensitized layers was about 13.7 μm and the dry thickness of all applied layers was about 19.5 μm.

Sample ML-102 was similar to Sample ML-101 except that Compound B-1 was added to Layer 2 at 0.043 g.

Sample ML-103 was prepared by adding 0.065 g of Compound C-42 to Layer 2, and adding 0.065 g of Compound C-42 to Layer 2.
Same as sample ML-102 except that 43 g was added to layer 3 and compound C-40 was added to layer 5 at 0.065 g and to layer 6 at 0.043 g.

In sample ML-104, the following compounds were added instead of compounds D-3, D-15, D-16, D-17 and D-18.
That is, 0.075 g of D-4 was added to the layer 2 and D-1 was added to the layer 3 at a concentration of 0.1 g.
032 g was added, 0.032 g of D-1 was added to layer 5, and D-
Sample ML-101 except that 0.011 g of No. 1 was added, 0.065 g of D-7 was added to Layer 8, and 0.043 g of D-7 was added to Layer 9.
Was similar to

Sample ML-105 was similar to Sample ML-104 except that Compound B-1 was added to Layer 2 at 0.043 g.

Sample ML-107 was identical to Sample ML except that the amount of silver chloride emulsion in layers 2, 3, 5, and 6 was doubled and the amounts of compounds D-1 and D-4 in these layers were also doubled. Same as -104.

Sample ML-108 doubled the amount of silver chloride emulsion in layers 2, 3, 5, and 6, and also reduced the amount of compounds D-3, D-15, D-16, and D-17 in these layers. It was the same as Sample ML-101 except that it was doubled. This change added about 1.0 μm to the film thickness.

Samples ML-201 to 205 and ML-207 to 208 were the same as in Samples except that the silver chloride emulsion was replaced in the photosensitive layer by a sensitized silver iodobromide emulsion consisting of about 3.7 mol% iodide as follows. ML
-101 to 105 and ML-107 to 108.

In layer 2: 0.215 g of red sensitized silver iodobromide emulsion, average equivalent circular diameter
0.5 μm, average grain thickness 0.08 μm; red-sensitized silver iodobromide emulsion,
Average equivalent circular diameter 1.0 μm, average grain thickness 0.09 μm.

In Layer 3: 0.538 g of (ML-201 to 205 and ML-207 to 208) red sensitized silver iodobromide emulsion, average equivalent circular diameter 1.2 μm, average grain thickness 0.13 μm.

Layer 5: 0.215 g of green sensitized silver iodobromide emulsion, average equivalent circular diameter
0.5 μm, average grain thickness 0.09 μm; green sensitized silver iodobromide emulsion at 0.592 g, average equivalent circular diameter 1.0 μm, average grain thickness 0.09 μm
m.

Layer 6: 0.538 g, green sensitized silver iodobromide emulsion, average equivalent circular diameter
1.2 μm, average particle thickness 0.13 μm.

In layer 8: 0.215 g blue sensitized silver iodobromide emulsion, average equivalent circular diameter
0.5 μm, average grain thickness 0.08 μm; blue-sensitized silver iodobromide emulsion at 0.215 g, average equivalent circular diameter 1.05 μm, average grain thickness 0.11 μm
m.

Layer 9: 0.323 g of blue sensitized silver iodobromide emulsion, average equivalent circular diameter
1.35 μm, average particle thickness 0.13 μm.

B. Density Measurement of Exposed and Developed Elements Samples were exposed to white light through a calibrated density test object and then developed using Kodak C-41 processing. The bleach used for the treatment was changed to consist of 1,3-propylenediaminetetraacetic acid.

The Status M density generated in the unexposed and undeveloped areas of each sample was measured after processing. The Status M density generated after processing at an exposure level of 10 stops above the ISO speed-point (ie, 3.0 log E) was measured. ISO Speed-Point is the exposure required to create a Status M density 0.15 above Dmin. The difference in concentration generation was calculated by subtraction. This difference represents the concentration generation for each sample. This value is shown in Table 15.

As can be seen, the density-producing ability of the multilayer multicolor element of the present invention is generally equal to or greater than that of an otherwise similar control sample containing a silver iodobromide emulsion.
In addition, elements made according to the present invention produced a more uniform density generation in the three color records than that obtained with the control sample. This greater uniformity in concentration generation
May be attributable to improved development in the underlying red sensitized layer in the element of the invention as compared to that in the control element.
This reduced dependence of dye density formation in a particular layer at the location of this layer of the element is a significant advantage of the present invention.

C. Measurement of photo-abrasion and pressure desensitization effect The pressure and abrasion sensitivity of the samples ML-101 to 105 and ML-207 to 208 were measured by attaching a steel wheel to which a part of each sample was sandblasted. Approximately 42 psi (2.9 × 10 ⁵
(Pascal). The hollows and ridges of the sandblasted wheel are, for example,
It mimics dirt particles or other imperfections on camera film transport mechanisms and the like.

Both pressurized and non-pressurized portions of each sample were exposed to white light through a calibrated density test object and then developed using a Kodak C-41 process. The bleach used for the treatment was changed to consist of 1,3-propylenediaminetetraacetic acid.

The magnitude of the pressure fog effect was quantified by comparing the blue status MDmin of the unpressurized portion of each sample to that of the pressurized portion of the same sample. The increase in density caused by the grinding wheel is pressure fog or light abrasion. The lower value of pressure fog indicates that this makes it less likely that a particular film composition will form unsightly marks and defects during use, for example, due to dirt or defects in the film transporter. Are better. This indicates an improved quality for prints made from such color films.

In related testing, by subjecting to a pressure of about 25psi a roller apparatus fitted with a polished wheel portion of each sample (1.7 × 10 ⁵ Pascal), it was evaluated separately for pressure desensitization samples. These samples were exposed and developed as described immediately above and the maximum difference in blue status M density between the pressed and unpressed samples was noted. The pressure from the polished wheel mimics the effect of pressure on the film sample, for example, as it occurs during winding or tight winding of the film or transporting on a tightly fitted clean roller mechanism. . Pressure tends to cause emulsion desensitization or density loss. Large density losses in photographic films should be avoided because prints made from such films can have unsightly marks and defects. For this reason, small values of pressure desensitization are desirable.

Table 16 shows the results of these light abrasion and pressure desensitization tests.

As can be seen, the samples prepared according to the present invention exhibited low pressure desensitization and significantly improved resistance to light abrasion when compared to control samples using a similarly sized silver iodobromide emulsion. .

D. Measurement of Masking Coupler Effect 1. Use of Cyan Dye-Forming, Preformed Magenta Dye Emitting Coupler Photographic Samples ML-102 and ML-103 are graduated and light passed through a density test object and Kodak Wratten 29 filter Exposure. This arrangement allows for red light separation exposure. The sample was then developed using the Kodak C-41 process. The bleach used for the treatment was changed to consist of 1,3-propylenediaminetetraacetic acid. The change between Dmin and Dmax in green status M density as a function of red light exposure was measured. This change in green density is shown in Table 17.

Sample ML-103 containing the masking coupler exhibited improved color separation properties, and the undesired green density associated with exposure and development of the red sensitized layer was reduced by the presence of the masking coupler C-42 in sample ML-103. Diminished.

2. Use of magenta dye-forming, preformed yellow dye-releasing coupler Photographic samples ML-102 and ML-103 were exposed to light through a calibrated density test object and Kodak Wratten 74 filter. This arrangement allows for green light separation exposure. The sample was then developed using the Kodak C-41 process. The bleach used for the treatment was changed to consist of 1,3-propylenediaminetetraacetic acid. The change between Dmin and Dmax in Blue Status M density as a function of green light exposure was measured. This change in blue density is shown in Table 18.

Sample ML-103 containing the masking coupler exhibited improved color separation properties, and the undesired blue density associated with exposure and development of the green photosensitized layer was reduced by the presence of the masking coupler C-40 in Sample ML-103. did.

E. Color Reversal Development Processing Photographic sample ML-101 was exposed to white light through a calibrated density test object and then developed according to Kodak E-6 reversal film processing.

 An inverted image suitable for direct viewing was formed.

Example 12-Preparation and testing of a multicolor multilayer photographic element A. Preparation of the element A color photographic element, Sample ML-301, was prepared by applying the following layers to the transparent support of cellulose triacetate in the order described. The amount of silver halide is g of silver
/ shown by m ^2. The amounts of other substances are given in g / m ² .

Organic compounds were used as emulsions or solutions containing coupler solvents, surfactants and stabilizers, both as commonly used in the art. The coupler solvents used in this photographic sample include tricresyl phosphate, di-n-butyl phthalate, N, N-di-n-ethyl lauramide, N, N-di-n-butyl lauramide, 4-di-t-amylphenol, N-butyl-N
-Phenylacetamide and 1,4-cyclohexylene dimethylene bis- (2-ethoxyhexanoate) were included. Mixtures of compounds were used as individual dispersions or as co-dispersions as is commonly done in the art. This sample further contains sodium hexametaphosphate,
3,5-disulfocatechol disodium, gold sulfide,
It consisted of propargyl-aminobenzoxazole and the like. The silver halide emulsion was stabilized with 2 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene per mole of silver.

Layer 1 {Antihalation layer}: gray silver at 0.323 g; gelatin at 2.44 g.

Layer 2 (lowest sensitivity red-sensitized layer): 0.269 g of red-sensitized silver iodobromide emulsion, about 4 mol% of iodide, average equivalent circular diameter 0.5 μm, average grain thickness 0.08 μm; red-sensitized at 0.538 g Silver iodobromide emulsion, about 3.7 mol% iodide, average equivalent circular diameter 1.0 μm, average grain thickness
0.09 μm; C-1 at 0.70 g; D-3 at 0.075 g; gelatin at 2.04 g.

Layer 3 {highest sensitivity red-sensitized layer}: 0.538 g of a red-sensitized silver iodobromide emulsion, about 3.7 mol% of iodide, average equivalent circular diameter of 1.2 μm, average grain thickness of 0.12 μm; 1; 0.065 g D-3; 2.15
Gelatin in g.

Layer 4 {Intermediate layer}: 1.29 g of gelatin.

Layer 5 {lowest sensitivity green sensitized layer}: green sensitized silver iodobromide emulsion at 0.269 g, iodide about 4 mol%, average equivalent circular diameter 0.5 μm, average grain thickness 0.08 μm; green sensitized at 0.538 g Silver iodobromide emulsion, about 3.7 mol% iodide, average equivalent circular diameter 1.0 μm, average grain thickness
0.09 μm; C-2 at 0.323 g; D-2 at 0.108 g; gelatin at 2.15 g.

Layer 6 {highest sensitivity green sensitized layer}: green sensitized silver iodobromide emulsion at 0.538 g, iodide about 3.7 mol%, average equivalent circular diameter 1.2 μm, average grain thickness 0.12 μm; 2; 0.065 g DIR compound D-16; 1.72 g gelatin.

Layer 7 {intermediate layer}: gelatin 1.29 g.

Layer 8 (lowest sensitivity blue sensitized layer): 0.161 g of blue sensitized silver iodobromide emulsion, about 4 mol% of iodide, average equivalent circular diameter 0.5 μm, average grain thickness 0.08 μm; blue sensitized at 0.269 g Silver iodobromide emulsion, about 3.7 mol% iodide, average equivalent circular diameter 0.72 μm, average grain thickness 0.09 μm; C-3 at 1.08 g; D-8 at 0.065 g; gelatin at 1.72 g.

Layer 9 (highest sensitivity blue sensitized layer): 0.646 g, blue sensitized silver iodobromide emulsion, about 9 mol% iodide, average equivalent circular diameter 1.3 μm;
g for C-3; 0.043 g for D-8; 1.72 g for gelatin.

Layer 10 {Protective layer-1}: DYE-8 at 0.108 g; DYE-9 at 0.161 g;
0.108 g of unsensitized silver bromide Lippmann emulsion; N, N, N-trimethyl-N- (2-perfluorooctylsulfonamide-
Ethyl) ammonium iodide; sodium tri-isopropylnaphthalenesulfonate; gelatin at 0.54 g.

Layer 11 {Protective Layer-2}: 0.026 g silicone lubricant; tetraethylammonium perfluorooctane sulfonate; t-octylphenoxyethoxyethylsulfonic acid sodium salt; 0.0538 g matte-preventing polymethyl methacrylate beads; 0.54 g gelatin.

This film was treated with 2% by weight of bis-
The film was hardened at the time of coating with vinylsulfonylmethane. Surfactants, coating aids, scavengers, soluble sorbent dyes and stabilizers were added to the various layers of this sample, as is commonly done in the art. The total dry thickness of the photosensitized layers was about 16.4 μm and the total dry thickness of all applied layers was about 21.7 μm.

Sample ML-302 was similar to Sample ML-301 except that the silver iodobromide emulsion was removed from Layers 8 and 9 and replaced with an equal weight silver chloride emulsion as described below.

In layer 8: cubic blue sensitized silver chloride emulsion at 0.43 g, average edge length 0.28 μm.

Layer 6: 0.646 g cubic blue sensitized silver chloride emulsion, average edge length 0.6 μm.

Photographic sample ML-303 was similar to photographic sample ML-301 except that the silver iodobromide emulsion was removed from layers 8 and 9 and replaced with an equal weight silver chloride emulsion as described below.

Layer 8: 0.43 g of {100} plane tabular blue-sensitized silver chloride emulsion, average equivalent circular diameter 1.2 μm, average grain thickness 0.14 μm.

Layer 9: 0.646 g, {100} plane tabular blue sensitized silver chloride emulsion, average equivalent circular diameter 1.4 μm, average grain thickness 0.14 μm.

B. Measurement of film optics in the lower layer of the processed element Sample ML-301, M to measure modulation transfer function (MFT) percent response as a function of spatial frequency in the plane of the film
L-302 and ML-303 were exposed to white light in a sinusoidal pattern. The sample was then developed using the Kodak C-41 process. The bleach used for the treatment was changed to consist of 1,3-propylenediaminetetraacetic acid. The exposed and processed elements were evaluated to determine the MFT percent response as a function of spatial frequency in the plane of the film. The specific details of this exposure-evaluation cycle can be found in the Journal of Applied P
hotographic Engineering, vol. 6, p. 1-8, Feb. 1980.
L. Lamberts and FCEisen, “A System for the Automat
ic Evaluation of Modulation Transfer Functions of
Photographic Materials ". A more general description of the measurement and meaning of MTF percent response curves is provided in the article cited in this reference.

MTF of green and red photosensitized layers of these multilayer multicolor films
Monitor percent response, 50 MTF percent response
The spatial frequency at which point falls to% was recorded. Higher spatial frequencies indicate films with excellent resolution. The average MTF percent response of the combined red and green records is also described. Table 19 shows the results of this test.

Samples ML-301 to ML-303 were the same except for the form and content of the emulsion contained in the blue sensitized layer. In these examples, the blue sensitized layer is closer to the exposure source than the green or red sensitized layer. According to the present invention, the blue light sensitized layer was sensitized to
By including a 0 ° plane tabular AgCl emulsion, the lower blue sensitized layer, as shown by comparison with results from control elements containing a cubic silver chloride emulsion or a tabular silver iodobromide emulsion, The resolution of the side layers was greatly improved. The MTF percent response at low spatial frequencies is also greatly improved.

Example 13-Preparation and testing of a multicolor multilayer photographic element having an inverted structure A. Preparation of the element A color photographic element, Sample ML-401, was prepared by applying the following layers to a transparent support of cellulose triacetate in the order described. Manufactured. The amount of silver halide is g of silver
/ shown by m ^2. The amounts of other substances are given in g / m ² .

Organic compounds were used as emulsions or solutions containing coupler solvents, surfactants and stabilizers, both as commonly used in the art. The coupler solvents used in this photographic sample include tricresyl phosphate, di-n-butyl phthalate, N, N-di-n-ethyl lauramide, N, N-di-n-butyl lauramide, 4-di-t-amylphenol, N-butyl-N
-Phenylacetamide and 1,4-cyclohexylene dimethylene bis- (2-ethoxyhexanoate) were included. Mixtures of compounds were used as individual dispersions or as co-dispersions as is commonly done in the art. This sample further contains sodium hexametaphosphate,
3,5-disulfocatechol disodium, gold sulfide,
It consisted of propargyl-aminobenzoxazole and the like. The silver halide emulsion was stabilized with 2 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene per mole of silver.

Layer 1- (AHU) {Antihalation agent}: DYE- at 0.043g
1; DYE-2 at 0.021 g; C-39 at 0.065 g; DYE-6 at 0.215 g; 2.1
Gelatin at 5g.

Layer 2- (SY) {lowest sensitivity blue sensitized layer}: Blue sensitized silver chloride at 0.43 g {100} planar tabular emulsion, average equivalent circular diameter 1.2 μm, average grain thickness 0.12 μm; yellow at 1.08 g Dye-forming image coupler C-3; D-18 at 0.108 g; gelatin at 1.72 g.

Layer 3- (FY) {highest light sensitivity blue sensitized layer}: blue sensitized silver chloride at 0.646 g {100} planar tabular emulsion, average equivalent circular diameter of 1.4 µm,
Average particle thickness 0.14 μm; yellow dye-forming image coupler C-3 at 0.129 g; D-18 at 0.086 g; gelatin at 1.72 g.

Layer 4- (IL) {Intermediate layer}: 1.29 g of gelatin.

Layer 5- (SC) {lowest sensitivity red sensitized layer}: red sensitized silver chloride at 0.807 g {100} tabular emulsion, average equivalent circular diameter 1.2 μm, average grain thickness 0.12 μm; cyan dye at 0.70 g Formable image coupler C-1; D-15 at 0.043 g; gelatin at 1.08 g.

Layer 6- (FC) {highest sensitivity red sensitized layer}: 0.538 g of red sensitized silver chloride {100} plane tabular emulsion, average equivalent circular diameter of 1.4 μm,
Average grain thickness 0.14 μm; cyan dye-forming image coupler C-1 at 0.129 g; D-15 at 0.048 g; gelatin at 1.08 g.

Layer 7- (IL) {Intermediate layer}: Gelatin 1.29 g.

Layer 8- (SM) {lowest sensitivity green sensitized layer}: 0.807 g of green sensitized silver chloride {100} plane tabular emulsion, average equivalent circular diameter 1.2 μm,
Average particle thickness 0.12 μm; magenta dye-forming image coupler C-2 at 0.323 g; D-17 at 0.065 g; gelatin at 2.15 g.

Layer 9- (FM) {highest sensitivity green sensitized layer}: 0.538 g of green sensitized silver chloride {100} plane tabular emulsion, average equivalent circular diameter of 1.4 μm,
Average particle thickness 0.14 μm; magenta dye-forming image coupler C-2 at 0.086 g; D-16 at 0.032 g; gelatin at 1.72 g.

Layer 10- (OC) {Protective layer}: DYE-8 at 0.108g; DYE at 0.118g
-9; unsensitized silver bromide Lippmann emulsion at 0.108 g; silicone lubricant at 0.026 g; tetraethylammonium perfluorooctane sulfonate; t-octylphenoxyethoxyethylsulfonic acid sodium salt; matt-preventing polymethyl methacrylate beads at 0.0538 g; 1.99 g In gelatin.

This film was treated with 2% by weight of bis-
The film was hardened at the time of coating with vinylsulfonylmethane. Surfactants, coating aids, scavengers, soluble sorbent dyes and stabilizers were added to the various layers of this sample, as is commonly done in the art. The total dry thickness of the photosensitized layers was about 10.5 μm and the total dry thickness of all applied layers was about 16.8 μm. Thus, the layer order of sample ML-401 was: support, AHU, SY, FY, IL, SC, FC, IL, SM, FM, OC.

In sample ML-402, 0.065 g of compound C-40 was added to layer 8- (SM).
And the same as Sample ML-401, except that 0.043 g was added to Layer 9- (FM).

In sample ML-403, 0.091 g of the compound C-43 was added to the layer 8- (SM).
And the same as Sample ML-401, except that 0.059 g was added to Layer 9- (FM). The amount of C-43 was equimolar to the amount of C-40 used in ML-402.

Sample ML-404 was prepared by applying the layers used in sample ML-401 to the support in the order AHU, SC, FC, IL, SM, FM, IL, SY, FY, OC as described below. .

Layer 1-(AHU) {Antihalation layer}: DYE at 0.043g
1; DYE-2 at 0.021 g; C-39 at 0.065 g; DYE-6 at 0.215 g; 2.1
Gelatin at 5g.

Layer 2- (SC) {lowest sensitivity red sensitized layer}: red sensitized silver chloride at 0.807 g {100} tabular emulsion, average equivalent circular diameter 1.2 μm, average grain thickness 0.12 μm; cyan dye at 0.70 g Formable image coupler C-1; D-15 at 0.043 g; gelatin at 1.08 g.

Layer 3- (FC) {highest light sensitivity red sensitized layer}: 0.538 g of red sensitized silver chloride {100} plane tabular emulsion, average equivalent circular diameter of 1.4 μm,
Average grain thickness 0.14 μm; cyan dye-forming image coupler C-1 at 0.129 g; D-15 at 0.048 g; gelatin at 1.08 g.

Layer 4- (IL) {Intermediate layer}: 1.29 g of gelatin.

Layer 5- (SM) {lowest sensitivity green sensitized layer}: 0.807 g of green sensitized silver chloride {100} plane tabular emulsion, average equivalent circular diameter 1.2 μm,
Average particle thickness 0.12 μm; magenta dye-forming image coupler C-2 at 0.323 g; D-17 at 0.065 g; gelatin at 2.15 g.

Layer 6- (FM) {highest sensitivity green sensitized layer}: 0.538 g of green sensitized silver chloride {100} plane tabular emulsion, average equivalent circular diameter of 1.4 μm,
Average particle thickness 0.14 μm; magenta dye-forming image coupler C-2 at 0.086 g; D-16 at 0.032 g; gelatin at 1.72 g.

Layer 7- (IL) {Intermediate layer}: Gelatin 1.29 g.

Layer 8- (SY) {Lowest sensitivity blue sensitized layer}: Blue sensitized silver chloride at 0.43 g {100} planar tabular emulsion, average equivalent circular diameter 1.2 μm, average grain thickness 0.12 μm; yellow at 1.08 g Dye-forming image coupler C-3; D-18 at 0.108 g; gelatin at 1.72 g.

Layer 9- (FY) {Highest sensitivity blue sensitized layer}: Blue sensitized silver chloride at 0.646 g {100} planar tabular emulsion, average equivalent circular diameter of 1.4 µm,
Average particle thickness 0.14 μm; yellow dye-forming image coupler C-3 at 0.129 g; D-18 at 0.086 g; gelatin at 1.72 g.

Layer 10- (OC) {Protective layer}: DYE-8 at 0.108g; DYE at 0.118g
-9; unsensitized silver bromide Lippmann emulsion at 0.108 g; silicone lubricant at 0.026 g; tetraethylammonium perfluorooctane sulfonate; t-octylphenoxyethoxyethylsulfonic acid sodium salt; matt-preventing polymethyl methacrylate beads at 0.0538 g; 1.99 g In gelatin.

For sample ML-405, 0.065 g of the compound C-42 was added to the layer 2- (SC).
And added to Layer 3- (FC) at 0.043 g to give Compound C-
40 was added to layer 5- (SM) at 0.065 g and layer 6- (FM) was added at 0.
Same as sample ML-404 except that 043 g was added.

B. Measurement of the Effect of the Masking Coupler Two different magenta dye-forming masking couplers, one containing the preformed yellow dye (C-4)
The results from the element containing (0) and the other (C-43) containing the protected dye, which became yellow only after processing, were compared.

Photographic samples ML-401 to ML-403 were exposed to light through a calibrated density test object and Kodak Wratten 74 filter. This arrangement allows for green light separation exposure. The sample was then developed using the Kodak C-41 process.
The bleach used for the treatment was changed to consist of 1,3-propylenediaminetetraacetic acid. The change between Dmin and Dmax in Blue Status M density as a function of green light exposure was measured. This change in blue density is shown in Table 20 below. Further, these samples were exposed to white light passing through a calibrated density test object, and the relative blue light sensitivity of the blue light sensitizing layer was monitored. These values are also shown in Table 20.

Samples ML-402 and ML-403 containing the masking coupler show improved color separation properties, and the undesired blue density associated with exposure and development of the green light sensitive layer is higher than that of masking coupler C-40 in sample ML-402. Presence and C in sample ML-403
Decreased by the presence of -43. It is also apparent that the blue light sensitivity has been substantially improved by the protected shifted masking function provided by C-43 as compared to the conventional masking function provided by C-40. So ML
-403 indicated a more desirable combination of blue sensitivity and color reproduction.

C. Influence of layer order on film optics of lower light red sensitized layer In samples ML-401 to ML-405, all of the photosensitive layers
It contains a 0-plane tabular silver iodobromide emulsion. Sample ML-404
And ML-405 have a standard layer sequence of a color film containing a silver iodobromide emulsion. That is, the blue sensitized layer is closer to the exposure source than the green or red sensitized layer. This layer order is such that when the silver iodobromide emulsion is all sensitive to blue light and a yellow colored filter layer is interposed between the layers spectrally sensitized to green or red light and an exposure source. It is standard for silver iodobromide emulsion films because good color separation is best obtained. The layer intended to be exposed by blue light is then located closer to the exposure source than the yellow filter layer. This layer order is no longer necessary because silver chloride emulsions have an inherent sensitivity to small blue light. Sample ML-401 to ML
-403 uses a reverse layer order in which the emulsion layer spectrally sensitized to blue light is more distant from the exposure source than the emulsion layer spectrally sensitized to green or red light. The resolution of the red sensitized layer is improved by removing the light scattering film components associated with the blue sensitized layer from the exposure light path for the red sensitized layer. This is shown below.

Sample ML-401 to measure modulation transfer function (MFT) percent response as a function of spatial frequency in the plane of the film
ML-405 was exposed to sinusoidal pattern white light. The sample was then developed using the Kodak C-41 process. The bleach used for the treatment was changed to consist of 1,3-propylenediaminetetraacetic acid. The exposed and processed elements were evaluated to determine the MFT percent response as a function of spatial frequency in the plane of the film. The specific details of this exposure-evaluation cycle are described in RLLamberts and FCEi above.
It is described in a report by sen.

The MTF percent response of the red sensitized layer of these multicolor multilayer films was monitored and the spatial frequency at which the MTF percent response dropped to 50% was recorded. Higher spatial frequencies indicate films with excellent resolution. Table 21 shows the results of this test.

As is readily apparent, film samples having the reverse layer order exhibited excellent resolution.

D. Measurement of Light Abrasion Effect Samples ML-401 through ML-405 were evaluated for pressure fog or light abrasion sensitivity as described above in Example 11-C.

The results of this evaluation are shown in Table 22 below. Smaller values of light abrasion indicate a film composition that is less sensitive to pressure events experienced during manufacture and use, such as pressures experienced during manufacturing and from rollers used to transport the film within the camera. . The resulting pressure marks cause unsightly defects in the final image.

As can be readily seen, all of these samples showed very low sensitivity to pressure fog or light abrasion.

Example 14-Preparation and Testing of Multicolor Multilayer Photographic Elements A. Preparation of Elements A color photographic element, Sample ML-501, was prepared by applying the following layers to a transparent support of cellulose triacetate in the order described. The amount of silver halide is g of silver
/ shown by m ^2. The amounts of other substances are given in g / m ² .

Organic compounds were used as emulsions or solutions containing coupler solvents, surfactants and stabilizers, both as commonly used in the art. The coupler solvents used in this photographic sample include tricresyl phosphate, di-n-butyl phthalate, N, N-di-n-ethyl lauramide, N, N-di-n-butyl lauramide, 4-di-t-amylphenol, N-butyl-N
-Phenylacetamide and 1,4-cyclohexylene dimethylene bis- (2-ethoxyhexanoate) were included. Mixtures of compounds were used as individual dispersions or as co-dispersions as is commonly done in the art. This sample further contains sodium hexametaphosphate,
3,5-disulfocatechol disodium, gold sulfide,
It consisted of propargyl-aminobenzoxazole and the like. The silver halide emulsion was stabilized with 2 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene per mole of silver.

Layer 1 (Antihalation layer): DYE-1 at 0.043 g; 0.021 g
DYE-2; C-39 at 0.065 g; DYE-6 at 0.215 g; gelatin at 2.15 g.

Layer 2 (lowest sensitivity red sensitized layer): 0.807 g, red sensitized silver chloride ｛1
00｝ tabular emulsion, average equivalent circular diameter 1.2 μm, average grain thickness 0.12 μm; 0.70 g, cyan dye-forming image coupler C
-1; 0.075 g for D-3; 2.04 g for gelatin.

Layer 3 (highest sensitivity red sensitized layer): 0.538 g of red sensitized silver chloride ｛1
00｝ tabular emulsion, average equivalent circular diameter 1.4 μm, average grain thickness 0.14 μm; 0.129 g, cyan dye-forming image coupler C
-1; 0.048 g for D-15; 2.15 g for gelatin.

Layer 4 {Intermediate layer}: 1.29 g of gelatin.

Layer 5 (lowest sensitivity green sensitized layer): 0.807 g of green sensitized silver chloride ｛1
00｝ tabular emulsion, average equivalent circular diameter 1.2 μm, average grain thickness 0.12 μm; magenta dye-forming image coupler C at 0.323 g
-2; 0.065 g for D-17; 2.15 g for gelatin.

Layer 6 (Green sensitized green sensitized layer): 0.538 g, green sensitized silver chloride
00 ° tabular emulsion, average equivalent circular diameter 1.4 μm, average grain thickness 0.14 μm; magenta dye-forming image coupler C-2 at 0.086 g; D-16 at 0.032 g; gelatin at 1.72 g.

Layer 7 {intermediate layer}: gelatin 1.29 g.

Layer 8 (minimum light sensitivity blue sensitized layer): 0.43 g blue sensitized silver chloride ｛10
0｝ plane tabular emulsion, average equivalent circular diameter 1.2 μm, average grain thickness 0.12 μm; 1.08 g, yellow dye-forming image coupler C
-3; 0.108 g for D-18; 1.72 g for gelatin.

Layer 9 (highest sensitivity blue sensitized layer): Blue sensitized silver chloride at 0.464 g
00 ° tabular emulsion, average equivalent circular diameter 1.4 μm, average grain thickness 0.14 μm; yellow dye-forming image coupler C-3 at 0.129 g; D-18 at 0.086 g; gelatin at 1.72 g.

Layer 10 {Protective layer}: DYE-8 at 0.108 g; unsensitized silver bromide Lippmann emulsion at 0.108 g; silicone lubricant at 0.026 g; tetraethylammonium perfluorooctanesulfonate; t-
Octylphenoxyethoxyethyl sulfonic acid sodium salt; 0.0538 g with anti-matte polymethyl methacrylate beads; 1.61 g with gelatin.

This film was treated with 2% by weight of bis-
The film was hardened at the time of coating with vinylsulfonylmethane. Surfactants, coating aids, scavengers, soluble sorbent dyes and stabilizers were added to the various layers of this sample, as is commonly done in the art. The total dry thickness of the photosensitized layers was about 14.4 μm and the total dry thickness of all applied layers was about 20.2 μm.

Sample ML-502 was similar to Sample ML-501 except that Compound B-1 was added to Layer 2 at 0.043 g.

Sample ML-503 was prepared by adding 0.065 g of Compound C-42 to Layer 2, and adding 0.065 g of Compound C-42 to Layer 2.
Similar to sample ML-502 except that 43 g was added to layer 3 and compound C-40 was added to layer 5 at 0.065 g and to layer 6 at 0.043 g.

In sample ML-504, the following compounds were added instead of compounds D-3, D-15 and D-18. That is, layer 2
, 0.075 g of D-1 was added to Layer 3, 0.048 g of D-1 was added to Layer 3, 0.108 g of D-7 was added to Layer 8, and D-7 was added to Layer 9.
Was the same as Sample ML-501 except that 0.086 g was added.

Sample ML-505 was similar to Sample ML-504 except that Compound B-1 was added to Layer 2 at 0.043 g.

Sample ML-506 contains 0.065 g of compound C-42 in layer 2, 0.0
Same as sample ML-505 except 43g was added to layer 3 and compound C-40 was added to layer 5 at 0.065g and to layer 6 at 0.043g.

Sample ML-507 doubled the amount of silver chloride emulsion in layers 2, 3, 5, and 6, and also reduced the amount of compounds D-1, D-4, D-16, and D-17 in these layers. It was the same as Sample ML-504 except that it was doubled. These changes add about 1.1 μm to the film thickness.

Sample ML-508 doubled the amount of silver chloride emulsion in layers 2, 3, 5, and 6, and also reduced the amount of compounds D-3, D-15, D-16, and D-17 in these layers. It was the same as sample ML-501 except that it was doubled.

B. Density Measurement of Exposed and Developed Elements Samples were exposed to white light through a calibrated density test object and then developed using Kodak C-41 processing. The bleach used for the treatment was changed to consist of 1,3-propylenediaminetetraacetic acid.

The status M density generated in the Dmin region of each sample was measured after the processing. The Status M density generated after processing at an exposure level of 10 stops above the ISO speed-point (ie, 3.0 log E) was measured. ISO Speed-Point is the exposure required to create a Status M density 0.15 above Dmin. The difference between Dmin and Dmax in density generation was calculated by subtraction. This difference represents the useful image density range for each sample. Table 23 shows Dmin or photographic fog density and useful image forming density.

As can be readily appreciated, the useful imaging densities of the multilayer multicolor elements prepared according to the present invention are equal to or greater than those of comparative commercial 100 speed film samples using silver iodobromide emulsions, but with fog. The value is smaller, resulting in improved image-fog discrimination. In addition, elements made in accordance with the present invention produced more uniform density generation in the three color records than commercial film samples.

C. Measurement of effect of masking coupler 1. Use of cyan dye-forming, preformed magenta dye-releasing coupler Photographic samples ML-502, ML-503, ML-505 and ML-506 are calibrated density test objects and Kodak Exposure to light through a Wratten 29 filter. This arrangement allows for red light separation exposure. The sample was then developed using the Kodak C-41 process. The bleach used for the treatment was changed to consist of 1,3-propylenediaminetetraacetic acid. The change between Dmin and Dmax in green status M density as a function of red light exposure was measured. Table 24 shows this change in green density.
Shown in

Samples ML-503 and ML-506 containing the masking coupler exhibited improved color separation properties, and the undesired green densities associated with exposure and development of the red sensitized layer were higher in Samples ML-503 and ML-5.
06 reduced by the presence of the masking coupler C-42.

2. Use of magenta dye-forming, preformed yellow dye-releasing coupler Light of photographic samples ML-502, ML-503, ML-505 and ML-506 passed through a calibrated density test object and Kodak Wratten 74 filter Exposure. This arrangement allows for green separation exposure. The sample was then developed using the Kodak C-41 process. The bleach used for the treatment was changed to consist of 1,3-propylenediaminetetraacetic acid. The change between Dmin and Dmax in Blue Status M density as a function of green light exposure was measured. This change in blue density is shown in Table 25.

Samples ML-503 and ML-506 containing the masking coupler exhibited improved color separation properties and reduced the undesired blue density associated with exposure and development of the green sensitized layer.

D. Overlay effect induced by solubilized thiol releasing couplers Samples ML-501, ML-502, ML-504 and ML-505 white light or Kodak Wratten through calibrated density test object
Exposed to red light using 29 filters. The sample was then developed using the Kodak C-41 process. The bleach used for the treatment was changed to consist of 1,3-propylenediaminetetraacetic acid.

The gamma of the cyan image formed in the red sensitized element of this sample was then measured under both exposure conditions. The ratio of the red density gamma formed after red light exposure divided by the red density gamma formed after white light exposure is the development suppression released into the green and blue light sensitizing elements during their development. Significant effect on red caused by product (onto red
It is a measure of the interimage effect). These products are not released from the green light sensitized layer and the blue light sensitized layer during the red light exposure and development process, but are released during the white light exposure and development process. In these film samples, the development inhibition product released is a development inhibitor released from the DIR compound intentionally added to the green and blue sensitized layers. Higher values of the gamma ratio measured in this way are indicative of greater color saturation in prints made from such negatives. Solubilized aliphatic thiol releasing compounds (compound B-1 is an example of such a solubilized thiol releasing compound) are known to hinder the inhibition reaction between the development inhibitor and the silver iodobromide emulsion. Have been. The samples evaluated in this test differ only in the presence or absence of compound B-1. Table 26 shows the results of this evaluation.

As can be seen, color saturation can be substantially suppressed by adding compounds capable of releasing solubilized aliphatic thiols in the elements of the present invention.

E. Overlay effect induced by development inhibitor releasing (DIR) compound Samples ML-501, ML-504, ML-507, ML-508 and commercially available 100 speed color negative film containing silver iodobromide emulsion Exposure to white light or red light using a Kodak Wratten 29 filter through a darkness test object. The sample was then developed using Kodak processing.
The bleach used for the treatment was changed to consist of 1,3-propylenediaminetetraacetic acid.

The gamma of the cyan image formed in the red sensitized element of this sample was then measured under both exposure conditions. The ratio of the red density gamma formed after red light exposure divided by the red density gamma formed after white light exposure is the development suppression released into the green and blue light sensitizing elements during their development. It is a measure of the layering effect on red caused by the product. These products are not released from the green light sensitized layer and the blue light sensitized layer during the red light exposure and development process, but are released during the white light exposure and development process. In these film samples, the development inhibition product released is a development inhibitor released from the DIR compound intentionally added to the green and blue sensitized layers. Higher values of the gamma ratio measured in this way are indicative of greater color saturation in prints made from such negatives. Table 27 shows the results of this evaluation.

As can be seen, substantial color saturation can be obtained in the elements of the present invention. Greater or lesser color saturation can be obtained as desired, depending on the choice of DIR compound used and the details of the construction of the element.

Example 15-Preparation and Testing of Multicolor Multilayer Photographic Elements A. Preparation of Elements A color photographic element, Sample ML-601, was prepared by applying the following layers in the stated order to a transparent support of cellulose triacetate. The amount of silver halide is g of silver
/ shown by m ^2. The amounts of other substances are given in g / m ² .

Organic compounds were used as emulsions or solutions containing coupler solvents, surfactants and stabilizers, as commonly used in the art. The coupler solvents used in this photographic sample include tricresyl phosphate,
Di-n-butyl phthalate, N, N-di-n-ethyl lauramide, N, N-di-n-butyl lauramide, 2,4
-Di-t-amylphenol, N-butyl-N-phenylacetamide and 1,4-cyclohexylene dimethylene bis- (2-ethoxyhexanoate) were included. Mixtures of compounds were used as individual dispersions or as co-dispersions as is commonly done in the art. This sample further consisted of sodium hexametaphosphate, disodium 3,5-disulfocatechol, gold (II) sulfide, propargyl-aminobenzoxazole, and the like. The silver halide emulsion contained 2 g of 4-hydroxy- / mol of silver.
Stabilized with 6-methyl-1,3,3a, 7-tetraazaindene.

Layer 1 (Antihalation layer): DYE-1 at 0.011 g; 0.013 g at DYE-1
DYE-2; C-39 at 0.065 g; DYE-6 at 0.108 g; DYE- at 0.075 g
9; gray colloidal silver at 0.215 g; SOL-1 at 0.005 g; SO at 0.005 g
L-2: 2.41 g gelatin.

Layer 2 {Intermediate layer}: 0.18 g, S-1; gelatin 1.08 g.

Layer 3 {lowest sensitivity red sensitized layer}: 0.538 g of red sensitized silver iodobromide emulsion, about 4 mol% of iodide, average equivalent circular diameter 0.5 μm, average grain thickness 0.08 μm; 1; 0.015 g D-15; 0.0
C-42 at 54 g; B-1 at 0.043 g; S-2 at 0.005 g; gelatin at 1.72 g.

Layer 4 (intermediate light sensitivity red-sensitized layer): 0.592 g of a red-sensitized silver iodobromide emulsion, about 3.7 mol% of iodide, average equivalent circular diameter of 1.0 μm, average grain thickness of 0.09 μm; 1; 0.015 g D-15; 0.0
C-42 at 32 g; D-17 at 0.005 g; S-2 at 0.005 g; gelatin at 1.72 g.

Layer 5 {highest sensitivity red-sensitized layer}: 0.592 g, red-sensitized silver iodobromide emulsion, about 3.7 mol% of iodide, average equivalent circular diameter 1.2 μm, average grain thickness 0.13 μm; 0.538 g; 0.086 g And C-1; 0.022 g and D
-15; 0.022 g for C-42; 0.016 g for D-17; 0.005 g for S-2;
Gelatin for 1,72g.

Layer 6 {intermediate layer}: 0.05-1 g S-1; gelatin 1.29 g.

Layer 7 {lowest sensitivity green sensitized layer}: 0.603 g of green sensitized silver iodobromide emulsion, about 4 mol% of iodide, average equivalent circular diameter of 0.57 μm, average grain thickness of 0.14 μm; 2; D-17 at 0.011 g; 0.0
C-40 at 43g; S-2 at 0.005g; gelatin at 1.4g.

Layer 8 (intermediate light sensitivity green sensitized layer): 0.592 g, green sensitized silver iodobromide emulsion, about 3.7 mol% iodide, average equivalent circular diameter 0.85 μm,
Average particle thickness 0.12 μm; C-2 at 0.086 g; D-17 at 0.016 g;
0.038 g for C-40; 0.005 g for S-2; 1.4 g for gelatin.

Layer 9 (highest sensitivity green sensitized layer): 0.592 g, green sensitized silver iodobromide emulsion, average equivalent circular diameter 1.05 μm, average grain thickness 0.12 μm;
0.086 g of C-2; 0.005 g of D-16; 0.038 g of C-40; 0.005 g
With S-2; 1.72 g with gelatin.

Layer 10 (middle layer): 0.05-1 g at S-1; 0.108 g at DYE-9; 0.108 g
And DYE-7; gelatin 1.29 g.

Layer 11 (lowest sensitivity blue sensitized layer): 0.172 g of blue sensitized silver iodobromide emulsion, about 4 mol% of iodide, average equivalent circular diameter 0.5 μm, average grain thickness 0.08 μm; blue sensitized at 0.172 g Silver iodobromide emulsion, about 3.7 mol% iodide, average equivalent circular diameter 0.70 μm, average grain thickness 0.09 μm; C-3 at 1.08 g; D-18 at 0.065 g; B-18 at 0.005 g.
1; S-1 at 0.011 g; gelatin at 1.08 g.

Layer 12 (highest sensitivity blue sensitized layer): Blue-sensitized silver iodobromide emulsion at 0.43 g, iodide about 3 mol%, average equivalent circular diameter 0.8 μm, average grain thickness 0.08 μm; 3; D-18 at 0.043g; 0.005
g at B-1; 0.011 g at S-2; 1.13 g at gelatin.

Layer 13 {Protective layer-1}: 0.118 g of DYE-8; 0.108 g of unsensitized silver bromide Lippmann emulsion; N, N, N-trimethyl-N- (2-perfluorooctylsulfonamido-ethyl) ammonium iodine Id; sodium tri-isopropylnaphthalenesulfonate; SOL-C1 at 0.043 g; DYE-1 at 1.06 g; 1.08 g
Gelatin in g.

Layer 14 {Protective Layer-2}: Silicone lubricant at 0.026 g; tetraethylammonium perfluorooctanesulfonate; t-octylphenoxyethoxyethylsulfonic acid sodium salt; 0.0538 g matte-preventing polymethyl methacrylate beads; 0.91 g gelatin.

This film was treated with 2% by weight of bis-
The film was hardened at the time of coating with vinylsulfonylmethane. Surfactants, coating aids, scavengers, soluble sorbent dyes and stabilizers were added to the various layers of this sample, as is commonly done in the art. The total dry thickness of the photosensitized layers was about 15.1 μm and the total dry thickness of all applied layers was about 23.1 μm.

Sample ML-602 was composed of layers 11 and 12 (two blue light-sensitized layers)
Sample ML-601 was similar except that the silver iodobromide emulsion therein was replaced with an equimolar amount of a cubic blue sensitized silver chloride emulsion as described below.

To layer 11, a blue-sensitized silver chloride cubic emulsion having an average edge length of 0.28 μm at 0.344 g was added, and to layer 12, a blue-sensitized silver chloride cubic emulsion having an average edge length of 0.43 g at 0.6 μm was added. Addition.

Sample ML-603 is composed of layers 11 and 12 (two blue light-sensitized layers)
The silver iodobromide emulsion in the above was added in an equimolar amount of ｛10
Sample M except that it was replaced with a 0｝ plane tabular blue sensitized silver chloride emulsion
Same as L-601.

Layer 11 has an average equivalent circular diameter of 0.344 g and 1.2 μm and 0.14
Blue sensitized silver chloride {100} face tabular emulsion having an average grain thickness of 0.1 μm was added to layer 12, 0.43 g at 1.43 μm average equivalent circular diameter and 0.14 μm.
Blue-sensitized silver chloride {100} plane tabular emulsion having an average grain thickness of m.

B. Measurement of film optics of the lower layer of the processed element Sample ML-601, M to measure the modulation transfer function (MFT) percent response as a function of spatial frequency in the plane of the film
L-602 and ML-603 were exposed to white light in a sinusoidal pattern. The sample was then developed using the Kodak C-41 process. The bleach used for the treatment was changed to consist of 1,3-propylenediaminetetraacetic acid. The exposed and processed elements were evaluated to determine the MFT percent response as a function of spatial frequency in the plane of the film. The specific details of this exposure-evaluation cycle are described in the aforementioned report by RLamberts and FCEisen.

The MTF percent response of the green and red sensitized layers of these multilayer multicolor films was monitored and the spatial frequency at which the MTF percent response dropped to 50% was recorded. Higher spatial frequencies indicate films with excellent resolution. Table 28 shows the results of this test.

The front reflection of the film sample was also measured as a function of the wavelength of the reflected light. The amount of light reflected at 600 nm from the front of the film sample is intended to be used with an auto-exposure camera that uses a light reflection monitor scheme to measure the scene illumination as part of an auto-exposure control sequence. It is important when you do. This value is also shown in Table 28.

Samples ML-601 to ML-603 were identical except for the form of the emulsion and the iodide content contained in the blue sensitized layer. In these samples, the blue sensitized layer is closer to the exposure source than the green or red sensitized layer. The {100} sensitized blue light sensitized layer according to the present invention, as can be seen by comparing results from control elements containing a cubic silver chloride emulsion or a tabular silver iodobromide emulsion in the upper blue sensitized layer. The resolving power of the lower layer was greatly improved by the inclusion of a planar tabular AgCl emulsion. {Ten
The reduced front reflection was also obtained by using the 0 ° plane tabular AgCl emulsion.

Example 16-Preparation and testing of a multicolor multilayer photographic element A. Preparation of the element A color photographic element, Sample ML-701, was prepared by applying the following layers in the order described to a transparent support of cellulose triacetate. The amount of silver halide is g of silver
/ shown by m ^2. The amounts of other substances are given in g / m ² .

Organic compounds were used as emulsions or solutions containing coupler solvents, surfactants and stabilizers, both as commonly used in the art. The coupler solvents used in this photographic sample include tricresyl phosphate, di-n-butyl phthalate, N, N-di-n-ethyl lauramide, N, N-di-n-butyl lauramide, 4-di-t-amylphenol, N-butyl-N
-Phenylacetamide and 1,4-cyclohexylene dimethylene bis- (2-ethoxyhexanoate) were included. Mixtures of compounds were used as individual dispersions or as co-dispersions as is commonly done in the art. This sample further contains sodium hexametaphosphate,
3,5-disulfocatechol disodium, gold sulfide,
It consisted of propargyl-aminobenzoxazole and the like. The silver halide emulsion was stabilized with 2 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene per mole of silver.

Layer 1 (Antihalation layer): DYE-1 at 0.011 g; 0.011 g at DYE-1
DYE-3; C-39 at 0.065 g; DYE-6 at 0.108 g; DYE- at 0.075 g
9; gray colloidal silver at 0.215 g; SOL-1 at 0.005 g; SO at 0.005 g
L-2: 2.41 g gelatin.

Layer 2 {Intermediate layer}: S-1 at 0.108g; B-1 at 0.022g; 1.08g gelatin.

Layer 3 (lowest sensitivity red sensitized layer): 0.538 g of red sensitized silver chloride ｛1
00｝ plane tabular emulsion, average equivalent circular diameter 1.2 μm, average grain thickness 0.12 μm; C-1 at 0.538 g; D-15 at 0.011 g; C-42 at 0.054 g; D-3 at 0.054 g; D-3; 0.032 g at C-41; 0.005 g at S-2;
Gelatin at 1.72g.

Layer 4 (intermediate photosensitivity red sensitized layer): 0.592 g with red sensitized silver chloride ｛1
00｝ plane tabular emulsion, average equivalent circular diameter 1.5 μm, average grain thickness 0.14 μm; C-1 at 0.075 g; D-15 at 0.011 g; C-42 at 0.032 g; D-17 at 0.032 g; D-17; 0.022 g at C-41; 0.005 g at S-
2; 1.72g gelatin.

Layer 5 (highest light sensitivity red sensitized layer): 0.592 g of red sensitized silver chloride ｛1
00｝ plane tabular emulsion, average equivalent circular diameter 2.2 μm, average grain thickness 0.12 μm; C-1 at 0.075 g; D-15 at 0.011 g; C-42 at 0.022 g; D-17 at 0.032 g; D-17; 0.011 g g at C-41; 0.005 g at S-
2; 1.72g gelatin.

Layer 6 {Intermediate Layer}: S-1 at 0.054 g; D-25 at 0.032 g; 1.08 g gelatin.

Layer 7 (lowest sensitivity green sensitized layer): 0.484 g, green sensitized silver chloride ｛1
00｝ plane tabular emulsion, average equivalent circular diameter 1.2 μm, average grain thickness 0.12 μm; C-2 at 0.355 g; D-17 at 0.022 g; C-40 at 0.043 g; D-8 at 0.022 g; D-8; 0.011 g for S-2; 1.13 g for gelatin.

Layer 8 (intermediate light sensitivity green sensitized layer): 0.592 g of green sensitized silver chloride ｛1
00｝ plane tabular emulsion, average equivalent circular diameter 1.5 μm, average grain thickness 0.14 μm; C-2 at 0.086 g; D-17 at 0.022 g; C-40 at 0.038 g; S-2 at 1.41 g; S-2; 1.4 Gelatin in g.

Layer 9 ｛Green sensitized layer with highest light sensitivity｝: 0.592 g, green sensitized silver chloride ｛1
00｝ plane tabular emulsion, average equivalent circular diameter 2.2 μm, average grain thickness 0.12 μm; C-2 at 0.075 g; D-16 at 0.022 g; C-40 at 0.038 g; D-7 at 0.022 g; 0.011 S-2 at g; gelatin at 1.35 g.

Layer 10 {Intermediate Layer}: S-1 at 0.054 g; DYE-7 at 0.108 g; 0.97 g gelatin.

Layer 11 (lowest sensitivity blue sensitized layer): 0.344 g of blue sensitized silver chloride cubic emulsion, average edge length 0.28 μm; C-3 at 1.08 g; 0.065
g at D-18; 0.065 g at D-19; 0.005 g at B-1; 0.011 g at S
-2; gelatin at 1.34 g.

Layer 12 ｛highest sensitivity blue sensitized layer｝: blue sensitized silver chloride cubic emulsion at 0.43 g, average edge length 0.6 μm; C-3 at 0.108 g; 0.043 g
D-18; 0.005 g at B-1; 0.011 g at S-2; 1.13 g at gelatin.

Layer 13 (Protective layer-1): DYE-8 at 0.054 g; DYE-9 at 0.108 g;
0.054 g DYE-10; 0.108 g unsensitized silver bromide Lippmann emulsion; N, N, N-trimethyl-N- (2-perfluorooctylsulfonamido-ethyl) ammonium iodide;
Sodium tri-isopropylnaphthalenesulfonate;
SOL-C1 at 0.043g; gelatin at 1.08g.

Layer 14 {Protective Layer-2}: Silicone lubricant at 0.026 g; tetraethylammonium perfluorooctanesulfonate; t-octylphenoxyethoxyethylsulfonic acid sodium salt; 0.0538 g matte-preventing polymethyl methacrylate beads; 0.91 g gelatin.

This film was treated with 2% by weight of bis-
The film was hardened at the time of coating with vinylsulfonylmethane. Surfactants, coating aids, scavengers, soluble sorbent dyes and stabilizers were added to the various layers of this sample, as is commonly done in the art. The total dry thickness of the photosensitized layers was about 12.1 μm and the total dry thickness of all applied layers was about 20.5 μm.

Sample ML-702 was composed of layers 11 and 12 (two blue light-sensitized layers)
Sample ML-701 was the same as Sample ML-701 except that the silver chloride cubic emulsion was removed therefrom and replaced by an equimolar amount of a {100} plane tabular blue-sensitized silver chloride emulsion as described below.

Layer 11 has an average equivalent circular diameter of 1.2 μm at 0.172 g and 0.12 g
blue-sensitized silver chloride {100} plane tabular emulsion having an average grain thickness of 0.1 μm and an average equivalent circular diameter of 1.5 μm at 0.172 g;
Blue-sensitized silver chloride {100} having an average grain thickness of 0.14 μm
Surface tabular emulsion was added. In layer 12, 0.43 g of 2.2 μm average equivalent circular diameter and 0.12 μm
Blue-sensitized silver chloride {100} plane tabular emulsion having an average grain thickness of m.

Sample ML-703 was similar to sample ML-702 except that coupler C-3 was removed from layers 11 and 12 and replaced with an equivalent amount of coupler C-29 as described below.

 To layer 11, 1.076 g of C-29 was added, and to layer 12, 0.108 g of C-29 was added.

Sample ML-704 was prepared using coupler C from layers 7, 8 and 9.
Except for -2, it was the same as sample ML-703 except that it was replaced with coupler C-18 as described below.

 To layer 7, 0.71 g of C-18 was added, to layer 8, 0.172 g of C-18 was added, and to layer 9, 0.151 g of C-18 was added.

Sample ML-705 was prepared using coupler C from layers 7, 8 and 9.
Except for -2, couplers C-15 and C-
Same as sample ML-703 except that it was replaced by 16.

To layer 7, 0.16 g of C-15 and 0.16 C-16 are added. To layer 8, 0.039 g of C-15 and 0.039 g of C-16 are added.
Then, to layer 9, 0.033 g of C-15 and 0.033 g of C-16 were added.

Sample ML-706 was prepared using coupler C from layers 7, 8 and 9.
Except for -2, the sample was the same as sample ML-703 except that the coupler C-15 was used as described below.

 Add 0.32 g of C-15 to Layer 7, 0.077 g of C-15 to Layer 8, and 0.068 g of C-15 to Layer 9.

Sample ML-707 was prepared by adding 0.006 g of DYE-2 to Layer 13 and adding 0.
Same as sample ML-706 except that 065 g of BA-1 was added to layer 1.

Sample ML-708 was prepared by adding 0.006 g of DYE-2 to Layer 13 and adding 0.
Same as sample ML-706 except that 258 g of BA-2 was added to layer 1.

B. Measurement of film optics of the lower layer of the processed element Samples ML-701 to ML-708 and a commercially available 100 speed color negative film comprising Exposure, then Kodak C
It was developed by -41 treatment. The sinusoidal pattern was evaluated to determine the percent MTF response as described in Example 14.

The MTF percent response of the red sensitized layer of these multilayer multicolor films was monitored and the spatial frequency at which the MTF percent response dropped to 50% was recorded. Higher spatial frequencies indicate films with excellent resolution. The results of this test are shown in Table 29.

As is readily apparent, the present invention provides a $ 10
The use of 0 ° tabular AgCl emulsions provided improved resolution in the lower layer as compared to those obtained using cubic silver chloride or silver iodobromide emulsions. This resolution was further improved by using a red light absorbing dye in the antihalation layer.

C. Measurement of Element Spark Sensitivity Samples ML-701 to ML-708 and a commercially available 100-speed color negative film consisting of a silver iodobromide emulsion in the radiation-sensitive layer were exposed to a spark discharge producing ultraviolet and visible light through the base. And then developed in Kodak C-41 processing with a modified bleach containing 1,3-propylenediaminetetraacetic acid. The relative sensitivity to white light and ultraviolet light of the red layer of the element using the silver chloride tabular emulsion according to the present invention and the control sample using the silver iodobromide emulsion were compared. The elements of the present invention, when adjusted to comparable visible light sensitivities, exhibit spark and electrostatic discharge characteristics of about 10
It showed a sensitivity to ultraviolet light that was reduced by a factor of 0 (ie, 1-0 logE).

Although the present invention has been described in detail with particular reference to preferred embodiments thereof, it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

 Hereinafter, specific embodiments of the present invention will be listed.

1. A color photographic element comprising a dispersion medium and silver halide grains and comprising a support having at least one radiation-sensitive emulsion layer having an image dye-forming compound in reactive association, comprising: A) at least 50% of the total grain projected area is occupied by tabular grains, each bound by {100} major faces having an adjacent edge ratio of less than 10, each having an aspect ratio of at least 2; A color photographic element wherein the emulsion layer also contains, in reactive association, a photographically useful group and a compound capable of reacting with an oxidized developing agent to thereby release the photographically useful group.

2. The color photographic element of embodiment 1 wherein the average aspect ratio is at least 5.

3. A color photographic element according to embodiment 1, wherein the average aspect ratio is greater than 8.

4. The color photographic element of embodiment 1, wherein the edge ratio is less than 5.

5. The color photographic element of embodiment 1, wherein the edge ratio is less than 2.

6. Embodiment 1 in which tabular grains have a thickness smaller than 0.3 μm
The described color photographic element.

7. Embodiment 1 in which tabular grains have a thickness smaller than 0.2 μm
The described color photographic element.

8. Embodiment 1 in which tabular grains have a thickness smaller than 0.06 μm
The described color photographic element.

9. The color photographic element according to embodiment 1, wherein the tabular grains contain at least 70 mol% chloride.

10. A color photographic element according to embodiment 1, wherein the tabular grains contain at least 90 mole percent chloride.

11. The color photographic element according to embodiment 10, wherein the tabular grains are silver iodochloride grains.

12. A color photographic element according to embodiment 1, wherein the photographically useful group is a development inhibitor.

13. A color photographic element according to embodiment 12, wherein the compound containing a development inhibitor is a coupler.

14. A color photographic element according to embodiment 12, wherein the development inhibitor is mercaptotetrazole, mercaptooxadiazole or mercaptothiadiazole.

15. A color photographic element according to embodiment 12, wherein the development inhibitor is benzotriazole or tetrazole.

16. The color photographic element of embodiment 1, wherein the photographically useful group is a bleach accelerator, development accelerator, competitive coupler, electron transfer agent, bleach inhibitor or dye.

17. A color photographic element according to embodiment 1, wherein the developing agent is a p-phenylenediamine developing agent.

18. The color photographic element according to embodiment 1, wherein the radiation-sensitive emulsion layer is blue-sensitized.

19. At least one red-sensitized silver halide emulsion layer, at least one green-sensitized silver halide emulsion layer, and at least one blue-sensitized silver halide emulsion layer, wherein at least one of these emulsion layers The color photographic element of embodiment 1 wherein the individual contains tabular grains bound by {100} major faces.

20. The color photographic element of embodiment 19 wherein at least one silver halide emulsion layer containing tabular silver chloride grains bound by {100} major faces is blue sensitized.

21. A color photographic element according to embodiment 19 wherein at least one silver halide emulsion layer containing tabular silver chloride grains bound by {100} major faces is red sensitized.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Blast, Thomas Brownell, New York, 14559, Rochester, Cottage Street 13 (72) Inventor Muscasky, Joe Edward United States, New York 14625, Rochester, Sherwood Drive 99 (72) Invention Hartsel, Debralin United States of America, New York 14612, Rochester, Snag Harbor Coat 42 (72) Inventor Black, Donald Lee United States of America, New York 14580, Webster, High Tower Way 803 (72) Inventor Marrill, James Parker United States of America, New York 14626 , Rochester, Club Apple Lane 156 (72) Bohan, Ann Elizabeth USA, 14610, New York, Rochester, Bamberg Avenue 71 Examiner Hiromi Ito (56) References JP-A-6-59360 (JP, A) JP-A-3-226730 (JP, A) JP-A-6 -242536 (JP, A) JP-A-7-225440 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03C 1/035

Claims (2)

(57) [Claims] 1. A color photographic element comprising a dispersion medium and a support comprising silver halide grains and having at least one radiation-sensitive emulsion layer having image dye-forming compounds in reactive association. (A) at least 50% of the total grain projected area is joined by {100} major surfaces having adjacent edge ratios less than 10,
Each being occupied by tabular grains having an aspect ratio of at least 2, wherein the tabular grains are silver iodochloride grains, and (B) the emulsion layer is also in a reactively related, Having a compound capable of reacting with an oxidized developing agent thereby releasing a photographically useful group;
A color photographic element wherein the photographically useful group is a development inhibitor, bleach accelerator, development accelerator, competitive coupler, electron transfer agent, bleach inhibitor or dye. 2. An emulsion layer comprising at least one red sensitized silver halide emulsion layer, at least one green sensitized silver halide emulsion layer and at least one blue sensitized silver halide emulsion layer. 2. The color photographic element of claim 1 wherein at least one of the above comprises tabular grains bound by {100} major faces.