JPH07507645A - Dye image-forming photographic elements - Google Patents

Abstract

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

Description

[Detailed description of the invention] Dye image-forming photographic elements field of invention The present invention relates to color photographic elements comprising radiation-sensitive tabular grain silver halide emulsion layers. related.

Background of the invention In the 1980s, improved strips in both single and porous layer formats were introduced. Peed sensitivity-granularity relationship, both on an absolute basis and as a function of binder hardening. Provides increased coverage, faster developability, increased thermal stability, and imaging sensitivity A wide range of features such as increased separation of intrinsic and spectral sensitization and improved image sharpness The discovery that the photographic advantages of Based on this, significant advances have been made in the field of silver halide photography.

An emulsion is classified as "tabular" when tabular grains account for at least 50% of the total grain projected area. grain emulsions). Its thickness in its equivalent circular diameter (ECD) When the ratio to grain size 1) is at least 2, the grains are generally tabular grains. It is believed that. The equivalent circular diameter of a particle has an area equal to the projected area of the particle It is the diameter of a circle.

The term "intermediate aspect ratio tabular grain emulsion" refers to an average tabular grain emulsion in the range of 5 to 8. It refers to an emulsion that increases the aspect ratio. The term “high aspect ratio tabular grain emulsion” J refers to emulsions having an average tabular grain aspect ratio greater than 8. term “Thin tabular grains” are tabular grains that generally have a thickness of less than 0.2 μm. It is understood that The term "ultrathin tabular grains" generally refers to grains with a thickness of 0.06 μm or less. They are understood to be tabular grains with a The term “high chloride” is low on a silver basis. Refers to particles containing at least 50 mol% chloride. Granules containing mixed halides Regarding children, halides are named in order of increasing molar concentration. For example, iodine Silveride has a higher molar concentration of chloride than iodide.

Tabular grain emulsions overwhelmingly contain tabular grains, which are irregular octahedral grains. It is. The regular octahedral particles each exist in a different +lit) crystallographic plane. Contains 8 identical crystal faces. The tabular irregular octahedron has (1111 two or more parallel twins separating two principal crystal planes that lie within a crystallographic plane Contains crystal planes. (111) major faces of tabular grains represent triangles or hexagons Shows triple symmetry. The tabular shape of the grains, if any, occurs after the inclusion of parallel twin planes. The twins become halogenated with the result that the grains grow on the sides with a slight increase in thickness. It is generally accepted that this results in the creation of favorable edge sites for silver precipitation. ing.

Although tabular grain emulsions have been used advantageously in a variety of photographic and radiographic applications, tabular grain emulsions have The need for row twinning plane formation and Both pose limitations. These drawbacks are considered in tabular grains containing high chloride concentrations. This is by far the most common case.

The silver chloride grains are regular cubic grains, i.e. bound by six identical +1001 crystal faces. It is generally recognized that particles tend to form. +111 in silver chloride emulsion Tabular grains bound by one face are often morphologically unstabilized and unbalanced. Return to flat plate shape.

Tabular grain silver bromide emulsions have been known in the art since the 1980s, but W The first tabular grain silver chloride emulsion was made in U.S. Pat. No. 4,399,215 to E. It was. These tabular grains exhibit +III) principal planes of triple symmetry existing in crystallographic planes. It was a twin crystal type. An ammoniacal double jet precipitation method was used.

The ammonia ripening agent makes the tabular grains thick (so the thickness of the tabular grains is was larger than that of silver bromide and silver bromoiodide tabular grain emulsions. Ammonia aging To achieve this, it is possible to create an increased minimum density (fog) in high chloride emulsions. It was also necessary to precipitate the emulsion at a known relatively high pH. Furthermore, inferior Tabular grains containing both bromide and iodide ions are used to prevent removed from the tabular grains early in their formation.

Wey, U.S. Pat. A twinning method has been developed to produce silver chloride bromide emulsions. This production method is high salt It was not successfully extended to chemical emulsions. The highest average reported in the example The average aspect ratio was 11.

Maskasky U.S. Patent No. 4.400.463 (hereinafter Maskasky I) has the significant advantage of allowing significant internal content of other halides. High salt containing tabular grains with parallel twin planes and (Ill　l major crystal planes) A strategy for producing compound emulsions was developed. This strategy applies specifically to selected synthesis points. The function of remer peptizer is to promote the formation of crystal planes. It was to be used in combination with a particle growth modifier. Adsorbed aminoa Zaindenes, preferably adenine and iodide ions, are useful grain growth modifiers. It was disclosed that.

Maskasky U.S. Patent No. 4.713.323 (hereinafter Maskasky II) is an aminoazaindene growth modifier and 3o micromol/g or less Parallel twin planes and +111) main using gelatin peptizer containing methionine technology by producing high chloride emulsions containing tabular grains with crystal faces. made significant progress in the standard. The methionine content of gelatin peptizers can be disadvantageously high. In some cases, a strong oxidizing agent (or alkylating agent, King et al., U.S. Pat. No. 4,942.1) MaSk aSkyII is a high bromide and iodine product made starting with conventional and general purpose peptizers. High chloride tabular grain emulsions containing chloride ions have been brought within the reach of the technology. .

Maskasky I and ■ produced high chloride emulsions with similar tabular grain contents. This stimulated further research on particle growth modifiers that can be used.

No. 4,804,621 to Tufano et al. as a particle growth modifier. Di(hydroamino)azines are used and are described in U.S. Pat. No. 4,78 by Takada et al. In No. 3.398, heterocycles containing divalent sulfur ring atoms are used, NiN15h U.S. Pat. No. 4,952,491 to Ika et al. discloses a spectral sensitizer and a divalent sulfur source. child-containing heterocycles and acrylic compounds are used, and the rice of Ishiguro et al. National Patent No. 4.983. -508, an organic bis-quaternary amine salt is used. There is.

Bogg U.S. Pat. No. 4.063.951 discloses that tabular grains are parallel (+001 The first tabular grain emulsions with major crystal faces have been reported. Bogg's tabular grains The grains exhibit square or rectangular major crystal faces and thus are similar to conventional tabular grains (Ill There was no triple symmetry of the l-principal crystal plane. In a unique example, Bogg is 4.1-1. Ammonia is used to produce silver bromoiodide tabular grains having aspect ratios within the range of 1. A near-ripening method was used.

The average aspect ratio of this emulsion was 2, with the highest aspect ratio grain (grain A in Figure 3) ) was reported to be only 4. Bogg stated that this emulsion contained less than 1% iodide. 99.5% bromide 0.5% iodide emulsion is shown. . Attempts to produce tabular grain emulsions by the Bogg method were unsuccessful.

Mignot, U.S. Pat. No. 4,386,156, uses square and rectangular primary crystals. Lack of ammonia ripening when producing silver bromide emulsions containing faceted tabular grains An improvement over Bogg is shown that avoids points. Mignot is especially suitable for bromide Silver halide ripening agents other than It requires aging in the absence of (ammonia).

Endo and Okaji, [Silver chloride crystal habit for forming tabular grains in emulsions] An Empirical Ru1e to Mod ifythe Habit of 5ilver Chloride to f orm Tabular Grains in anEmulsion) J , The Journal of Photographic 5science , 36 volumes.

pp. 182-188, 1988, produced in the presence of a thiocyanate ripening agent. A silver chloride emulsion is disclosed. Emulsion preparation according to the disclosed method involves mixing ( Ill) and a few tabular grains within the general grain population exhibiting (100) crystal faces. An emulsion was prepared containing:

Mumaw and H'augh, [Silver Halide Precipitation Coagulation Method (Silver H alide Precipitation Coalescence Process sses) J, Journal of Imaging Science, Volume 30, No. 5, September/October, 1986, pages 198-299 are essentially E. It is a repetition of ndo and Oka j i, and 5ection IV-B is particularly relevant. It's connected.

Symposium: Torino 1963, photography 5 science, C.

Semerano and Ll, &IazzucatoW, Focal Pre ss, pages 52-55 discloses the aging of cubic grain silver chloride emulsions for several hours at 77°C. has been done. During ripening, tabular grains appear and the original cubic grains undergo Ostwald ripening. decreased due to the growth of After 3 hours of aging, as shown by Preparation ■ below, the plate The shaped grains account for only a small portion of the total grain projected area, and only a small portion of the tabular grains account for 0.3 The thickness was less than μm. more than proceeding beyond the actual teaching given In the study, prolonged aging removed many smaller cubic particles, but also Many tabular grains were degraded to thicker forms.

January 26, 1990 Japanese Publication H No. 2-024643 KaPCTilfN Cited as related to the tabular grain structure described in the scope of the report However, in the inventor's opinion, they are not related. The present invention relates to hydrazide derivatives and 0. Directed to negative-working emulsions containing tabular grains with an equivalent circular diameter of 6 to 0.2 μm. ing. Only conventional tabular grain production is disclosed, including silver bromide and silver bromoiodide. Emulsions are merely exemplified.

The above-cited U.S. Pat. No. 4,952,491 to NiN15hika et al. Using tabular silver halide emulsions with high chloride content in color photographic elements is disclosed. The tabular grains described in this patent are shown in Figures 1 and 1 of that patent. As illustrated in FIG. 2, they are bonded by the (111) main crystal plane.

The use of image-forming compounds in color photographic elements has been known for many years. Ru. Typically, these compounds interact with the silver halide emulsion layers in such elements. used in a reactively related state. During the development process, the dye-forming compounds are oxidized It reacts with a developing agent (hereinafter referred to as oxidized developing agent) to form a dye. developed The greater the dye density that can be obtained for a given amount of silver, the higher the photosensitivity The silver halide grains are smaller and give more dye density than the less sensitive grains. The texture of the silver halide grains in the emulsion layer greatly affects Ru. Therefore, silver halide that can provide both high sensitivity and high dye density formation There remains a need for combinations of emulsions and image dye-forming compounds. . This need is due to the fact that high chloride content desirably allows faster and easier development, bleaching, and High salt as it allows for faster and easier processability including whites and fixes This is particularly evident in silver halide emulsions with a high oxide content. Unfortunately, the high Silver halide emulsions with high chloride content that also exhibit true sensitivity are difficult to produce. be.

The silver halide emulsion layer contains photographically useful groups released by reaction with oxidized developing agents. Advantageous effects can be obtained when used in color photographic elements consisting of compounds containing It is also known that Such compounds have an interlayer effect. fruit or interimage effect or image accu To obtain the desired effect, such as the in+age accutance effect. used for These compounds are simply [photographs] as described more fully later. It is said to be a radical-releasing compound j that is useful in 4.409.323 and 4.861.701 and European patent applications No. 354.532. Such photographically useful group-releasing compounds Examples are development inhibitor releasing (D[R) compounds known in the photographic art. D.I.R. The compounds release development inhibitors during photographic processing, and such development inhibitors Can be used to give various photographic effects like reduction, curved shape It can be used to control. Unfortunately, development inhibitor-releasing compounds has limited utility in cubic silver halide emulsions with high chloride contents. Ru. It is important to note that when such compounds are used with such emulsions, latitude This is because it tends to have a slight influence on de or gamma. Furthermore, DIR compound Often there is a loss of sensitivity with such emulsions.

Image-forming compounds and DIR compounds that do not suffer from the disadvantages described above are well known in the art. tabular silver halide in combination with photographically useful group-emitting compounds such as Radiation-sensitive tabular grain emulsion layer consisting of grains, especially grains with high chloride content Clearly, it would be highly desirable to have a color photographic element containing . Main departure It is the object of the present invention to provide such color photographic elements.

Related patent applications In a continuation-in-part of U.S. Patent Application No. 764.868, filed September 24, 1991. A continuation in part of U.S. Patent Application No. 955.010, filed IO 1/1992. Maskasky U.S. Patent Application No. 1, filed on the same date as the present application. , Name of the invention rHigh Tabularity High Chloride Emulsions with [nherently 5table Gra in FacesJ (commonly assigned, hereinafter referred to as Maskasky III) contains no iodide internally and contains tabular grains with 1001 major faces. High aspect ratio tabular grain high chloride emulsions are disclosed. in a desirable shape Therefore, in Maskasky III, in order to facilitate the formation of the floo l main surface, a common Organic compounds containing a nitrogen atom with a ring-stabilizing pi-electron pair have been used.

In a continuation-in-part of U.S. Patent Application No. 826.338, filed January 27, 1992. Continuation-in-part of U.S. Patent Application No. 940.404, filed September 3, 1992. House, Brust, Harts filed on the same date as the present application. U.S. Patent Application No. ell and Black, Title: rHigh Aspe ctRatio Tabular Grain Emulsions J (it Commonly assigned) have an adjacent principal surface edge ratio of less than 10 and an edge ratio of less than 0.3 μm. Selected based on small thickness criteria, all remaining flats satisfying these criteria having a higher aspect ratio than the platelet particles, (1) an average aspect ratio greater than 8; and (2) internally at the nucleation site iodide and at least 50 mole percent Bonded by the +1001 principal plane, which contains chloride and accounts for 50% of the total grain projected area. Emulsions are disclosed containing tabular grains that have been modified.

Brust, House, which was filed on the same date as the present application and has been normally assigned.

Hartsell and Black U.S. Patent Application No. rMode rate Aspect Ratio Tabular Grain Emul sions and ProcessesTheir Preparation J discloses a radiation-sensitive emulsion consisting of a dispersion medium and silver halogenide grains. ing. At least 50% of the total grain projected area has an adjacent edge ratio of less than 10. are joined by +1001 major surfaces having aspect ratios of at least 2 and 8, respectively. has an average aspect ratio of less than or equal to iodide and at least Also dominated by tabular grains containing 50 mol% chloride. of this emulsion A manufacturing method is also disclosed.

In a continuation-in-part of U.S. Patent Application No. 826.338, filed January 27, 1992. Continuation-in-part of U.S. Patent Application No. 940.404, filed September 3, 1992. House, Brust, filed on the same date as the present application.

1 (artsell, Black, Antoniades, Tsaur and and Chang's U.S. Patent Application No. 1, titled rProcesses of P reparing Tabular GrainEmulsionsJ (it (commonly assigned to each) has an adjacent principal surface edge ratio smaller than IO and less than 0.3 μm. Selected on the basis of small thickness criteria and internally contains iodide and Containing at least 50 mol% chloride, accounting for 50% of the total grain projected area (1 001 A method for producing an emulsion containing tabular grains bonded by major faces, the method comprising: 1) Introducing silver and halide salts into the dispersion medium to eliminate the halogens present in the dispersion medium. tabular in the presence of iodide with chloride accounting for at least 50 mol% of the genide to cause particle nucleation and to bring the pct of the dispersion medium within the range of 0.5 to 3.5. and (2) maintaining an average aspect ratio of tabular grains greater than 8 following nucleation. Grain growth is completed under conditions that maintain the (+00) principal plane of the tabular grains until the A method comprising a step of tying is disclosed.

PUCkett's U.S. patent application filed on the same date as the present application and normally passed Y1 No., Name of Invention rOrigomer Modified TabularG Rain Emulsions J describes radiation-sensitive emulsions and their manufacturing methods. Disclosed. At least 50% of the total particle projected area is comprised of adjacent particles smaller than IO. having a zigzag ratio (100') joined by major surfaces, each having at least 2 asperes. and on average at least one pair of groups, period 5 and 6. High chloride tabular containing metal ions at adjacent cation sites within its crystal lattice dominated by particles.

Partial continuation of U.S. Patent Application No. 826.338 filed on January 27, 1992 A partial continuation of U.S. Patent Application No. 940.404 filed September 3, 1992. Brust, House, filed on the same date as the present application.

Name of invention rcoordination Complex Ligandλ1o defined TabularGrain Emulsions J (each (commonly assigned) has an adjacent principal surface edge ratio of less than 10 and an edge ratio of less than 0.3 μm. selected based on thin thickness criteria and any remaining slabs that satisfy these criteria (1) have an average aspect ratio greater than 8; and (2) internally at the nucleation site iodide and at least 50 mole percent salt. Bonded by the (+00) main surface that contains compounds and occupies 50% of the total grain projected area Emulsions are disclosed containing tabular grains that have been modified.

The tabular grains contain non-halide coordination complex ligands.

Budz, Ligtenber filed on the same date as the present application and commonly assigned U.S. Patent Application No. g and Roberts, title of the invention rDigi talI Maging With Tabular Grain Emulsions J includes a dispersion medium and a halogen containing at least 50 mole percent chloride, based on silver. A photograph that digitally forms an image containing a tabular grain emulsion consisting of silveride grains. elements are disclosed. At least 50% of the total grain projected area is less than 1o having an adjacent edge ratio (1001 connected by major faces, each having at least 2 as It is dominated by tabular grains with a specific aspect ratio.

Szajewski U.S. patent application filed on the same date as this application and commonly assigned. The name of the invention, rFi1m and Caa+era J, includes a dispersion medium. and silver halide grains containing at least 50 mole % chloride, based on silver. roll films and rolls comprising at least one emulsion layer comprising tabular grain emulsions; A camera containing film is disclosed. The total particle projected area is small (both 50% , connected by (100) major planes that grow adjacent edge ratios smaller than lO, respectively. It is dominated by tabular grains having an aspect ratio of at least 2.

Lok and Budz patent applications filed on the same date as this application and commonly assigned. Request tube number, name of invention rTabular Grain EmulsionsCo taining Antifoggants and 5 tabilizer sJ includes a dispersion medium, a halogen containing at least 50 mole percent chloride, based on silver; a silver oxide particle and at least one selected antifoggant or stabilizer. A platelet grain emulsion is disclosed. The total particle projected area is small (both 50% and 10%). have a smaller adjacent edge ratio (connected by 1001 major surfaces, each with at least It is dominated by tabular grains with an aspect ratio of 2.

Commonly assigned U.S. patent application filed by IJaskasky on the same date as the present application. Request tube number, name of invention rModerate Aspect Rati.

Tabular Grain High Chloride Emulsion s with Inherently 5tableGrain FacesJ is internally iodide-free and at least 50 mole percent chloride at the grain nucleation sites. An emulsion is disclosed that includes a population of grains consisting of: At least the particle population projected area 50% each have an aspect ratio of at least 2, with an average of 7.5 or less The floO' aspect ratio is occupied by tabular grains.

Buchanan and Szaje filed on the same date as the present application and commonly assigned. U.S. patent application number of wski, title of invention Q (method of process) sing Photographic Elements Containin g　Tabular　GrainEmulsions　J lists the species described therein. Development of dye image-forming photographic elements containing high chloride (100+ tabular grain emulsions) An image and desilvering method are disclosed.

Summary of the invention According to the present invention, the inventors have determined that (by the 1001 main surface) Novel tabular grain silver halide emulsions containing bonded tabular grains that It has been found that it has a unique morphology that makes it particularly useful in color photographic elements. Therefore, - In one aspect, the present invention comprises a dispersion medium and silver halide grains and a reactive a radiation-sensitive emulsion of at least lal having an image dye-forming compound in associated states; This invention relates to a color photographic element having a layered support. At least the total particle projected area Also 50% have an adjacent edge ratio less than 10 (connected by 1001 major surfaces) are dominated by tabular grains each having an aspect ratio of at least 2. . This emulsion layer also contains photographically useful groups that react with and bind oxidized developing agents. is in reactive association with a compound capable of releasing this photographically useful group. Ru.

An important feature of the invention is that this color photographic element can be developed by conventional color processing techniques. It is possible to obtain processed elements that exhibit exceptional image sharpness when imaged. . Additionally, as shown in the Examples below, oxidized developing agents (i.e., oxidized developing agents) The present invention comprises photographically useful groups such as development inhibitor groups released upon reaction with Color photographic elements are comparable to prior art halides consisting of cubic silver halide grains. The magnitude of the latitude is completely unexpected in the light of the results obtained with silver emulsions. provides the desired reduction in gamma with a simultaneous increase. Also, as shown in the later example As such, the present invention provides compounds that release various photographically useful groups in the practice of the present invention. Great flexibility in choosing the specific photo activity desired as it can be used with provide sex. For example, suitable photographically useful groups include development inhibitors, development accelerators, etc. , bleach inhibitors, bleach accelerators, electron transfer agents or couplers such as racing couplers. be caught.

The present invention is facilitated by the discovery of a novel approach to forming tabular grains. flat Formed to produce tabular properties, thereby producing tabular grains having (111) major faces. When manufacturing, instead of containing parallel twin planes in the grain, a selected pcl range is The high chloride nucleation process, coupled with keeping chloride ions in solution within the When iodide is present in the dispersion medium, the tabular grains are It has been discovered that this results in the formation of a bonded tabular grain emulsion.

The above approach to forming tabular grains allows for the creation of previously unrealized grain compositions and grain thickness (tabular grains bound by +001 crystal faces) Put it within the range. For example, if the particles are connected by +100) crystal faces, Thin tabular grain emulsions can be obtained. As described herein in a preferred form The proposed method produces medium and high aspect ratio tabular grains with high salt content that exhibit high levels of grain stability. can be used to provide compound emulsions. The tabular grain has (+111 main face Unlike high chloride tabular grain emulsions, which have a It does not require morphological stabilizers adsorbed to the major surface of the particles to maintain its morphology. most Later, although obviously applicable to the high chloride pore side, the present invention Each can be prepared by various precipitation methods that do not require the presence of iodide. It extends to silver chloride emulsions and silver bromochloride emulsions that can be used.

Brief description of the drawing FIG. 1 shows exemplary emulsion preparation, typical emulsions useful in color photographic elements of the present invention. Shadowed button microphotograph of carbon particle replica of a typical emulsion produced by Production I It is.

Figure 2 shows a sample of carbon grain replicas of the control emulsion produced by Example Emulsion Production and Production ①. This is a microscopic photograph of II with Yadou.

Description of preferred embodiments The identification of emulsions satisfying the requirements of this invention and the significance of the selection parameters are typical of This can be better understood by considering the emulsion. Figure 1 shows example 1 below. Shadowed carbon grain replicas of representative emulsions of the invention described in detail in This is a microscopic photograph of the glume. Most of the particles have rectangular (square or rectangular) faces. It is immediately clear that it has. These are +1 for the rectangular shape of the particle surface. This shows that it is a 001 crystal plane.

The projected area of a few particles in a sample that does not have a square or rectangular surface is the projected area of all particles. Although noted for inclusion in the product calculation, these particles clearly have a [001 principal surface is not part of the tabular grain population.

A few particles that are needle-shaped or rod-shaped particles (hereinafter referred to as rod-shaped particles) may be observed. do not have. These particles are more than 10 times longer in one dimension than all other dimensions; Excluded from the desired tabular grain population based on a high percentage of edge lengths. stick-shaped object The projected area occupied by is low, but when rod-shaped objects exist, their projected area is noted to determine the total particle projected area.

All remaining particles have square or rectangular major faces exhibiting the +001 crystal plane. Ru. To identify tabular grains, for each grain the ECD thickness 1) It is necessary to determine the ratio, ie ECD/t.

ECD is determined by measuring the projected area (product of edge length) of the top surface of each particle. be done. The ECD of the particle is calculated from the particle projected area. Particle thickness is usually individual Determined by oblique illumination of the particle population which causes the particles to cast shadows. lighting angle From the knowledge of (shadow angle), calculate the thickness of the particle by measuring its shadow length. It is possible to at least two ECDs each with square or rectangular faces; Grains having a ratio of /t are tabular grains having (100) major faces. (100 ) When the projected area of tabular grains accounts for at least 50% of the total grain projected area, The emulsion is a tabular grain emulsion.

In the emulsion of Figure 1, tabular grains account for more than 50% of the total grain projected area. Ru. From the above definition of tabular grains, the average aspect ratio of tabular grains is the minimum limit. It is clear that we can only get close to 2. In fact, the present invention Tabular grain emulsions typically exhibit average aspect ratios of 5 or greater, with high flat grain emulsions. An average aspect ratio (>8) is preferred. That is, preferred emulsions according to the present invention have high as It is a tabular grain emulsion. In particularly preferred emulsions according to the invention, flat plate The average aspect ratio of the shaped particle population is at least 12, optimally at least 20. Ru. Typically, the average aspect ratio of the tabular grain population is in the range of 50 or less, High aspect ratios of 100.200 or greater are possible. average ass Emulsions within the meaning of this invention whose aspect ratio approaches the minimum average aspect ratio limit of 2 are , further gives a surface area to volume ratio that is 200% of that of a cubic particle.

This tabular grain population has any grain thickness consistent with the average aspect ratio above. You may also indicate However, in particular, selected tabular grain populations have high average When indicating aspect ratio, the grains included in the selected tabular grain population are expressed as 0.3μ further limiting to those exhibiting a thickness of less than m, optimally less than 0.2 μm. is preferable.

The aspect ratio of a tabular grain limits its equivalent circular diameter or increases its thickness. It is acknowledged that restrictions can be imposed by That is, a collection of tabular grains When the average aspect ratio of the group is within the range of 2 to 8, the total projected area of the particles is at least The tabular grains, which account for 50% of the grains, are also smaller than 0.3 μm or 0.2 μm, respectively. Indicates smaller grain thickness. Nevertheless, within the aspect ratio range of 2-8 In particular, certain photographic applications benefit from larger tabular grain thicknesses. There is. For example, when constructing the pre-recording emulsion layer with the maximum achievable sensitivity, an average of 1μ It has been found that tabular grain thicknesses of m or even greater can be tolerated. Especially intended. This is because the eye is minimally sensitive to blue records, and even more so. This is because a high level of image granularity (noise) can be tolerated without objection. blue record It is sometimes difficult to match the highest sensitivity achievable with line recording and optical recording. In blue records, there is an additional incentive to use larger particles. this difficulty The source of this is the lack of blue photons in sunlight. Based on energy standards, sunlight has blue, green, and red light. The shorter the wavelength, the higher the energy the particle has. So Based on photon distribution standards, sunlight is slightly lacking in blue.

The tabular grain population preferably has a major surface edge of less than 5, optimally less than 2. Indicates length ratio. The closer the main surface edge length ratio (i.e., equal edge length) , the probability of a significant rod population being present in the emulsion is reduced. Furthermore, smaller Tabular grains with edge ratios appear to be less susceptible to pressure desensitization.

In one particularly preferred texture of the invention, at least 50% of the total grain projected area The tabular grain population, which accounts for . In other words, the emulsion in this example is a thin tabular grain emulsion.

Surprisingly, ultrathin tabular grain emulsions satisfy the requirements of the present invention by manufactured. The ultrathin tabular grain emulsion has a selected tabular grain population of 0.06 μm. Made from tabular grains having a smaller thickness. Prior to this invention exhibits a cubic crystal lattice structure known in the art. One ultrathin tabular grain emulsion contains tabular grains bound by (1111 major faces). It was rare. In other words, to obtain ultra-thin dimensions, the parallel twin plane inclusion mechanism It was considered essential to form plate-like particles. Tabular grain population is 0.0 The present invention has an average thickness down to 2 μm, even down to o, oi μm. emulsions can be produced. Ultrathin tabular grains have extremely high surface-to-volume ratios. do. This allows ultra-thin particles to be photographically processed at an accelerated rate. Change When spectrally sensitized, ultrathin tabular grains exhibit a non-responsive effect compared to the spectral region of their native sensitivity. It shows the sensitivity ratio in the spectral region of constant high sensitization. For example, the ultra-thin flat plate according to the present invention Platy grain emulsions have a completely negligible level of blue sensitivity and thus receive blue light. green or light recording in photographic products that exhibit minimal blue contamination even when placed in can give.

The characteristics of tabular grain emulsions that distinguish them from other emulsions are the grain ECD thickness 1). This is the ratio. This relationship has been quantitatively expressed in terms of aspect ratio. flat plate Another quantification that is believed to more accurately assess the importance of grain thickness is tabularity. .

T = ECD / t2 = AR / where T is the flatness, AR is aspect ratio, ECD is the equivalent circular diameter in micrometers (μm), and t is the particle thickness in micrometers.

The high chloride tabular grain population, which accounts for 50% of the total grain projected area, is preferably greater than 25 exhibits a tabularity of greater than 100, most preferably greater than 100.

This tabular grain population can be ultra-thin, so it can range up to 1000 and higher. It is clear that extremely high flatness of the enclosure is within the contemplation of the present invention.

This tabular grain population may exhibit an average ECD of any size that is photographically useful. stomach. Although the average ECD in most photographic applications may rarely exceed 6 μm, An average ECD of less than 10 μm is contemplated for photographic utility. Requirements of the invention In ultrathin tabular grain emulsions that satisfy It is possible to provide intermediate aspect ratios with ECD of platelet grain populations. To those skilled in the art As more commonly understood, selected tabular grains with higher ECD Emulsions containing populations are advantageous for obtaining relatively high levels of photographic sensitivity, while , selected tabular grain populations with lower εCD obtain low levels of granularity. It is advantageous for

The population of tabular grains satisfying the above parameters accounts for at least the total grain projected area. 50%, a photographically desirable grain population is available. +1001 main surface The advantageous properties of the emulsions of this invention are greatly increased when the population of tabular grains having It is permitted to do so. Preferred emulsions according to the invention have a total grain projected area of at least 70%, optimally at least 90%, of tabular grains with (100) major faces. It is something that can be occupied by The selection of ranked tabular grains accounts for 7 of the total grain projected area. The above grain description extends to enough tabular grains to account for 0% or even 90% It is specifically intended to provide an emulsion that satisfies the following.

As long as tabular grains having the above desired properties account for the required proportion of the total grain projected area. The rest of the total particle projected area is occupied by any combination of co-precipitated particles. It's okay. Of course, blending emulsions to obtain specific photographic objectives is This is a common method in the technical field. At least one component emulsion is in the above flat plate. Blended emulsions satisfying the grain description are specifically contemplated.

Tabular grains that do not satisfy the tabular grain population requirements account for 50% of the total grain projected area. If so, the emulsion does not meet the requirements of this invention and is generally photographically inferior. It is an emulsion. Most applications (especially those requiring spectral sensitization and those requiring rapid processing) For applications requiring minimum silver coverage and/or has all tabular grains or a relatively thick emulsion, e.g., a thickness greater than 0.3 μm. Emulsions containing high proportions of tabular grains are photographically inferior.

More generally, defective emulsions that do not meet the requirements of this invention are cubic, twinned, non-tabular. There is an excess proportion of the total particle projected area occupied by shaped particles and rods.

Such an emulsion is shown in FIG. Most of the particle projected area is occupied by cubic particles. It is. It can also be asserted that the number of rod-like objects is much larger than in FIG. slightly tabular grains are present; these only make up a small portion of the total grain projected area. stomach.

The tabular grain emulsion of FIG. 1 and the predominantly cubic grain emulsion of FIG. 2 which satisfy the requirements of the present invention A daughter emulsion was prepared under identical conditions except for iodine control during nucleation.

The emulsion in Figure 2 is a silver chloride emulsion, while the emulsion in Figure 1 additionally contains small amounts of iodide. ing.

Obtaining a tabular grain emulsion that satisfies the requirements of the present invention was achieved through the discovery of a novel precipitation method. achieved by. In this method, nucleation occurs with iodide ions in a high chloride environment. In the presence of (occurs under conditions favorable for the appearance of 100+ crystal faces, grain formation occurs When the cubic crystal lattice formed by the silver ions and the remaining halide ions The inclusion of iodide in the It is extremely disintegrating. The contained iodide ions are distributed regularly during the next grain growth process. This results in crystalline irregularities resulting in tabular grains rather than cubic grains.

When iodide ions are included in the crystal structure at the beginning of nucleation, one or more Cubic particle nuclei with one or more screw dislocations are formed in the cubic crystal planes of I believe it will happen. Cubic crystal plane containing at least one screw dislocation is then accelerated compared to regular cubic crystal planes (i.e., those lacking screw dislocations). accepts silver halide at a given rate. Only one of the cubic crystal faces has a screw dislocation , grain growth on a single plane is accelerated and the grain structure obtained with continued growth is The structure is a stick. Only two opposing parallel planes of the cubic crystal structure have screw dislocations. The same result occurs when . However, any 2g adjacent cube When the crystal planes contain screw dislocations, continued growth accelerates growth on both planes, forming a flat plate. create a particle structure. The emulsion of the present invention has two or three tabular grains containing screw dislocations. Or, it is believed to be made from these particle nuclei having four faces.

Monitor the dispersion medium as well as the halide ion concentration in the dispersion medium at the beginning of precipitation A reaction vessel containing a conventional silver and reference electrode is used for the reaction. at least 50 mol % is chloride, i.e. the number of halide ions in the dispersion medium is Halide ions, half of which are chloride ions, are placed in the dispersion medium. dispersion medium The pcl of the body is ++001 due to nucleation? In order to favor the formation of fi-copter surfaces, i.e. within the range 0.5 to 3.5, preferably within the range 1.0 to 3.0, optimally 1 ．． Adjust within the range of 5 to 2.5.

Particle nucleation occurs when the silver jet is opened to introduce silver ions into the dispersion medium. Start the construction process. Iodide ions are preferably applied at the same time as the opening of the silver node or Optimally it is introduced into the dispersion medium before opening. Effective tabular grain formation occurs in silver chloride. This can occur over a wide range of iodide ion concentrations up to the iodide saturation limit. salt The saturation limit of iodide in silveride was determined by H. Hirsch in “Photograph ic Emulsion Grains with Cores: Part 1 ．． “Evidence for the Presence of Cores” , J. of Photog, 5science, vol. 10 (1962), It is reported to be 13 mol% by pages 129-134. equimolar proportions of chloride In silver halide grains containing bromide ions and bromide ions, 27 Up to mol% of iodide can be contained in the grains. Precipitation of the separated silver iodide phase In order to avoid densities and thereby avoid creating additional types of unwanted particles, It is preferred to perform grain nucleation and growth below the iodide saturation limit. in dispersion medium It is common to maintain the iodide ion concentration below 10 mol% at the beginning of nucleation. preferred. In fact, only trace amounts of iodide are needed during nucleation to obtain the desired tabular grain population. It is necessary to Initial iodide ion concentration lowered to 0.001 mol% be done. However, for reasons of reproducibility of results, at least 0.01 mol% of Optimally it is preferred to maintain an initial iodide concentration of at least 0.05 mol%. .

In a preferred form of the 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. nucleation during which at least 50 moles of halide in the grain core, which is chloride, is added to the dispersion medium. Bromide ion may be present in such an amount as is compatible with %. In the particle nucleus Preferably at least 70 mol%, optimally less than 90 mol%, based on silver. Contains damage ions.

Particle 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 It is extended for a convenient period of time, typically from 5 seconds to less than 1 minute.

As long as the pct is maintained within the range mentioned above, additional There is no need to add chloride ions. However, during the nucleation process silver salts and Preferably, both halide salts are introduced at the same time. silver through the nucleation process The advantage of adding halide salts at the same time as salts is that this allows silver ions to be added. All particle nuclei formed after initiation are essentially identical to the initially formed particle nucleus. It is guaranteed that the product has a low logenide content. During the nucleation process Particularly preferred is the addition of iodide ions. The deposition rate of iodide ions is lower than that of other halides. iodide is lost from the dispersion medium unless replenished. There will be.

Any convenient conventional sources of silver and halide ions can also be used during the nucleation process. can be used. The silver ions are preferably mixed with an aqueous silver salt solution, such as a silver nitrate solution. and introduce it. The halide ions are preferably lithium, sodium and/or is an alkali halide such as potassium chloride, bromide and/or iodide or Introduced as an alkaline earth halide.

During the nucleation step, silver chloride or silver iodochloride Lippmann particles are introduced into the dispersion medium. It is possible, but not recommended. In this case, particle nucleation has already occurred and the nucleus The production process shown above is actually a process that introduces particle surface irregularities. . The disadvantage of delaying the introduction of grain surface irregularities is that this is less than what would otherwise be obtained. The goal is to produce thick tabular grains.

The dispersion medium contained in the reaction vessel before the nucleation step is water, the above dissolved halogen It consists of chloride ions and a peptizer. The dispersion medium can be any silver halide precipitation tank. The pH may be within a convenient conventional range, typically between 2 and 8. dispersion medium It is preferred, but not necessary, to maintain the pH of the do not have. To minimize fog, the preferred pH range for precipitation is 2.0-5. ．． It is 0.

Mineral acids such as nitric or hydrochloric acid and alkali hydroxides are used to adjust the pH of the dispersion medium. Bases such as li can be used. It is also possible to contain a pl buffer. be.

Peptizers are useful in the precipitation of photographic silver halide emulsions, especially tabular grain silver halide emulsions. It may take any convenient conventional shape known to be useful. subordinate An overview of modern peptizers is provided in Re5earChDisclosure, Vol. 308, 198. December 9, Item 308119.5section1X. R e5earch Disclosure is Kenneth Mason Pu blications.

Ltd, Emsworth, Hampshire POLO7DD, UK Published by the country.

Maskasky I, cited above and incorporated herein by reference. Although synthetic polymeric peptizers of various types can be used, gelatin peptizers (e.g. , gelatin and gelatin derivatives) are preferably used. Manufactured and used in photos When using gelatin, it is recommended to use a deionized gelatin peptizer using known methods. However, gelatin peptizers typically contain significant concentrations of calcium ions. There is. In the former example, alkaline earth or earth metal ions, preferably magnetic Divalent or trivalent gold such as sia, calcium, barium or aluminum ions It is preferable to compensate for calcium ion removal by adding ions. stomach. A particularly preferred peptizer is a low methionine seratin peptizer (i.e. 1 gram peptizer) containing less than 30 micromoles of methionine per contains less than 12 micromoles of methionine per gram of glue; These peptizers and their manufacture are previously cited, the disclosures of which are hereby incorporated by reference. Maskasky II and King et al. however, Types of grains taught to be included in Maskasky I and ■ emulsions Grain growth modifiers (e.g., adenine) may cause these grain growth modifiers to cause twinning and f III In the dispersion medium of the present invention, since it promotes the formation of tabular grains having l main surfaces. It should be noted that it is not suitable for inclusion in Generally, the finished emulsion is shaped At least about 10%, typically 20-80%, of the dispersion medium comprising the nucleation step is Present in the reaction vessel at the beginning. Relatively low levels of peptizer, typically finished emulsion Maintaining 10-20% of the peptizer present in the reaction vessel at the beginning of precipitation. or conventional methods. Formed during nucleation (thin tabular grains with 1001 faces) The concentration of peptizer in the dispersion medium is increased at the beginning of the nucleation process in order to increase the ratio of It is preferably within the range of 0.5 to 6% by weight based on the total weight of the dispersion medium. After precipitation Ceratin, gelatin derivatives and other vehicles are used to produce emulsions for coating. It is conventional practice to add fillers and vehicle fillers. After precipitation is complete Any naturally occurring levels of methane in the added gelatin and seratin derivatives. Onin may be present.

The nucleation step is carried out at any convenient conventional temperature for precipitation of silver halide emulsions. It can also happen. Near ambient temperature, e.g. in the range from 30°C to about 90°C. Temperatures within the range of 35-70°C are preferred.

Since grain nucleation occurs almost instantaneously, only a very small proportion of the gold and silver can be nucleated. It is necessary to introduce it into the reaction vessel during the process.

Typically, about 0.1-10 mole percent of gold-silver is introduced during the nucleation step.

Grain nuclei are removed until tabular grains with (+001 major faces) of desired average ECD A growing particle growth step follows the nucleation step. The purpose of the nucleation step is to achieve the desired inclusion The objective of the growth process is to form a grain population with a certain crystal structure disorder. The goal is to add additional silver halide while avoiding or minimizing the formation of additional grains. (growing) on top of the existing particle population. added during the growth process. If additional particles are formed, the polydispersity of the emulsion increases and the conditions in the reaction vessel become Additional particles produced during the growth process unless maintained as above for the production process The population will not have the desired tabular grain properties described above.

In its simplest form, the process for making emulsions according to the invention involves the production of silver from start to finish. Can be performed as a single jet precipitation without interrupting iontophoresis . As generally recognized by those skilled in the art, as the size of the particle nucleus increases, new At a sufficiently high rate that new particles cannot be generated, the particle nuclei are separated by silver ions and halogens. The particle nuclei are removed from the dispersion medium by silver ions and halides until they reach the point where they receive the oxide ions. A constant rate of silver ion introduction as it increases the rate of receiving halide ions However, a spontaneous transition from particle production to particle growth occurs.

Although a simple operation, single-jet precipitation reduces halide content and profile. generally results in a more polydisperse population of particles.

The goal is to produce photographic emulsions that develop the most geometrically uniform grain populations achievable. Generally preferred. It is through this that a higher percentage of the total particle population is photographed. This is because it is optimally sensitized for the application and optimally manufactured in other cases.

Additionally, a single polydisperse emulsion that matches the desired sensitometric profile is to obtain the desired sensitometric profile rather than precipitation. , it is generally more convenient to blend relatively monodisperse emulsions.

In producing the emulsion according to the present invention, upon completion of the nucleation step and the emulsion as desired. Introduction of silver and halide salts before proceeding to the growth step to final size and shape It is preferable to interrupt. The emulsion is nucleated within the temperature range mentioned above for grain nucleation. Hold for a sufficient period of time to reduce dispersion. Retention periods range from 1 minute to several hours Typical holding periods range from 5 minutes to 1 hour. During the retention period, the ratio The relatively small grain nuclei undergo Ostwald ripening on the remaining relatively large grain nuclei. The overall result is a reduction in particle dispersion.

If desired, the rate of ripening can be increased by the presence of a ripening agent in the emulsion during the holding period. degree can be increased. The traditional simple approach to accelerating ripening is , increasing the halide ion concentration in the dispersion medium. This is for maturing Forms a complex of silver ions with multiple accelerating halide ions. This approach When using chloride, it is preferred to increase the chloride ion concentration in the dispersion medium.

That is, lowering the pct in the dispersion medium to a range where increased silver chloride solubility is observed. It is preferable. In addition, by using conventional ripening agents, ripening can be accelerated. and (of the total grain projected area occupied by 1001 tabular grains) percentage can be increased. Preferred ripening agents are thioethers and thioethers. Sulfur-containing ripening agents such as oisocyanates. Typical thioisocyanate No. 2,222,264 to N1etz et al., U.S. Patent No. 2,222,264 to Lowe et al. No. 2.448.534 and [IIingsworth U.S. Pat. No. 3.320. No. 069 (these disclosures are incorporated by reference in Book Unknown@1).

Typical thioether ripening agents are described in U.S. Pat. No. 57, Jones U.S. Pat. No. 3.574.628 and Rosencran No. 3,737,313 to tz et al., the disclosure of which is incorporated herein by reference. (included in).

Furthermore, the use of crown thioethers as ripening agents has recently been suggested.

primary or secondary amino units such as imidapools, glycine or substituted derivatives. The ripening agent contained is also effective. Sodium sulfite is also produced by [001 tabular grains] has been shown to be effective in increasing the percentage of total grain projected area occupied. It was.

Once the desired population of grain nuclei has been formed, grain growth to obtain the emulsions of the invention is carried out by ( 100) Any suitable method for precipitating silver halide grains bound by grain planes. It may proceed by any convenient conventional precipitation method. Iodide and chloride ions are must be incorporated into the particle during nucleation so that it is not completed at the internal nucleation site. It exists in crystalline grains, but is known to form a cubic crystal lattice structure. Any halide or combination of halides may be used during the growth process. I can do it. Irregular grain core surfaces that result in tabular grain growth, once introduced, continue Halides or halides, regardless of which halides precipitate during grain growth. will remain as long as the combination forms a cubic crystal lattice, so the growth process There is no need for the particles to contain either compound or chloride ions. This is More than 13 mol% (preferably 6 mol%) of iodide when precipitating silver chloride level of 40 mol % (preferably 30 mol %) when precipitating silver iodobromide. Precipitating silver iodohalide containing high iodide levels and bromide and chloride. Exclude proportionate intermediate levels of iodide in densification. During the growth process silver bromide also When depositing silver iodobromide, the pBr in the dispersion medium is 1.0 to 4.2, preferably is preferably maintained within the range of 1.6 to 3.4. Growth process of silver, oxide When depositing silver chloride, silver bromochloride or pure silver chloride, pci in the dispersion medium is nucleated. It is preferable to maintain it within the ranges described above when describing the formation process.

Tabular grain thickness can be improved by incorporating specific halides during grain growth. It has been found quite unexpectedly that a reduction of less than 20% in . surprised Preferably, between 0.05 and 15 mol%, preferably 1-, based on silver, during the growth process. Addition of bromide in the range of 10 mol% results in the same precipitation in the absence of bromide ions. tabular grains are produced that are relatively thinner (too l) than can be achieved under the conditions It was observed that Similarly, during the growth process 0.001 to 1 mol%, based on silver, Adding iodide within the range achieved under the same precipitation conditions in the absence of iodide ions It was observed that +1001 tabular grains were produced that were relatively thinner than those that could be produced. Ta.

During the growth process, both the silver salt and the halide salt are preferably introduced into the dispersion medium. Ru. In other words, with the remaining halide salt, if any, or in a separate jet. Double-jet precipitation is intended, with added iodide salt introduced through Ru. The rate at which silver salts and halide salts are introduced increases the rate of renucleation - i.e., new grain populations. is adjusted to avoid the generation of Addition rate adjustment to avoid re-nucleation is W ilgus German Patent Publication No. 1 [j (OLS) No. 2.107.118, Ir. 1e U.S. Pat. No. 3.650.757, Kurz U.S. Pat. No. 3.672.9 No. 00, 5aito U.S. Pat. No. 4.242.445, Teltschied et al. European Patent Application No. 801022.12 and Wey [in gelatin solution] ``Growth Mechanism of A gBr Crystals in Gelatin 5 solution”).

Photographic 5science and Engineering , Volume 21, Issue 1, January/February.

1977, as shown from page 14 onwards, it is generally well known in the technical field. Are known.

In the simplest form of the invention, the nucleation and growth steps of particle precipitation are the same and opposite. occurs inside the reaction vessel. However, two-particle precipitation is particularly important after the nucleation step is completed. It is preferable to cut it off. Additionally, two separate reaction vessels can be combined into the single reaction vessel described above. It is preferable to replace it instead of . The nucleation step of particle precipitation is carried out in the upstream reaction vessel ( The process can be carried out in a nucleation reaction vessel (hereinafter also referred to as a nucleation reaction vessel), and the dispersed particle nuclei are Transfer to the downstream reaction vessel (hereinafter also referred to as growth reaction vessel) where the growth process of be able to. In one arrangement of this type, Po5se et al., US Pat. No. 790.386, Forster et al., U.S. Pat. No. 3,897.935, Fi U.S. Pat. No. 4,147,551 to Nnicum et al. As shown by National Patent No. 4.171.224 (incorporated herein by reference) Closed type to receive and mix reactants upstream of the growth reaction vessel, as shown in A nucleation vessel can be used. In these arrangements, the inside of the growth reaction vessel The contents are recycled to the nucleation reaction vessel.

In the present invention, the particle shape, such as pl, l]Ag, aging, temperature and residence time. The various parameters important for the regulation of nucleation and growth are It is contemplated that it can be adjusted independently within the reaction vessel. particle nucleation, nucleation It is completely independent of particle growth occurring in the growth reactor downstream of the production reactor. A portion of the contents of the growth reactor may be recycled to the nucleation reactor in order to Shouldn't. The preferred arrangement for separating particle nucleation from the contents of the growth reaction vessel is , U.S. Patent No. 4.334.012 to λlignot (this patent includes Also disclosed are useful features of ultrafiltration between U.S. Pat. No. 879.208 and Published European Patent Application No. 326.852, No. 326 , No. 853, No. 355.535 and No. 370.116 of Ichizo. Published European Patent Application No. 0368275, Published European Patent Application No. 0368275, Urabe et al. Patent application No. 0374954 and Japanese Patent Application Laid-Open No. 2-172817 by Onishi et al. (1990).

Iodidation method of grain nucleation to create the crystalline disorder required for tabular grain formation As mentioned above, other methods of nucleation have been devised. Shown in the example below. This method uses iodine during nucleation to create tabular grains. Any requirement for the presence of oxide ions is also removed. Furthermore, these other people The method is compatible with the use of iodide ions during nucleation. That is, these The method can be fully relied upon during nucleation for tabular grain production or can be relied upon along with iodide ions during nucleation to create tabular grains. Wear.

Significant levels of dispersion media supersaturation with halide and silver ions can lead to nucleation. Rapid nucleations, including the so-called dump nucleations that exist It has been observed that fast grain nucleation accelerates the introduction of grain irregularities that can correspond to tabularity. It was. Since nucleation is essentially instantaneous, from initial supersaturation the above preferred Immediate excursions into the pci range are completely constant with this approach.

Maintaining the level of peptizer in the dispersion medium below 1% by weight during particle nucleation It has also been observed that increasing tabular grain formation increases tabular grain formation. The aggregation of particle-nuclei pairs is , at least partially to introduce crystalline disorder that induces tabular grain formation. I believe it could be a cause.

Limited flocculation is due to the absence of peptizer in the dispersion medium or by the initial introduction of peptizer. This can be facilitated by limiting the concentration.

Mignot U.S. Pat. No. 4.334.012 describes Particle nucleation in the absence of peptizer by removing soluble salt reaction products has been demonstrated. has been done. Since limited agglomeration of particle nuclei is considered desirable, particle nucleus aggregation Mignot's active intervention to eliminate can be removed or relaxed. particle surface By using one or more peptizers that exhibit reduced adhesion to It is also intended to increase limiting particle agglomeration. For example, MaskaskyII Low methionine seratin of the type disclosed by It is generally accepted that seratin is more weakly adsorbed to the particle surface than seratin containing nin. ing. A further moderated level of particle adsorption can be achieved by using the so-called “synthetic deflocculant J, i.e. It can be obtained with a deflocculant made from a polymer. limited agglomeration of particle nuclei and The maximum compatible amount of peptizer is, of course, related to the strength of adsorption on the particle surface. particle nucleus Immediately after the introduction of the silver salt, once the formation is complete, reduce the peptizer level for the remainder of the precipitation process. Can be elevated to all convenient conventional levels.

The emulsions of the present invention include silver chloride, silver iodochloride emulsions, silver iodochloride emulsions, and silver iodochlorobromide emulsions. be caught. up to 1 O-2 moles per mole of silver, typically 10-' per mole of silver Dopants may be present in the particles at submolar concentrations. copper, thallium , lead, mercury, bismuth, zinc, cadmium, rhenium and group II metals (e.g. iron, ruthenium, rhodium, palladium, osmium, iridium and platinum) present during particle precipitation, preferably during the growth phase of the precipitation. You may do so. Modification of photographic properties is related to the level and location of dopants within the grain are doing. The metal forms part of a coordination complex, such as a hexacoordination complex or a tetracoordination complex. In some cases, ligands may be included within the particles, and the ligands may further influence the photographic properties. It can be done. halo, ako, cyano, cyanate, thiocyanate, nitrosyl, chisai Ligands such as nitrone, oxo and carbonyl ligands are contemplated and have photographic properties. can be expected to denature.

Dopants and their addition are described in US Pat. No. 1.195.432 to Arnold et al. , U.S. Patent No. 1.951.933 to Hochstetter, Trivell U.S. Pat. No. 2,448.060 to i et al., U.S. Pat. No. 2.62 to Overman. No. 8.167, LIueller et al., U.S. Pat. No. 2.950.972, ^Ic Br1de, U.S. Pat. No. 3,287,136; Sidebotham, U.S. Pat. No. 3,488,709, US Patent No. 3,737 to Rosecrants et al. No. 313, 5pence et al., U.S. Pat. No. 3,687,676, Gilman et al. U.S. Patent No. 3.761.267, U.S. Patent No. 3.790.3 to Hiba et al. No. 90, Ohkubo et al., U.S. Pat. No. 3,890,154, Iwaosa et al. U.S. Patent No. 3.901.711, U.S. Patent No. 4.173.483 to Habu et al. No. 4,269,927 to Atwell, Janusonis et al. U.S. Pat. No. 4.835.093, McDugle et al. U.S. Pat. No. 4.933. No. 272, No. 4.981.781 and No. 5,037.732, Keev U.S. Pat. No. 4.945.035 to ert et al. and U.S. Pat. No. 5 to Evans et al. ．． No. 024.931, the disclosures of which are incorporated herein by reference. It is. Background on alternatives known in the art , Attention B.H.Carroll.

“Iridium 5 sensitizat review” ion:　ALiterature　Review”),　Photogra phic 5science and Engineering.

24, No. 6, November 7, December 1980, pp. 265-257, and Grze Directed to Published European Patent Application No. 0264288 of Skowiak et al.

(Conventional high chloride tabular grain milk with tabular grains bound by III The agent is inherently unstable and morphologically difficult to prevent particles from reverting to a nontabular shape. Since the present invention requires the presence of stabilizers, high chloride (more than 50 mole %) High chloride) is particularly advantageous in providing tabular grain emulsions. Features according to the present invention Preferred high chloride emulsions contain more than 70 mol% (optimally more than 90 mol%). ) Contains chloride.

Although not essential to the practice of the present invention, it is possible to Another method that can be used to increase the 100) By containing a drug that can suppress the appearance of particle crystal faces. Ru. When used, this inhibitor inhibits particle nucleation, particle growth or precipitation. may be active throughout.

A useful inhibitor under the intended conditions of precipitation is a nitrogen atom that possesses a resonance-stabilizing π-electron pair. It is an organic compound containing. Resonant stabilization is a method for reducing nitrogen sources under the relatively acidic conditions of precipitation. Prevent protonation of offspring.

Aromatic resonance may be expected due to 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: Represents the atoms necessary to complete the aromatic ring structure, preferably carbon and nitrogen ring atoms. It is acceptable to satisfy the following criteria: Preferred aromatic rings contain 1, 2 or 3 nitrogen atoms. It contains elementary atoms. Particularly contemplated ring structures include 2H-pyrrole, pyrrole, ru, imidazole, pyrazole, 1. 2. 3-1-riazole, 1.2.4 -triazole, l, 3.5-triazole, pyridine, pyrazine, pyrimidine and pyridazine.

When the stabilized nitrogen atom is a ring substituent, preferred compounds have the formula: (In the formula, Ar is an aromatic ring structure containing 5 to 14 carbon atoms, and R1 and R2 is independently hydrogen, Ar or any convenient aliphatic group; and form a 5- or 6-membered ring).

Ar is preferably a carbocyclic aromatic ring such as phenyl or naphthyl. Also, above Any nitrogen- and carbon-containing aromatic ring shown below may also be bonded to the nitrogen atom of formula ■ via a ring carbon atom You may do so. In this example, the resulting compound satisfies both formulas ■ and ■. Ru. A wide variety of aliphatic groups can also be selected. the simplest Purely intended aliphatic groups are alkyl groups, preferably C1-IO alkyl groups. , most preferably an alkyl group having 1 to 6 carbon atoms. Compatible with silver halide precipitation Any functional substituents of alkyl groups known to be present may be present.

5- or 6-membered rings such as cycloalkanes, cycloalkenes and oxygen and/or Cycloaliphatic substituents indicating aliphatic heterocycles such as those containing a nitrogen heteroatom It is also intended to be used. cyclopentyl, cyclohexyl, pyrrolidinyl, Particularly contemplated are piperidinyl, furanyl and similar heterocycles.

The following are representative of compounds intended to satisfy Formula 1 and/or (2).

F, A-2 RA-3 β-Naphthylamine RA-4 RA-5 mosquito Rubazol norharman RA-’7 B roll stomach Ndor pyridine 1,10-phenanthroline RA-15 imidazole Ordinary person-20 Pteridine RA-25 3-amino-! , 2. 4-triazole 3,5-diamino-1,2,4-1- Riazolehencitriazole RA-30 Selection of preferred inhibitors and their useful concentrations are obtained by the selection method described below. . Compounds considered for use as inhibitors have an average particle edge of 0.3 μm. Addition to a silver chloride emulsion consisting essentially of cubic grains with length. This emulsion is vinegar 0.2 M in sodium chloride and has a pct of 2.1 and the compound considered has a pH that is at least one unit greater than the pKa of the substance. This emulsion is Maintain at 75°C for 24 hours with drug. II microscopic examination after 24 hours revealed that the cube Sharper HO than the control, which differs only in that the particles lack the compound considered O) If the introduced compound has an edge on the crystal plane, it will not function as an inhibitor. Fulfilling. T100) The meaning of sharper edges at the intersection of crystal planes is that the particle edge It is said that the azalea is the most active site on the particle with respect to ions re-entering the dispersion medium. It's true. By retaining sharp edges, the inhibitor can be curled up, e.g. A work that suppresses the appearance of non-+100+ crystal planes that exist at edges and corners. running errands. In some instances, dissolved particles deposit exclusively on the edges of cubic particles. Instead of silver chloride, a new collection of grains bound by (100+ crystal faces) A group is formed. Optimum inhibitor activity is achieved when the new grain population is +10 tabular grains. 0) Occurs when the grains are a group of tabular grains connected by main crystal planes.

The silver salt can be epitaxially deposited onto the tabular grains that act as hosts. Especially intended. Conventional epitaxial deposition on high chloride silver halide grains is Maskasky U.S. Pat. No. 4.435.501 (particularly Example 24B), Og. U.S. Pat. No. 4,786,588 and U.S. Pat. No. 4,791,053 to awa et al. U.S. Pat. No. 4,820,624 and U.S. Pat. No. 4,865,962 to Asebe et al. , Sugimoto and Miyake's colloidal AgC with rBr− ions. 1 Mechanism of halide conversion method of microcrystals ride conversion Process of Co11oidal AgC1&l1crocrystals byBr-[ons"), Part 1 and and Part ■, Journal of Co11oid and Interfac e5science, Vol. 140, No. 2, December 1990, pp. 335-361.

U.S. Patent No. 5.035.992 to Houle et al. and JP-A-3-252649 Publication No. (priority date: 1990.03.02-JP 051165 Japan) and Japanese Patent Application Publication No. Publication No. 3-288143 (priority date 1990.04.04-JP 089380 Japan). The disclosures of the above US patents are incorporated herein by reference.

The emulsion used in the present invention is described in "The Theory of Photographic Processing" by T. H. James. Theory of the Photographic Process) J, 4th edition, Macmi fan.

1977, pp. 67-76, or Re5. earth Disclosure, Volume 120, April 1974, Item 12008. Re5earch Disclosure, Volume 134, 19 June 1975, Item 13452.5 Heppard et al. U.S. Patent No. 1.62 No. 3.499, U.S. Pat. No. 1.673.522 to AIaethies et al., Wa U.S. Pat. No. 2,399,083 to Ller et al., U.S. Pat. U.S. Patent No. 2,642.361, U.S. Patent No. 3,297.4 to IcVeigh No. 47, U.S. Patent No. 3.297.446 to Dunn, &fcBride UK Patent No. 1. ] No. 5.755, U.S. Pat. No. 3.772.03 to Berry et al. , Gilman et al., U.S. Patent No. 3.761.267, Ohi et al., U.S. Pat. No. 3,857,711, U.S. Pat. No. 3,565,633 to Klinger et al. U.S. Patent Nos. 3.901.714 and 3.904.41 to Oftedahl No. 5 and Simons British Patent No. 1.396.696. at a temperature of 30-80'C at a pH level of 5-8 at a PAg level of 5-1O. Sulfur, selenium, tellurium, gold, platinum, palladium, iridium, osmium, rhenium can be chemically sensitized with phosphorus or phosphorus sensitizers or a combination of these sensitizers. and optionally chemical sensitization as described in Damschroder U.S. Pat. No. 2.642.36. Thiocyanate derivatives such as those described in Lowe et al., U.S. Pat. ．． No. 521.926, U.S. Pat. No. 3.021.215 to Williams et al. and Bigelow, U.S. Pat. No. 4,054,457. Oether Compounds, Dostes U.S. Pat. No. 3.411.914, Kuwa U.S. Patent No. 3,554,757 to bara et al., U.S. Patent No. 3 to Oguchi et al. , No. 565.631 and Ofteda's former U.S. Pat. No. 3.901.714. Azaindene, azapyridazine and azapyrimidine, Lli as listed European patent application EP 294.149 of Yoshi et al. and Tanaka Elemental forms as described in European patent application EP 297.804 of et al. Sulfur and NiN15hika et al. European Patent Application EP 293.917 in the presence of a thiosulfonate as described in No. additionally or Alternatively, the emulsions are described, for example, in U.S. Pat. No. 3,891,44 to Janusoni S. No. 6 and U.S. Pat. No. 3,984,249 to Babcock et al. treated with hydrogen, low pAg (e.g., lower than 5), high pH (e.g., higher than 8). No. 2,983,609 to A11en et al. et al.'s Re5earch Disclosure, Volume 136, August 1975, I tem 13654. Lowe et al. U.S. Patent No. 2.518.698 and No. 2.739.060, U.S. Patent No. 2.743.182 to RObert S et al. 2.743.183, U.S. Pat. No. 3.026.2 to Chambers et al. No. 03 as well as U.S. Pat. No. 3.361.564 to Bigelow et al. such as stannous chloride, thiourea dioxide, polyamines and amineporanes. Reduction sensitization can be performed using a reducing agent.

Chemical sensitization is described in U.S. Pat. No. 4,439,520 to Kofron et al., U.S. Patent No. 4,439,520 to Dickerson No. 4.520.098, U.S. Pat. No. 4.435.50 to Maskasky No. 1, Ihama et al., U.S. Pat. No. 4,693.965, and Ogawa, U.S. Pat. 4.791.053 in the presence of a spectral sensitizing dye. be able to. Chemical sensitization is described in British Patent Application No. 2.038.792 of Haugh et al. A and Mifune et al., published European patent application EP 302.528. Directed to a specific region or crystallographic plane of a silver halide grain as shown in good. The sensitivity center obtained from chemical sensitization is described in Morgan U.S. Pat. ．． No. 485, Becker U.S. Pat. No. 3.966, 476 and Re5ear ch Disclosure, Volume 181, May 1979, Item 18 Twin-jet addition or silver salt and halogenation as described in 155 Addition of silver halide using such means as 94g circulation with alternating additions of salts. It may be partially or totally occupied by precipitation of the layer. Also quoted above Chemical sensitizers can increase the production of additional silver halide, as described in Morgan. It can also be added before or at the same time. Chemical sensitization is as per Hasebe et al. halides as described in EP 273.404 may occur during or after the conversion of In many instances, selected tabular grain sites (e.g. For example, epitaxial deposition on edges or corners) favors chemical sensitization. or itself for exerting the function normally exerted by chemical sensitization. It can be used for

This emulsion can be spectrally sensitized with dyes from a variety of classes, including the polymethine dye class. Types of polymethine dyes include cyanines, merocyanines, and complex cyanide. cyanines and merocyanines (i.e. tri-, tetra- and polynuclear cyanines and merocyanines) nin), styryls, merostyryls, streptocyanins, hemicyanins aryritins, allopolar cyanines ines) and enamine cyanines.

Cyanine spectral sensitizing dyes include quinolinium, pyridinium, isoquinolinium, 3H-indolium, benzoindolium, oxacillium, thiazolium, se Renacillinium, imidazolium, benzoxacillium, benzothiazolium , benzoselenazolium, henzotellazolium, benzimidazolium, naph toxacilium, naphthothiazolium, naphthoselenazolium, naphthothiazolium Lium, thiazolinium, dihydronaphthothiazolium, birylium and imida linked by a methine linkage, such as those derived from zopyrazinium quaternary salts. It contains two basic heterocyclic nuclei.

The merosoanine spectral sensitizing dye contains one cyanine linked by a methine bond. Dye-type basic heterocyclic nucleus, barbylic acid, 2-thiobarbylic acid, rhoda Nin, hydantoin, 2-thiohydantoin, 4-thiohydantoin, 2-bira Purin-5-one, 2-inoxazolin-5-one, indan-1,3-dione , cyclohexane-1,3-dione, 1,3-dioxane-4,6-dione, dione Lapurin-3,5-dione, pentane-2,4-dione, alkylsulfonylar Setonitrile, hexylacetonitrile, malononitrile, malonamide, soquinolin-4-one, chroman-2゜4-dione, 5H-furan-2-one, 5H-3-pyrrolin-2-one, 1. I,3-trianopropene and tellurium and acidic nuclei, such as those derived from chlorhexanedione.

One or more spectral sensitizing dyes can be used. Entire visible and infrared spectrum Dyes with sensitization maxima over wavelengths that vary widely in spectral sensitization curve shape It has been known. The choice and relative proportions of the dyes depend on the region of the spectrum where sensitivity is desired. depending on the region and the shape of the desired spectral sensitivity curve. have overlapping spectral sensitivity curves Dyes are often combined to increase the sensitivity at each wavelength within the region of overlap. This will yield a curve approximately equal to the sum of the sensitivities of the individual dyes.

In other words, a spectral sensitivity curve with a maximum value intermediate between the maximum sensitization value of each dye is calculated. It is possible to use a combination of dyes with different local maxima to obtain be.

Supersensitization - i.e., all concentrations of one dye alone in a spectral region; or a spectral enhancement that results in a greater spectral sensitization than that obtained from the added effect of the dye. Combinations of sensitive dyes can be used. Super sensitization involves the use of spectral sensitizing dyes, stabilizers and fogging agents. such as inhibitors, development accelerators or inhibitors, coating aids, optical brighteners and antistatic agents. can be achieved in selected combinations with other additives. Cause of supersensitization One of several possible mechanisms and compounds is described by Gilman as Pho. tographic 5science and Engineering, 18 Vol., 1974, pp. 418-430.

Spectral sensitizing dyes can also affect emulsions in other ways.

For example, spectral sensitizing dyes increase photographic sensitivity within the spectral region of inherent sensitivity. can be done. Brooker et al., U.S. Pat. No. 2.131.038, Ill. U.S. Patent No. 3.501.310 to ingsworth et al., Webster et al. U.S. Patent No. 3.630.749, U.S. Patent No. 3.718.4 to 5pence et al. No. 70 and U.S. Pat. No. 3,930,860 to Hiba et al. The spectral sensitizing dye may also contain anti-capri agents or stabilizers, development accelerators or inhibitors, It can also function as a reducing agent or nucleating agent and a halogen acceptor or electron acceptor.

Particularly useful spectral sensitizing dyes for sensitizing the emulsions described herein are No. 742.112, Brooker U.S. Pat. No. 1,846.300; 1.846.301, 1.846.302, 846.3 No. 03, No. 1.8 = I6.304, No. 2.078.233 and No. 2, No. 089.729, Brooker et al., U.S. Pat. 2.213.238, 2.493.747, 2.493.748 , No. 2, 526,632, No. 2.739.964 (Reissue No. 24.29) 2), No. 2, 778.823, No. 2.917.516, No. 3.35 No. 2.857, No. 3, 411.916 and No. 3.431,111, Sp U.S. Pat. No. 2,503.776 to Rague, U.S. Pat. No. 3.28 to Nys et al. No. 2.933, U.S. Pat. No. 3.660.102 to Riester, Kampf. U.S. Patent No. 3.660.103 to er et al., U.S. Patent No. 3.33 to Taber et al. 5.010, 3.352.680 and 3.384.486, Li U.S. Patent No. 3,397,981 to ncoln et al., U.S. Patent No. 3 to Fumia et al. ．． No. 482.978 and No. 3.623.881, U.S. Patents of 5pence et al. No. 3.718.470 and Mee U.S. Pat. No. 4.025.349 (which et al., the disclosures of which are incorporated herein by reference.

Useful supersensitizing dye combinations include non-light absorbing additives that function as supersensitizers. Examples of useful dye combinations include U.S. Pat. No. 2,933,390 to klcFall et al. No. 2,937,089 to Jones et al., U.S. Patent No. 2,937,089 to Motter. No. 3,506,443 and Schwan et al., U.S. Pat. No. 3,672,898. (the disclosures of which are incorporated herein by reference).

Spectral sensitizing dyes may be added at any stage during emulsion preparation. These are Wall , Photographic Emulsions, American P photographic Publishing Co., Boston, 1 No. 929, p. 65, Hill U.S. Pat. No. 2,735.766, Ph1li No. 3,628,960 to ppaerts et al., U.S. Patent No. 3,628,960 to Locker No. 4.183.756, Locker et al., U.S. Pat. No. 4.225.666; Re5earch Disclosure, Volume 181, May 1979, Ite m 18155 and published European patent application EP 301.508 of Tan1 et al. It can be added at the beginning or during the precipitation, as described in No. this No. 4,439,520 to Kofron et al., Dickerso et al. U.S. Patent No. 4.520.098 to n, U.S. Patent No. 4.4 to klaskasky No. 35.501 and Phi 1ippaerts et al. cited above. It can be added before or during chemical sensitization so as to These are Asami et al. Published European Patent Application EP 287.100 and published by Metoki et al. - Before emulsion cleaning as described in EP 291,399 Or it can be added in between. This dye is described in U.S. Pat. No. 2, Colins et al. 912.343, just before the sheathing.

A small amount of iodide is added as described by Dickerson, cited above. It can be adsorbed onto emulsion grains to promote aggregation and adsorption of spectral sensitizing dyes.

As described in Dickerson, post-processing dye contamination is caused by fine high iodide grains. It can be reduced by the proximity of the child to the dyed emulsion layer. to their solubility Depending on the spectral sensitizing dye, U.S. Pat. water or methanol dissolved in a surfactant solution as described in as a solution in a solvent such as tanol, acetone or pyridine, or as an owe In U.S. Pat. It can be added to the emulsion as a dispersion as described. A11fun As described in published European patent application EP 302,528 of E et al. , this dye is used to identify emulsion grains as a means of suppressing chemically sensitized centers relative to other surfaces. can be selectively adsorbed onto the crystallographic planes of Publication of Miyasaka et al. -Roppa Patent Application No. 270,079, No. 270.082 and No. 278.510 As described in the issue, spectral sensitizing dyes are used together with less adsorbed luminescent dyes. can be used.

The following illustrates specific spectral sensitizing dye selections.

S-1 Anthitro 5'-chloro-3'-di(3-sulfopropyl)naphtho(1,2 -d) Thiazolothiacyanine hydroxide, sodium salt S-2 anhydro-5'-chloro-3'-di(3-sulfopropyl)naphtho(1,2 -d) Oxazolothiacyanine hydroxide, thianhydro-4,5-benzo -3'-methyl-4'-phenyl-1-(3-sulfopropyl)naphtho(1,2 -d) Thiazolothiathiazocyanine hydroxide 1.1'-diethylnaphtho(1,2-d)thiazolo-2'-cyanianhydro -1.1'-tmethyl-5,5'-di(trifluoromethyl)-3-(4-st) (rufobutyl)-3’-(2,2,2-trifluoroethyl)benzimidazolo Carbocyanine hydroxide S-6 Anthitro 3,3'-(2-methoxyethyl)-5,5'-diphenyl-9 -Ethyloxacarbocyanine, sodium salt S-7 Anthitro 11-ethyl-1,1'-di(3-sulfopropyl)naphtho(1 , 2-d) Oxazolocarbocyanine hydroxide, amphitrow 5.5'- Fuchloro9-ethyl-3,3'-di(3-sulfopropyl)oxaselenaka Rubocyanin hydroxide, sodium salt 5.6-dichloro-3',3'-dimethyl-1,1',3-triethylbenzoy Midazolho 3H-Indolocarbocyanine Bromide anhydro-5,6-dichloro-1,1-diethyl-3-(3-sulfopropyl ) Benzimidazolooxacarbocyanine Hydroamphitro 5.5'-dichloride Rolo-9-ethyl-3,3'-di(2-sulfoethylcarbamoylmethyl)thi Acarbocyanine hydroxide, sodium salt.

Anchtrow 5',6'-dimethoxy-9-ethyl-5-phenyl-3-(3- sulfobutyl)-3'-(3-sulfopropyl)oxathiacarbocyanine Hydroxide, sodium salt amphitrow 5.5'-dichloro-9-ethyl- 3-(3-phosphonopropyl)-3'-(3-sulfopropyl)thiacarboxy Anianhydro-3,3'-di(2-carboxyethyl)-5,5'-dichloro rho-9-ethylthiacarbocyanine promidanhydro-5,5'-dichloro -3-(2-carboxyethyl)-3'-(3-sulfopropyl)thiacyani Sodium salt 5S-16 9-(5-barbylic acid)-3,5-dimethyl-3'-dithylteratia Pocyanin bromide Anhydro 5.6-methylenedioxy-9-ethyl-3-methyl-3'-( 3-Sulfopropyl) tellulatiacarbocyanine 3-ethyl-6,6'-t Methyl-3'-pentyl-9,11-neopentylene dicarbocyanine lomidanhydro-3-ethyl-9,11-neopentylene-3'-(3-su (lufopropyl) thiadicarbocyanine hydroxide anhydro-3-ethyl- 11,13-neopentylene-3'-(3-sulfopropyl)oxathiatri Carbocyanine hydroxide, anhydro-5-chloro-9-ethyl-5'- Phenyl-3'-(3-sulfobutyl)-3-(3-sulfopropyl)oxathi Acyanine Hydrokid, Sodium Salt Anthitro 5.5'-Diphenyl- 3,3'-di(3-sulfobutyl)-9-ethyloxacarbonanine hydride Roxid, thianthitro 5,5'-dichloro-3,3'-di(3-sulfoplast) ropyru)-9-ethylthiacarbocyanine hydroxide, triethyl ammonium um salt anhydro-5,5'-dimethyl-3,3'-di(3-sulfopropyl)-9 -Ethylthiacarbocyanine hydroxide, nathanhydro-5,6-dichloro lo-1-ethyl-3-(3-sulfobutyl')-1'-(3-sulfopropyl ) Benzimidazolonaphtho(1,2-d)thiazolocarbocyanine hydroxy Trienhydro-11-ethyl-1,1'-di(3-sulfopropyl) Naphtho(1,2-d) oxazolocarbocyanine hydroxide, Anthitro 3,9-diethyl-3'-methylsulfonylcarbamoylmethyl-5-phenyl Oxathiacarbocyanin p-) Luanchtrow 6,6'-dichloro-1,1 '-Diethyl-3,3'-di(3-sulfopropyl)-5,5'-bis(tri fluoromethyl)benzimidazolocarbocyanine hydroxide, natoanhi Dro-5'-chloro-5-phenyl-3,3'-di(3-sulfopropyl)o Xathiacyanine hydroxide, sodium salt ropyru) thiacyanin hydroxide, sodium salt S-31 3-ethyl-5-(1,4-dihydro-1-(4-sulbutyl)pyridine-4 -ylidene] rhodanine, triethylammonium salt S-32 1-Carboxyethyl-5-C2-(3-ethylbenzoxapurine 4-[2- ((1,4-dihydro-1-dodenruviridine-iriderrhodanine S-35 1,3-diethyl-5-f(1-ethyl-3-(3-sulfobutyl 5-(2- (3-ethylbenzoxazolin-2-ylidene) ethylidene 1-methyl-2 -dimethylamino-4-oxo-3-phenylimidabrinium-p-toluene Sulfonate S-37 5-(2-(5-carboxy-3-methylbenzoxazolin-2-ylidene)et tylidene-3-cyano-4-phenyl-1-(4-methylsulfonamide-3 -pyrrolin-5-one S-38 2-(4-(hexylsulfonamido)benzoylcyanomethine]-2-(2- (3-(2-methoxyethyl)-5-((2-methquinethyl)sulfonamide ]Benzoxazolin-2-ylidene)ethylidene)acetonitrile S-39 3-Methyl-4-C2-(3-ethyl-5,6-dimethylbenzotellazoline- 2-ylidene)ethylidene)-1-phenyl-2-3-heptyl-■-phenyl -5- +4- (3-(3-sulfobutyl)-naphtho(1,2-cl)thiazo Phosphorus]-2-butenylidene)1,4-fuconylenebis(2-aminovinyl-3 -Methyl-2-anthitro 4-(2-[3-(3-sulfopropyl)thiazo Phosphorus-2-ylidene]ethylidene-2-+3-(3-(3-sulfopropylene) ) Thiazolin-2-ylidene] propenyl-5-oxacillium hydrokyl Sodium salt S-43 3-carboxymethyl-5-(3-carboxymethyl-4-oxo-5-methyl -1,3,4-thiasiapurin-2-ylidene)ethylidenephthiazine-2- Ylidene) rhodanine, dipotassium salt S-44 1,3-diethyl-5-[1-methyl-2-(3,5-dimethylbenzotellap) Phosphorus-2-ylidene) ethylidene-2-thiopal-3-methyl-4-(2-(3 -ethyl-5,6-dimethylbenzotellaprine-2-ylidene)-]-methyl ethylidene)-1-phenyl-2-pyrazolin-5-one S-46 1,3-diethyl-5-[l-ethyl-2-(3-ethyl-5,6-dime) Cybenzotellaprine-2-ylidene) ethylidene] = 2-thiobarbital acid S-47 3-ethyl-5-(((ethylbenzothiazolin-2-ylidene)-methyl)- [(1,5-dimethylnaphtho(1,2-d)selenazolin-2-ylidene)methy methylene) rhodanine S-48 5-(bis[(3-ethyl-5,6-dimethylbenzothiazolin-2-ylidene) ) methyl] methylene l-1,3-jethyl-barbi-3-ethyl-5-1 ((3- Ethyl-5-methylbenzotellazolin-2-ylidene)methyl)(1-ethyl naphtho(1,2-d)-tellazolin-2-ylidene)methyl]methylene)rho Danin Anhtrow 5,5'-diphenyl-3,3'-di(3-sulfopropylene) ) Thiacyanin hydroxide, triethylammonium salt anhydro-5-chloroO-5'-phenyl-3,3'-di(3-sulfopropylene) ) Thiananine hydroxide, triethylammonium salt Instability, which increases the minimum density (i.e., fog) of negative emulsion coatings, can be caused by stabilizers, Antifogging agent, antiking agent, latent image stabilizer Preservation agents and similar additives can be incorporated into the emulsion and adjacent layers prior to coating. can be protected. C.E., “The Theory of Photographic Processing” by Mees theory of the Photographic Process, )J 2nd edition, Macmillan, 1954, pp. 677-680. As such, most of the antifoggants effective in the emulsions used in this invention are present in the developer solution. It can also be classified under a few general headings.

To avoid such instability in emulsion coatings, halide ions (e.g. , bromide salt), as shown in U.S. Pat. No. 2,566,263 to Trivelli et al. chloropalladates and chloropalladates, as shown in chloropalladites, Jones's US special No. 2,839.405 and Sidebotham U.S. Pat. No. 3.488. Magnesium, calcium, cadmium, cobal as shown in No. 709 water-soluble inorganic salts of manganese and zinc, as disclosed in Alen et al., US Pat. No. 2,728. Mercury salts such as those shown in Brown et al., British Patent No. 1.336. No. 570 and British Patent No. 1.282.303 to POllet et al. Selenols and diselenides such as A11en et al., U.S. Pat. No. 2.694.7. No. 16, Brooker et al., U.S. Pat. No. 2.131.038, Graham U.S. Patent No. 3,342.596 and U.S. Patent No. 3.954.47 to Arai et al. No. 8, quaternary ammonium salts, such as those shown in U.S. Pat. No. 3.630.744, azomethine desensitizing dyes, Herz et al. U.S. Pat. No. 3,220.839 and Knott et al. U.S. Pat. No. 2.514.6 US Pat. No. 3.5 of the isothiourea, 5cavron, as shown in US Pat. 65.625, Maffet, U.S. Pat. Peptide derivatives such as those shown in No. 3.274.002, Welsh, USA. No. 3,161,515 and U.S. Pat. No. 2,751,297 to Hood et al. pyrimidines and 3-pyrazolidones as shown in Baldassarr. Azotriazole as shown in U.S. Pat. No. 3,925.086 to Heimbach U.S. Pat. No. 2.444.605 , U.S. Patent No. 2.933.388 to Knott, U.S. Patent No. 2.933.388 to Williams No. 3.202.512, Research Disclosure, Volume 134, June 1975, Item 13452 and Volume 148, August 1976, Ite m 14851 and Nepker et al. UK Patent No. 1.338.567. azaindenes, especially tetraazaindenes, ) (enda　l　l　 U.S. Pat. No. 2.403.927 to Kennard et al., U.S. Pat. No. 3.26 to Kennard et al. 6, No. 897, Re5earch Disclosure, Volume 116, 1973 December, Item 11684. U.S. Patent No. 3.397 to Luckey et al. No. 987 and 5alesin U.S. Pat. No. 3.708.303. such as mercaptotetrazole, mercaptotriazole and mercaptone azo U.S. Pat. No. 2,271.229 to Peterson et al. and R, cited above. e5earch Disclosure, Item 11684. Azoles such as 5heppard et al., U.S. Pat. No. 2.319.090, B Re5earchDi to irr et al., U.S. Pat. No. 2,152,460, cited above. sclosure, Item 13452 and French Patent No. 2 of Dostes et al. ．． No. 296.204, purines such as those shown in Aleck et al., US Pat. 3.926.635 (and/or 1. Gunther, a polymer of 3-carhamokine)-2-methylenepropane Tetrazole, tetrazole, as shown in U.S. Pat. No. 4,661,438 by et al. Razol, tellrazolinium salts and tellrazolium salts and Gunther's rice National Patent No. 4.581.330 and Przyklek-Elling et al. 4,661.438 and 4.677, 202. Use stabilizers and antifoggants such as aromatic oxatellazinium salts Can be done. High chloride emulsions are used, especially during chemical sensitization, as published by Miyoshi et al. European patent application EP 294.149 and Tanaka et al. Elemental sulfur as well as Ni as described in patent application EP 297,804 As described in published European patent application EP 293.917 of N15hika et al. It can be stabilized by the presence of thiosulfonates such as Wear.

A particularly useful stabilizer for gold sensitized emulsions is disclosed in U.S. Pat. No. 2.5 to YutZY et al. Benzothiazoles, benzoxazoles, as shown in No. 97.915; Water insolubility of naphthothiazole and certain merocyanine and cyanine dyes gold compounds, as well as those shown in U.S. Pat. No. 3,498,792 to N15hio et al. It is a sulfinamide.

A particularly useful stabilizer in layers containing poly(alkylene oxide) is Car U.S. patent of ro I I et al? 2.716.062, British Patent No. 1,466 , No. 024 and Habu et al., U.S. Pat. No. 3,929,486. Especially ■ Tetraazaindene or resorcinol induction in combination with metals Quaternary bodies, of the type shown in Piper U.S. Pat. No. 2.886.437. Ammonium salts, as shown in Alaffet U.S. Pat. No. 2.953.455 Water-insoluble hydroxides such as Phenols, as shown in Dersc No. 2.955.038 and Dersc ethylene diurea, W as shown in U.S. Pat. No. 3,582,346 to Barbylic acid as shown in U.S. Patent No. 3,617,290 to derivatives, as shown in Bigelow U.S. Pat. No. 3.725.078. borane, 3 as shown in Wood's British Patent No. 1.158.059. - pyrazolidinones as well as those shown in Butler et al. British Patent No. 988.052. Aldoximines, amides, anilides such as and ester.

This emulsion is shown in U.S. Pat. No. 3,236,652 to Kennard et al. Sulfocatecholic compounds such as those described in Carroll et al. British Patent No. 623,4 Aldoximine and the Draisbach U.S. patent as shown in No. 48 Additives such as meta- and polyphosphates as shown in subheading No. 2.239.284. excipients as well as ethylenediamine as shown in British Patent No. 691.715. By containing tetraacetic acid, trace amounts of metals such as copper, lead, tin, iron, etc. can protect against fog and desensitization caused by

Contains synthetic polymers of the type used as vehicles and to improve covering power. A particularly useful stabilizer in the layer comprising is described in Forsgard, US Pat. Monohydric and polyhydric phenols as shown in British Patent No. 3.697, British Patent No. 897. ．． No. 497 and British Patent No. 1.039.471 to Stevens et al. sugars such as those shown in Dersch et al., U.S. Pat. No. 3,446,618. It is a quinoline derivative such as

A particularly useful stabilizer in protecting emulsion layers against dichroic fog is Barbi No. 3,679,424 and US Pat. No. 3,820,998 to er et al. Salts of nitrones such as those described in Willems et al., U.S. Pat. No. 3,600.17. mercaptocarboxylic acids as shown in No. 8 as well as E.

J, Blrr, r Stabilization of Photographic Silver Halide Emulsions (“5tabilizat ion of Photographic 5ilver) talide Em ulsion”), Focal Press, London, 1974, Additives such as those described on pages 126-218.

A particularly useful stabilizer in protecting emulsion layers against development fog is B100[ British Patent No. 1.356.142 and U.S. Patent No. 3.575.699 to Il et al. , Rogers, U.S. Pat. No. 3,473,924 and Carlson et al. azabenzimidazole, B as shown in Patent No. 3,649.267; Rooker et al., U.S. Pat. No. 2.131.038; Land, U.S. Pat. No. 704.721, as shown in Rogers et al., U.S. Pat. No. 3.265.498. Substituted benzimidazoles, benzothiazoles, benzotriazoles such as et al., U.S. Pat. No. 2,432,864 to Dimsdale et al., U.S. Pat. U.S. Pat. No. 3,081.170, Weyerts et al., U.S. Pat. No. 3,260.5 No. 97, U.S. Patent No. 3.674.478 to Grasshoff et al. and Aron mercapto-substituted compounds as shown in U.S. Pat. No. 3,706,557 of d. products, such as mercaptotetrazole, Herz et al., US Pat. No. 3,220,83. Isothiourea derivatives such as those shown in No. 9, as well as von Konig's rice National Patent No. 3.364.028 and British Patent No. 1.18 of Won Konig et al. Additives such as thiodiazole derivatives as shown in No. 6.441 .

When aldehyde-type hardeners are used, the emulsions are prepared by the US patent of 5heppard et al. Monohydric and polyhydric phenols of the type specified in subheading No. 2.165.421, Ree Nitro-substituted compounds of the type disclosed in British Patent No. 1.269.268 to S et al. 1.151.914 to Valbusa. li(alkylene oxide) and A11en et al., U.S. Pat. No. 3,232.761. and in combination with urazol as indicated in No. 3.232.764. or even as shown in U.S. Pat. No. 3,295,980 to Rees et al. Preserve with antifoggants such as mucohalogen acids in combination with maleic hydrazide. can be protected.

To protect the emulsion layer coated on a linear polyester support, Anders Parabanic acid, hydrogen, as shown in U.S. Pat. No. 3,287,135 to on et al. Dantoic acid hydrazide and urazole and Rees et al., U.S. Pat. No. 3.39 6.023, especially in combination with aldehyde type hardeners, like piazines, which contain two symmetrically fused six-membered carbocycles. additives can be used.

King desensitization of emulsions is shown in Overman U.S. Pat. No. 2.628.167. Thallium nitrate, as described in Jones et al., U.S. Pat. No. 2.759.82. Compounds of the type disclosed in No. 1 and No. 2.759.822, polymer lattes Dispersions, Re5earch Disclosure, Volume 116, 1 December 973.

Azoles and mercaptotetrazos of the type disclosed in Item 11684 U.S. Pat. No. 3,033,680 to λilton et al. Plasticized gelatin compositions of the type disclosed in Rees et al., U.S. Patent No. 3. Water-soluble interpolymers of the type disclosed in No. 536.491; Polymer), disclosed in U.S. Patent No. 3.772.032 to Pearson et al. Produced by emulsion polymerization in the presence of poly(alkylesioxide) as indicated polymer latex and Rakoczy U.S. Pat. No. 3,837.861. by incorporating a gelatin graft copolymer of the type disclosed in No. can be reduced.

The color photographic elements of this invention are processed at high bath or drying temperatures to In the absence of pressure desensitization and/or increased fog, AbbOlt et al. 3.295.976, Barnes et al., U.S. Pat. No. 3,545,971, 5 U.S. Pat. No. 3,708,303 to Alesin, U.S. Pat. No. 3,615,619, U.S. Pat. No. 3,623,873 to Brown et al. U.S. Pat. No. 3.671.258 to Taber, U.S. Pat. No. 3.7 to Abele No. 91.830, Re5search Disclosure, Volume 99, 19 July 1972, Item 9930° Florence et al. U.S. Patent No. 3.843 ．． No. 364, U.S. Pat. No. 3,867,152 to Priem et al., Adachi et al. U.S. Pat. No. 3.967,965 and Llikawa et al. U.S. Pat. No. 3.9 47.274 and 3.954.474, additives, controlled by selected combinations of vehicle, hardener and/or processing conditions. I can do it.

Raising the pH or lowering the pAg of the emulsion is known to retard latent image regression. In addition to adding gelatin and gelatin, Ezekiel's British Patent No. ．． 335.923, 1.378.354, 1.387.654 and 1.391.672, and British Patent No. 1.394.3 to Ezekiel et al. No. 71, U.S. Patent No. 3.843.372, to Jefferson British Patent No. 1,412.294 to Son et al. and British Patent to Thurston No. 1.343.904, 5eiter et al. Hydroxybenzene or aromatic as shown in Patent No. 3.424.583 Carbonyl-Bisulfite Addition Products in Combination with Group Amine Developers, Beck Cycloalkyl as shown in U.S. Pat. No. 3,447,926 to ett et al. Lu-1,3 dione, as shown in U.S. Pat. No. 3.600.182 to Matejec et al. A catalase enzyme, such as that described in Kumai et al., U.S. Pat. No. 3,881. 933, in combination with certain cyanine dyes. denaturing agents, as shown in U.S. Pat. No. 3,386,831 to Lonig et al. hydrazides, as shown in U.S. Pat. No. 3,954,478 to Arai et al. Una alkenylbenzothiazolium salt, Thurston British Patent No. 1.3 No. 08.777 and British Patent No. 1.347.544 of Ezekiel et al. Hydroxy-substituted benzylidene derivatives as shown in No. 1.353.527 conductors, the species disclosed in U.S. Pat. No. 3,519,427 to 5Utherns mercapto-substituted compounds of the Llatejec et al. U.S. Patent No. 3.639.12 No. 8, metal-organic complexes of the type disclosed in Ezekiel's British Patent No. 1. Penicillin derivatives, such as those shown in No. 389.089, von Konig Benzimidazole as shown in U.S. Pat. No. 3,910,791 to et al. , propynylthio derivatives such as pyrimidine, Yamasue et al., US Pat. No. 3.9. The combination of iridium compounds and rhodium compounds as disclosed in No. 01.713 combinations, such as those shown in Noda et al., U.S. Pat. No. 3,881,939. Thonone or sydone imine, Ezekiel British Patent No. 1.458.197 Thiazindine derivatives as shown in Re5search Discl. osure.

Thio as shown in Volume 136, August 1975, Item 13651. Latent image stabilizers can be included, such as ether-substituted imidazoles.

In particular, regarding the method for producing tabular grain emulsions and the tabular grains produced by this method, Apart from the features mentioned, further uses of these in color photographic elements of the invention include , may take any convenient conventional form. Conventional color photographic elements It is generally contemplated that the emulsion may be replaced with the same or similar silver halide composition. , silver halide emulsions may be placed with different silver halide compositions, especially other tabular grain emulsions. It is also possible to change the Low levels of high chloride (100) tabular grain emulsions The inherent blue speed of a photographic element, including tabular grain emulsions, depends on the layer order arrangement and other factors. For both conventional features, Kofron et al., U.S. Pat. (the disclosure of which is incorporated herein by reference) Enables the emulsion to be used in any desired layer order arrangement of multicolor photographic elements, including . Conventional features are further set forth by the disclosure below, which is incorporated by reference.

IcBR-I Research Disclosure, Volume 308, 198 December 9th, Item 308.119; IcBR-2Re5earch Disclosure, Volume 225, 198 January 3, [tem22.534: IcBR-3Wey et al., U.S. Patent No. 4.414.306, November 8, 1983 Published: IcBR-4 Solberg et al. U.S. Pat. No. 4.433.048, 1 Published February 21, 984: ICBR-5 Wilgus et al. U.S. Pat. No. 4.434.226, 19842 Published on the 28th of the month: IcBR-6 Maskasky U.S. Pat. No. 4.435.501, 1984 Published on March 6th.

JCBR-71! askaskY U.S. Pat. No. 4.643.966, 1987 Published on February 17th.

JCBR-8 Daubendiek et al. U.S. Pat. No. 4.672.027, 19 Published January 9, 1987; [CBR-9 Daubendiek et al., U.S. Pat. No. 4.693.964, 19 Published September 15, 1987.

[CBR-10 Maskasky U.S. Pat. No. 4.713.320, 1987 Published December 15th: [CBR-115aitou et al., U.S. Pat. No. 4.797.354, 1989 Published on January 10th.

[CBR-12 Ikeda et al., U.S. Pat. No. 4.806.461, 1989.2 Published on the 21st of the month.

ICBR-13 Makino et al. U.S. Pat. No. 4.853.322, 1989 Published on August 1st, and [CBR-14 Daubendiek et al., U.S. Pat. No. 4.914.014, 1 Published April 3, 990: As used herein, the term simply "rPUG-releasing compound" [ ``Dye image-forming compounds'' and ``Photographically useful group-releasing compounds'' (Photogr. aphically useful group-releasing com This is a description of J.

Dye image-forming compounds are typically coupler compounds, dye redox releasing compounds , dye developing agent compound, oxychrome developing crude drug compound or bleaching dye or color It is an elementary precursor compound. Image transfer processing method (image transfer pr Dye redox release useful in color photographic elements that can be used in The developing agent, dye developing agent, and oxychrome developing herbal compound are described in [Theory of Photographic Processing (T. he Theory of the Photographic Process ) J, 4th edition, T, H, James & I, Macmillan.

New York, 1977, Chapter 12, Section V, and Kenneth L. lason Publications, Ltd., Dudley Annex, 12a North 5treet, Emsworth.

Hampshire POIO7DQ, Re5earch published by UK Disclosure.

December 1989, Item 308119, 5section XXI[ has been done. Dye compounds useful in color photographic elements used in dye bleaching processes are: It is described in "Theory of Photographic Processing", 4th edition, Chapter 12, Section ■.

Preferred dye image-forming compounds react with oxidized color developing agents to form colored products or A coupler compound that forms a dye. A coupler compound has an acid in the coupling reaction. Contains a coupler unit C0LIP that combines with a chemical species during development to form a dye structure. There is. In addition, the coupler compound has a oxidized color developing agent. A group called a coupling-off group that is attached to a coupler unit by a bond that cleaves to may contain a group. Coupling-off groups include chloro, bromo, fluoro and couplers by halogens like iodine or atoms like oxygen, sulfur, nitrogen, phosphorus etc. It may be an organic group bonded to one unit.

PUG-release gold compounds contain truly useful groups and react with oxidized color developing agents to It is a compound that can release a group. Such PlJG-releasing compounds have a single carrier. position and a leaving group, which are formed by bonds that are cleaved upon reaction with oxidized developing agents. are combined. The leaving group can be used as a preformed species or released from the carrier. After cleavage of the deradical, the protected species or precursor volume reacts further to form P[JG. This includes PUGs that may exist as Oxidized developing agent and PUG-releasing compound The reaction produces colored or colorless products.

Carrier unit (CAR) is hydroquinone that undergoes cross-oxidation by oxidized developing agent. , catechols, aminophenols, sulfonamidophenols, sulfonamides, Contains amide naphthols, hydrazides, etc. Preference among PUG-releasing compounds A desirable carrier unit is a colored species that is bound to an oxidized color developing agent in a cleavage reaction. or a coupler unit capable of forming a dye. One unit of carrier is C0UP When , the leaving group is called a coupling-off group. Generally speaking, leaving groups are discussed above. As previously mentioned, the coupling-off group can be used as a preformed species or as a protected species or contains PUG as the precursor volume. Even if a single coupler unit is ballasted, It does not have to be last. This can be a monomer (or PUG) When two or more groups are contained in the coupler, dimer, oligomer or It may be part of a polymeric coupler, or PLIG may be a unit of two couplers. It may form part of a bis compound that forms part of the bond between.

PIG is any group typically made available in a photographic element in an image-like format. There may be. The PUG may be a photographic reagent or a photographic dye. As described herein Photographic reagents that further react with components in the photographic element upon release, such as development inhibitors, Development accelerators, bleach inhibitors, bleach accelerators, electron transfer agents, couplers (e.g., competitive dye-forming couplers or development inhibitor-releasing couplers), dye precursors, colors raw materials, developing agents (e.g. competitive developing agents, dye-forming developing agents or silver halide developing agents) main ingredient), silver complexing agent, fixing agent, image toner, stabilizer, hardener, tanning agent, turnip υ agents, ultraviolet absorbers, antifoggants, nucleating agents, chemical or spectral sensitizers or It is an ingredient similar to a sensitizer.

PtJG 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, PUG is The development inhibitor may be formed or the development inhibiting function may be in the coupling-off group. The bond to the carbonyl group bonded to PUG may be protected. other Examples are preformed dyes, dyes protected to shift their absorption and leuko It is a pigment.

The PUG-releasing compound has the formula: CAR-(TILIE), -PUG (wherein, (TI-containing IE) is a binding or time-regulating group, and n is 0. l or 2, moshi When CAR reacts with an oxidized developing agent, PIG (when n is 0) or P UG precursor (TIME) 1-PIG or (TIME), -PUG ( n is 1 or 2) is one unit of carrier that releases imagewise). can be posted. (TIME) 1-PLIG or (TIME), -P The next reaction of IG produces PIG.

When present, the linking group (TILIE) can be linked to molecules such as esters, carbamates, etc. A group that undergoes base-catalyzed cleavage involving endonucleophilic substitution, thereby releasing PUG. . When n is 2, (TILIE) may be the same or different. time adjustment Suitable groups, also known as groups, are described in U.S. Pat. ．． No. 051.345, No. 5.006.448, No. 4.409.323, 4.248.962, 4.847.185, 4.857.44 No. 0, No. 4.857.447, No. 4.861.701, No. 5, 021 ．． 322, 5.026.628 and 5.021.555 (all (incorporated herein by reference). Particularly useful linking groups include the U.S. Patent No. 4.409.323, Patent No. 5.151.343 and Patent No. 5,006. p-hydroxyphenylmethylene units as shown in US Pat. 0 disclosed in Patent No. 5.151.343 and Patent No. 5.021.555 -hydroxyphenyl-substituted carbamate groups, which release Pt1G It undergoes intramolecular cyclization.

When bound to TIME or coupe, it is activated by reaction with oxidized color developing agent. The group may be bonded at the position where it is released from the coupler. Preferably, T lλ(E is bonded to the coupling position of one unit of the coupler, and thus the coupler and Upon reaction with an oxidized color developing agent, T[&IE forms a coup? will be released.

TIME may also be disposed of as a result of the reaction between the coupler and the oxidized color developing agent. It may also be in the uncoupled position of a coupler unit that can be replaced. TIME is C0U When in the uncoupled position of P, other groups containing conventional coupling-off groups It may be in the pulling position. In addition, the same or different inhibitors as described in the present invention may also be used. Pharmaceutical units can also be used. Also, coup is the coupling position and non-coupling position. Each ring position may have T[Mε and PIG. Therefore, in the present invention Useful compounds are capable of releasing more than 1 mole of PUG per mole of coupler. Wear.

TIME binds CAR to PIG unit and after cleavage from CAR, puc unit It may also be an organic group that is cleaved from. This cleavage is preferably carried out by e.g. , U.S. Patent No. 4. Intramolecular nucleophilic substitution reactions of the type described in No. 248.962 or as described in, for example, U.S. Pat. No. 4,409,323. By electron transfer along the chain.

The term [intramolecular nucleophilic substitution reaction] used in the present invention refers to Reacts at other sites in the compound that are jointly charged electron centers via intervening molecules Refers to a reaction that causes substitution of a group or atom bonded to an electron center. like this Compounds are composed of nuclear groups that are spatially related due to the configuration of the molecule to facilitate reactive proximity. It has both an electron group and an electron group. Preferably the claimed nuclear and electronic groups are cyclic organic rings or Intramolecular reaction in which a transient cyclic organic ring involves a nuclear center and an electron center Useful time-modulating groups placed in the compound to be easily formed by the structure: (where Nu is the CAR it replaces during the reaction of the CAR with the oxidized developing agent) E is the nuclear group attached to the upper position, and E is the electric group attached to the inhibitor unit as described above. is a child group and can be substituted from there by Nu after Nu has been substituted from CAR. LINK spatially relates Nu and E to determine the displacement of Nu from CAR. In this case, an intramolecular nucleophilic substitution reaction accompanied by the formation of a 3- to 7-membered ring is carried out, and PU is a linking group for releasing a G unit).

In this specification, a nuclear group (Nu) is defined as a group of atoms, one of which is electron-rich. to justify Such an atom is called a nuclear center. In this specification, the electronic group (E) is defined as a group of atoms in which one of the atoms is electron deficient. Such an atom is called an electron center To tell.

That is, in the PUG-releasing compound described herein, the time-regulating group includes a nuclear group and a nuclear group. may contain electronic groups, and these groups are spatially separated with respect to each other by the bonding group. , so that upon emission from the CAR, the charge nuclear center and the electron center are opposed. Displacement of the PUG unit from the time regulating group occurs accordingly. released from CAR units The nuclear center must be prevented from reacting with the electron center until the electron The center must be resistant to external impacts such as hydrolysis.

Early reactions time the CAR unit at the nuclear center or atom in relation to the claimed nuclear center. The cleavage of the time-modulating group and PUG unit from the CAR by coupling it to the CAR does not protect the nuclear center. by making them react with electrophilic centers or by adjusting the position of nuclear and electronic groups. can be prevented by preventing them from coming into reactive proximity until release. Ru. Time control groups may include additional photographically useful groups (PUGs) or their precursors. additional substituents may be included, which remain attached to the time control group. It may also be released.

This is due to the intramolecular reaction that occurs between the charge nucleogroup and the electronic group in the time-modulating group. The groups are spatially related after cleavage from CAR so that they can react with each other. It will be recognized that it is indispensable. Preferably, the requested nuclear group and electronic group are Intra-molecular nucleophilic substitution reactions include 3- to 7-membered rings, most Preferably the formation of 5- or 6-membered rings is included.

Additionally, due to the intramolecular reactions that occur in alkaline aqueous solutions encountered during photographic processing, In order to to form a bond between and break the bond between the electronic group and PIG. It will be appreciated that the group should be selected accordingly. all All possible combinations of nuclear groups, bonding groups and electronic groups are included in the bond between the electronic group and the PIJG unit. This does not result in favorable thermodynamic relationships for breaking the bond. However, above It is within the technical field to select an appropriate combination by taking into account the energy relationships described below. is within the technical range of

Typical Nu groups include electron-rich oxygen, sulfur, and nitrogen atoms.

Typical E groups include electron-deficient carbonyl, thiocarbonyl, phosphonyl, and thiocarbonyl. Contains phosphonyl units. Other useful Nu and E groups will be apparent to those skilled in the art. Probably.

The linking group can be alkylene, such as methylene, ethylene or propylene. or aromatic groups such as phenylene or naphthylene or furan. , thiophene, pyridine, quinoline or henzoxazine. It may be a cyclic group such as Preferably LINK is alkylene or arylene be. Group Nu and group Ei, bound to tLINK, release of Nu from CAR At the time of Provide a person in charge. When LINK is a cyclic group, Nu and E are the same ring or different May be bonded to a ring. Aromatic group in which Nu and E are bonded to adjacent ring positions is a particularly preferred LINK group.

TIME may be unsubstituted or substituted. Substituents include fluoro, chloro, Halogen, nitro, alkyl having 1 to 20 carbon atoms, carbon containing bromo or iodo Acyl such as ruboxy, carboxyalkyl, alkoxycarbonyl, alkoxy xycarbonamide, sulfoalkyl, alkanesulfonamide, alkyl sulfonamide reaction rate, diffusion rate or substitution rate, such as onyl, solubilizing group, ballast group, etc. These may include stabilizers, antifoggants, pigments (e.g. separately present in the photographic element, such as filter dyes or solubilized masking dyes). It may be a substituent that is used. For example, solubilizing groups increase the rate of diffusion and The last group decreases the rate of diffusion, and the electron-withdrawing group decreases the rate of substitution of PUG. There will be.

As used herein, the term "electron transfer down a conjugated chain" refers to Refers to the movement of electrons along a chain of atoms that exist together. Conjugated chains are common in organic chemistry shall be understood to have the same meaning as used in This is also double Contains a TIME group that can undergo a fragmentation reaction in which the number of bonds is zero. be caught. Electron transfer down a conjugated chain is described, for example, in U.S. Pat. No. 4.409.323. Are listed.

As mentioned above, one or more consecutive TIME units may be usefully used. can. Useful TlλIE units have finite or very short half-lives. It's okay. The half-life can be controlled by the specific structure of the TIME unit and is You can choose to best optimize the photo features you want to view. 0.001 seconds TIIIE unit half-lives from shorter to more than 10 minutes are applicable to the technology. known in the wild. TIMs with shorter half-lives to make development inhibitor units Two methods using E units are known in the art; A TIME unit with a phase is used in PIG-releasing compounds to yield a development inhibitor unit. often preferred. TIME unit is released from CAR and then PUG May be released spontaneously or may further react with other species present in the processing solution. The Pt1G may be liberated only after processing or the photographic element may be brought into contact with processing solutions. PUG may be liberated during this period.

The following describes representative coupler compounds containing C0LIP groups useful in the present invention. This is a list of patents and publications listed.

Couplers that form cyan dyes upon reaction with oxidized color developing agents are described in U.S. Pat. 772.162, 2.895.826, 3.002.836, 3.002.836, No. 3.034.892, No. 2.474.293, No. 2.423.730 No. 2, 367, 531, No. 3.041.236, No. 4.333. Farbkuppl, published in issue 999, Agfa Mitteilungen. er-eine Literateurubersicht”.

Volume ■, pages 156-175 (1961) and Re5earch Disclo Sure, Item 308119, December 1989 5ection ■D are described in representative patents and publications such as Preferably a coupler like this - are phenols and naphthols.

A coupler that forms a magenta dye upon reaction with an oxidized color developing agent is disclosed in U.S. Pat. ．． No. 600.788, No. 2.369.489, No. 2.343.703, Same No. 2.311.082, Same No. 3.152.896, Same No. 3.519.42 No. 9, No. 3, No. 062.653, No. 2.908.573, Agfa Mi #Farbkuppler-eine Li published in tteilungen teraturubersicht”, Volume ■, pp. 126-+56 (1961 ) and Re5earch Disclosure, [tem 308119. Described in representative patents and publications such as 5ection D in December 1989 has been done.

Preferably such couplers are pyrazolones or pyrazolotriazoles. Ru.

Couplers that form yellow dyes upon reaction with oxidized color developing agents are described in U.S. Pat. ．． No. 875.057, No. 2.407.210, No. 3.265.506, Same No. 2.298.443, Same No. 3.048.194, Same No. 3.447.92 'Farb, published in issue 8, Agfakl i t te i lungen. Kuppler-eine Literaterubersch.

Volume ■, pages 112-126 (1961) and Re5earch Disclo sure, Item 308] 19. December 1989 5ection VI Described in representative patents and publications such as rD. Preferably like this Couplers are benzoylacetamides and pivaloylacetamides.

Couplers which form colorless products on reaction with oxidized color developing agents are described in British Patent No. 61.138, U.S. Patent No. 3.632.345, U.S. Patent No. 3.928.041 , 3.958.993 and 3.961.959. It is stated in the permit. Preferably such couplers react with oxidized color developing agents. However, it is a cyclic carbonyl-containing compound that does not form a pigment.

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

PUG that releases to form a development inhibitor PUG that releases to form a development inhibitor National Patent No. 3.227.554, National Patent No. 3.384.657, National Patent No. 3.615. 506, 3.617.291, 3.733.201 and British patents No. 1,450,479. Useful development inhibitor The inhibitors include iodides, mercaptotetrazoles, selenotetrazoles, and mercaptotetrazoles. Butohenzothiazoles, selenohendithiazoles, mercaptobenzoxa sol, selenobenzoxazole, mercaptobenzimidazole, Lenobenzimidazoles, oxadiazoles, benzotriazoles, pens jDiazoles, oxazoles, thiazoles, noanols, triazoles compounds, thiadiazoles, oxathiazoles, thiatriazoles, tetrazoles compounds, benzimidazoles, indazoles, isoindazoles, merca putoxazoles, mercaptothiadiazoles, mercaptothiazoles, Mercaptotriazoles, mercaptooxadiazoles, mercaptone azo mercaptooxathiazoles, tellurotetrazoles or benzoiso They are heterocyclic compounds such as diazoles. The structure of a typical development inhibitor unit is shown below. As written.

IM It is an aryl. These substituents may be repeated two or more times as substituents. stomach. R”, R”, R”l R”l R”l R1, R” and R1v are also placed pyridine, virol, furan, thiophene, in which the substituents are selected from those mentioned above; Pyrazole, thiazole, imidazole, 1,2,4-triazole, oxazo ole, thiadiazole, indole, benzothiophene, benzimidazole, A substituted or unsubstituted heterocyclic group selected from groups such as benzoxazole, etc. You can.

Rz=, Rz=, Rto, R2 "and R" are R", Rid, Rzb, R 11゜R21, R2h, R1@ and R'', or individual each with one or more halogens such as chloro, fluoro or pro. and p is O, I, 2.3 or 4.

2. PUG that is a dye or forms a dye upon release into suitable dyes and dye precursors. is azo, azomethine, abphenol, abnaphthol, azoaniline, azo Pyrazolone, indoaniline, indophenol, anthraquinone, triary lumethane, alizarin, nitro, quinoline, indigoid and phthalocyanine colors as mentioned above, such as elementary or leuco dyes, tetrazolium salts or shifted salts. Contains dye precursors. These dyes may be metal complexed or It may be chemically resistant. A typical patent describing such dyes is U.S. Pat. ．． No. 880.658, No. 3, No. 931.144, No. 3.932.380, 3.932.381, 3, 942.987 and 4.840.8 It is No. 84. Preferred dyes and dye precursors are Ab, Azomethine, Azophenol. azonaphthol, azoaniline and indoaniline dyes and dye precursors. Ru. The structures of typical dyes and dye precursors are as follows.

Suitable azo, azomethine and methine dyes are described in U.S. Pat. No. 4,840,884. It is expressed by the formula in column 8, lines 1 to 70.

Dyes can be used, for example, in J. .

"Light Absorption of Organic Colorants" by Abian and H. Hartmann. Absorption] f　Organic　Co1orants)　J You can choose from, but are not limited to, those listed below.

A typical dye has the following formula: %formula% (wherein, X is a petro atom such as an oxygen atom, a nitrogen atom and a sulfur atom, and Y is a Contains at least one unsaturated bond having a conjugated relationship with the Ab group, the unsaturated bond is a group of atoms bonded to X through atoms constituting Z, and Z can be conjugated with an azo group is a group of atoms containing at least one unsaturated bond, which is included in Y and Z. the number of carbon atoms is 10 or more) It is an azo dye having a group represented by

Furthermore, Y and Z are each preferably an aromatic group or an unsaturated heterocyclic group. aromatic group Preferred is a substituted or unsubstituted phenyl group or naphthyl group. unsaturated heterocycle At least one group selected from nitrogen atom, sulfur atom and oxygen atom Preferred are 4- to 7-membered heterocyclic groups containing a terroratom, which are benzene-fused ring systems. It may be a part of it. This heterocyclic group is virol, thiophene, furan, imidazo I, 2,4-triazole, oxazole, thiadiazole, pyridine, of indole, benzothiophene, benzimidazole or benzoxazole means a group having such a ring structure.

Y may be substituted with other groups as well as with X and an azo group. Others like this Examples of groups include aliphatic or cyclic hydrocarbon groups, aryl groups, acyl groups, alkoxy groups, Cycarbonyl group, aryloxycarbonyl group, acylamino group, alkylthio group, arylthio group, heterocyclic group, sulfonyl group, halogen atom, nitro group, nitro Roso group, cyano group, -COOM (M=H, alkali metal atom or NH,), hydro Roxy group, sulfonamide group, alkoxy group, aryloxy group and acyl group Contains an xy group. Furthermore, carbamoyl group, amino group, ureido group, sulfamo group yl group, carbamoylsulfonyl group and hydrazino group. These groups are further substituted, for example once or twice, with groups such as those repeatedly disclosed above. You can stay there.

Substituents for Y when Z is a substituted aryl group or a substituted unsaturated heterocyclic group The groups described as can be used in a similar manner for Z.

When Y and Z contain aliphatic or alicyclic hydrocarbon units as substituents, aliphatic in the case of hydrocarbon units having 1 to 32, preferably 1 to 20 carbon atoms; In the case of cycloaliphatic hydrocarbon units, from 5 to 32 carbon atoms, preferably from 5 to 20 g. Any substituted or unsubstituted saturated or unsaturated or linear or Branched groups can also be used. When the substitution is repeated, like this The maximum number of carbon atoms in the resulting substituent is preferably 32.

Y and Zl: When an aryl unit is included as a substituent, the carbon atom of this unit The number of is generally from 6 to 1O, preferably it is a substituted or unsubstituted phenyl group. be. In the present invention, the groups in the formulas shown above and below are defined as follows. .

Acyl group, carbamoyl group, amino group, ureido group, sulfamoyl group, carbamoyl group Moylsulfonyl group, urethane group, sulfonamide group, hydrazino group, etc. Substituted with an unsubstituted group and an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aryl group represents those substituted groups which are substituted to form a mono-, di-, or tri-substituent. However, acylamino groups, sulfonyl groups, sulfonamide groups, acyloxy groups, etc. Each represents an aliphatic group, an alicyclic group, and an aromatic group.

Typical examples of the group represented by the above formula for Abu pigments include, for example: , U.S. Pat. No. 4.424.156 and U.S. Pat. No. 4.857.447, No. 6 column, lines 35-70.

3. PUG which is a coupler The coupler released may be a non-diffusive color-forming coupler, a non-color-forming coupler or a diffusive coupler. May be a sexually competitive coupler. Representative patents and publications describing competitive couplers Written by W, Pu5chel, “On the ChemistryOf~’/h ite Couplers'', Agfa-Gevaert AG Mitte Ilungen and derForschungs-Laboratorium der Agfa-Gevaert AG, Springer Verlag .

1954, pp. 352-367, U.S. Pat. No. 2.998.314, U.S. Pat. No. 2.8. No. 08.329, No. 2.689.793, No. 2.742.832, Doi British Patent No. 1.168.769 and British Patent No. 907.274. helpful The structure of the competition coupler is as follows.

(wherein R4° is hydrogen or alkylcarbonyl such as acetyl, and R4b and R'' are individually hydrogen or sulfo, aminosulfonyl and carboxy ).

(wherein R'' is R'' or R'' as defined above, and R4° is haloken, a lylthion, arylthio or phenylmercaptotetrazole or ethylthion Development inhibitors such as mercaptotetrazoles such as lumercaptotetrazole ).

4. PUG that forms the developing agent The developing agent released is a color developing agent, a black and white developing agent, or a cross-oxidized developing agent. That's fine. These include aminophenols, phenylenediamines, hydroxy Contains virapritons and birapritons.

Representative patents include U.S. Patent No. 2.193.015 and U.S. Patent No. 2.108.243. , same No. 2.592.364, same No. 3.656.950, same No. 3.658.5 No. 25, No. 2, No. 751.297, No. 2.289.367, No. 2.77 2.282, 2.743.279, 2.753.256 and 2.753.256. No. 2.304.953.

The structure of a suitable developing agent is as follows.

(In the formula, R'''' is hydrogen or alkyl having 1 to 4 carbon atoms, and R'b is water. one or more halogens or methyl, such as chloro or bromo; C1-C4 alkyl such as ethyl or butyl group).

f-1 (wherein Rsb is as defined above).

(In the formula, R6' is hydrogen or alkyl having 1 to 4 carbon atoms, and Rs'I R “, R”, R” and R”l;! individual, hydrogen, carbon such as methyl or ethyl Alkyl with a prime number of 1 to 4, carbon such as hydroxymethyl or hydroxoethyl hydroxyalkyl having 1 to 4 prime numbers or sulfoalkyl having 1 to 4 carbon atoms).

5. PUG, a bleach inhibitor Representative patents include U.S. Patent No. 3.705.801, U.S. Patent No. 3.715.208, and and German Published Patent No. 2.405.279. The structure of a typical bleach inhibitor is It is as follows.

(In the formula, R@" is alkyl or aryl having 6 to 20 carbon atoms.)

or (In the formula, R?c, R7-, R7° and R'' and S are as defined above. A solubilizing functional group is often preferred.

Other PUG representative examples of bleach accelerators include, for example, U.S. Pat. No. 4.705.021; No. 4.912.024, No. 4.959゜299, No. 4.705.021 No. 5, No. 063.145, columns 21-22, lines 1-70 and EP Patent No. 0 ．． No. 193.389.

7 Electron transfer agent (ETA) PIG ETA useful in the present invention is 1-aryl- 3-pyrazolidinone derivative, which, when released, yields the desired dye image. It becomes an active electron transfer agent that can promote development under the processing conditions used for the development.

Pyrazo, an electron transfer agent that has been found to be useful in providing development accelerating functions. The lysinone unit is disclosed in U.S. Patent Nos. 4,209,580 and 4,463.081. , No. 4.471.045 and No. 4.481.287, and JP-A-62- They are generally derived from compounds of the type described in Publication No. 123172. this Such compounds include 3-pyrazolidino compounds having an unsubstituted or substituted aryl group in the l-position. It consists of a main structure. There are also combinations disclosed in U.S. Pat. No. 4,859,578. It is for use. Preferably, these compounds are present at the 4- or 5-position of the pyrabridinone ring. Contains one or more alkyl groups.

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

(In the formula, R1'' is hydrogen, R1 and Rlo are each independently hydrogen, a carbon number 1 (such as hydroxyalkyl); -about 8 substituted or unsubstituted alkyl, carbamoyl or about 6 to about 10 carbon atoms Represents substituted or unsubstituted aryl, R'' and Rlo each independently represent hydrogen, Substituted or unsubstituted alkyl having 1 to about 8 carbon atoms or substituted or unsubstituted alkyl having 6 to about 10 carbon atoms or unsubstituted aryl, R1', which may be present at the ortho, meta or para position of the benzene ring, is a halogen, Substituted or unsubstituted alkyl having 1 to about 8 carbon atoms or substituted or unsubstituted alkyl having 1 to about 8 carbon atoms represents unsubstituted alkoxy or sulponamide, and when R is greater than t months ``''The substituents may be the same or different, or together may be carbocyclic or heterocyclic. A ring, for example a benzene ring or an alkylene dioxy ring, may be formed; and t is 0 or 1-3).

When Rah and R'' groups are alkyl, they preferably have 1 to 3 carbon atoms. Delicious. When RIb and Rlc represent aryl, they are preferably phenyl. It is le.

R1 and Rlo are preferably hydrogen.

When R'' represents sulfonamide, it may be, for example, methanesulfonamide, Tansulfonamide or toluenesulfonamide are useful in the present invention [RR has , hydroquinone, catechol, pyrogallol, 1,4-naphthohydroquinone, 1 ．． 2-naphthohydroquinone, sulfonamide phenol, sulfonamide naphtho and hydrazide derivatives, which, upon release, then produce the desired dye. Hydroxytoiodine reacts with a nucleating agent under the processing conditions used to obtain the image. It becomes an active inhibitor redox release agent that can release development inhibitors such as . This way Redox releasing agents are disclosed in U.S. Pat. No. 4,985.336, No. 3a, No. 10- Formula (II) on line 25 and formula (II[) in column 14, line 54 to line 17&l, line 11 and (IV). Other redox releasing agents have European patents. It is described in the application number 0.285.176. Typical redox releasing agents include Includes the following.

Couplers containing other suitable redox releasing agents are disclosed, for example, in U.S. Patent No. 4.98 5.336 Specification No. 17-621! [It is described in.

The following formula represents a 5-16- or 7-shell nitrogen-containing unsaturated heterocyclic group having 2 to 6 carbon atoms. This is linked to the carrier unit via the nitrogen atom, and the sulfone is attached to the ring carbon atom. It has an amide group and a development inhibitor group or a precursor thereof. Z together with the nitrogen atom 5-16- or 7-membered nitrogen-containing unsaturated heterocyclic group containing 2 to 6 carbon atoms DI represents a development inhibitor group, and R6 represents a represents a substituent, and DI is represented by Z via the heteroatom contained therein. and the sulfonamide group is represented by Z Bonded to a carbon atom of a heterocyclic group. However, the heterocycle can be connected to a single carrier through it. The nitrogen atom bonded to the position and the nitrogen atom of the sulfonamide group are, for example, Ken Drupe, as described in ``Theory of Processing'', 4th edition, pp. 298-325. They are arranged so as to satisfy the Kendall-Pelz rule.

The group represented by the above formula is a group that can be oxidized by the oxidation product of the developing agent. be. More particularly, the sulfonamide group is oxidized to a sulfonylimino group. The development inhibitor is then cleaved.

Specific examples of development-inhibiting redox release agents described herein include the overdevelopment-inhibiting redox release agents described below. Other examples of gas-releasing agents are described, for example, in European Patent Application No. 0.362.870. Found in the couplers shown on page 13, line 25 to page 29, line 20 of the specifications. I can do it.

In a preferred embodiment, the PLIG-releasing compound is a development inhibitor-releasing (DIR) compound. It is a compound. These DfR compounds are all known in the art: in the same layer as the emulsion of the invention, in reactive association with this layer or in other layers of the photographic material. may be contained in

These DIR compounds may enable release of higher transportable inhibitor units. or less transportable inhibitors classified as “diffusible” meaning It is one of those classified as "non-diffusible," meaning that it can release It's fine. Old R compounds consist of time-modulating or linking groups known in the art. It's fine.

The inhibitor units of the DIR compound must not change as a result of exposure to photographic processing solutions. Good too. However, this inhibitor unit, as a result of photographic processing, was No. 2.099.167, European Patent Application No. 167.168, JP-A-58 -205150 or as disclosed in U.S. Patent No. 4.782.012. The structure may change and be affected by the formula.

When the DIR compounds are dye-forming couplers, they can be used, for example, with red sensitized emulsions. Reacts with complementary sensitization/10-genide silver emulsions like cyanide dye-forming DIR couplers yellow dye-forming DI in a mixed state or in a mixed format, e.g. with a green sensitized emulsion. It may also be included with R couplers, all known in the art.

DIR compounds are also described in U.S. Pat. No. 39, and bleach accelerator-releasing couplers as described in U.S. Pat. ．． Bleach accelerators disclosed in 865.956 and 4.923.784 It may also be included in reactive association with a releasing coupler. See all these patents and is incorporated herein by reference.

Specific DIR compounds useful in the practice of the present invention are described in the references cited above, and are available for commercial use. and examples illustrating the practice of the invention contained herein.

Dye image-forming compounds and PUG-releasing compounds can be used with equipment and devices known in the photographic art. They can be incorporated into the photographic elements of the present invention by any of the following methods. dye image-forming compounds A photographic element containing a PLIG-releasing compound and a PLIG-releasing compound comprises a support and a single halogen compound. It may be a single color element consisting of a silveride emulsion layer, or it may be a single color element consisting of a support and a plurality of halogen emulsion layers. It may be a multicolor, multilayer element consisting of silver emulsion layers. The above compound is silver halide at least one of the emulsion layers and/or at least one other such as an adjacent layer. layer, in which case the other layer is reactive with the silver halide emulsion layer. related state, thereby produced by the development of silver halide in the emulsion layer Can react with oxidized developing agents. Additionally, silver halide emulsion layers and other The layer may include additives conventionally contained in such layers.

A typical multicolor, multilayer photographic element has an associated cyan dye image-forming compound. red-sensitive silver halide emulsion unit with associated magenta dye image formation A green-sensitive silver halide emulsion unit containing a yellow compound and a yellow emulsion unit associated therewith. - a blue-sensitive silver halide emulsion unit having a dye image-forming compound thereon; It may consist of a support having. Each silver halide emulsion unit is one or more as known in the art and as indicated by the layer order format below It may consist of more layers, and the various units and layers may have different relationships to each other. They may be placed in different positions.

In the elements of the invention, the layer or unit affected by PIG is the layer or unit in the element. Including, at appropriate locations, layers that limit the action of the PUG on desired layers or units. and can be controlled by. That is, at least 1 flil of the photographic element. The layer may be, for example, a scavenger layer, a mordant layer or a barrier layer. this Examples of such layers are, for example, U.S. Pat. No. 892, No. 4.504.569, No. 4.865.946, and No. 5. No. 006.451. This element also includes an antihalation layer, Additional layers may be included, such as filter layers and the like. This element is typically 5 It will have a total thickness excluding the support of ~30 μm. Improvements with developing processing solution Thinner formulations of 5-25 μm are known to provide Generally preferred. For the same reason, more swellable film structures are also preferred. Change The present invention is based on Re5search Disclosure, item 3439. 0゜November 1992, page 869. It is useful for

In the following description of materials suitable for use in elements of the invention, references are made to Re5earch Disclosure, December 1989, Item No. 308,119, the disclosure of which is incorporated herein by reference.

Suitable dispersion media for the emulsion layer and other layers of the elements of this invention include Re5e arch Disclosure, December 1989, [tem 30811 9, Section 5 and publications therein.

In addition to the compounds described herein, elements of the invention include Re5earchDis closure, December 1989, Item 308119 5ecti additions as set forth in A-E and H and the publications cited therein; Dye image-forming compounds and Re5earch Disclosure, 19 December 1989, Item 308119 5ection VI [F and G and Additional PtJG-releasing compounds as described in the publications cited therein may be included.

All elements of the invention include Re5earch Disclosure, 1989. December.

Optical brightener (Section V) as described in Item 308119, Turnip Anti-stinting agents and stabilizers (Section VT), anti-stinting agents and image dyes Stabilizers (Section VI [I and J), Light absorption and scattering agents (Section ), hardener (Section X), coating aid (Section XI) , plasticizers and lubricants (Section XI), antistatic agents (Section XII[), matting agent (Section XVI) and developer modifier (Sec. tion XXI) may be contained.

The elements of the present invention are Re5search Disclosure Item 5ec tionX■ and various supports as described in the literature cited therein. can be applied to.

The elements of the present invention are Re5search Disclosure Item 308 More details later as described in Sections X and XIX of 119. The latent image is typically exposed to actinic radiation in the visible region of the spectrum as described in can be formed and then processed to form a visible dye image. typical Processing to form a visible dye image involves contacting the element with a color developing agent. The process includes the steps of: reducing the developable silver halide; and oxidizing the color developing agent. be caught. 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-methy Ru-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-a Mino-3-β-(methanesulfonamido)ethyl-N,N-diethylaniline salt acid salt and 4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidi Particularly preferred is di-p-1-luenesulfonic acid.

With negative-working silver halide, the processing steps described above give a negative image. The above factors are preferred For example, the Br1tish Journal of P in 1988 As described in Photography Annual, pages 196-198 Known Kodak '71/Kushicolor (Kodak Flexicolor) Developed using C-41 color processing. To give a positive (or inverted) image, The color development process is a non-color development process that develops exposed silver halide but does not form a dye. First development with imaging agent, then uniform overlay of the element to unexposed halogenation This can be done by making silver developable.

The Kodak E-6 process is a typical inversion process.

Development followed by bleaching, fixing or bleach-fixing to remove silver or silver halide; Wash and dry.

The table below lists compounds useful in the practice of this invention.

Table 1 includes formulas for typical dye image-forming coupler compounds.

Table 2 lists typical PUG-releasing compounds that release development inhibitor groups or their precursors. Include expressions. Table 3 shows the 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 elements of the invention. vinegar.

Table 1: Typical Dye Image-Forming Coupler Compounds H C-8 CONH H C-27 C-28 131 Table 2 Typical PUG-releasing type D-10 that releases development inhibitor groups or their precursors D-12 D-17 CM2Co2C,I(,-n CH2Co2C3H, -n H Table 3 Typical PUG-releasing compound dyes that release groups other than development inhibitors B-36 C650 C-52 Table 4 Typical photographic compounds YE-I YE-2 YE-3 YE-4 DYE26 YE-7 YE-8 DYE-9 DYE-40 QL-4 Mixture of isomeric didodecylhydroquinones BA-1 Ag-5-CH2CH2CO2)I A-2 Of course, the color photographic elements of the present invention may include, for example, an underlayer, an overcoat stone, an interfacial active layer, etc. Generally, chemicals such as sexing agents and plasticizers (some of which have been previously described in detail) Any additional layers and compounds known to be useful in photographic elements. It may also include things like this. These are, for example, Industrial 0p ports Ltd.

f(omewell Havant, Hampshire, PO91EF , Re5earch Disclosure, published by the UK, 1989 December, Item 308117. 5ection XV coating and drying method ( All applicable applications, including those set forth in the disclosures herein incorporated by reference). It can be coated onto a suitable support using any suitable method.

A photographic element containing a radiation-sensitive (1001 tabular grain emulsion layer) according to the present invention comprises: in the ultraviolet and visible (e.g. actinic) and infrared regions of the electromagnetic spectrum, as well as in the electronic beam and beta radiation, gamma rays, x-rays, alpha particles, neutron radiation and non-interference Either the (random phase) type or the interferometric (in-phase) type such as that produced by a laser. Painted with various forms of energy, including particulates and other forms of wave-like radiant energy. Imagewise exposure is possible. Exposure can be monochromatic, orthochromatic or may be panchromatic. T. H. James, Theory of Photographic Processing, Vol. 4th edition, Ltacmillan, 1977, 4. Chapter 6.17.18 and 23 High or low intensity exposure, continuous or intermittent exposure, from minutes to milliseconds as shown in Exposure times ranging from relatively short durations down to microseconds and overexposures (s high and low temperatures of the environment, including olarizing exposure) and/or pressure as determined by conventional sensitometric techniques. Use within a useful response range This fabrication is suitable for use in the color photographic elements of this invention. The preparation of ultrathin tabular grain silver iodochloride emulsions that meet the requirements described above is demonstrated.

1.75% by weight low methionine gelatin (treated with an oxidizing agent to reduce its methionine content) gelatin whose amount has been reduced to less than 30 micromol/g), 0.011M of sodium chloride and 1.48 x 10-'M potassium iodide. 2030 mL was made in a stirred reaction vessel.

The contents of the reaction vessel were maintained at 40°C and the pCl was 1.95.

While vigorously stirring this solution, add 30 mL of 1.0 M silver nitrate solution and 0.99 M silver nitrate solution. Add 30 mL of sodium chloride and 0.01M potassium iodide solutions to 30 mL each. They were added simultaneously at a rate of L/min. As a result, particle nucleation occurs, and 2 Crystals formed with an initial iodide concentration of mol%.

The mixture was then held at a temperature that remained at 40°C for 10 minutes. Following this hold Then add 1.0M silver nitrate solution and 1.0M sodium chloride solution to 1 pct. ．． It was added for 40 minutes at a rate of 2m/min while maintaining the temperature at 95%.

The resulting emulsion was a tabular grain silver iodochloride emulsion containing 0.5 mol % of iodide based on the silver base ratio. It was a drug. 50% of the total grain projected area is The aspect ratio of all (1001 tabular grains) with a smaller major face edge length ratio Average ECD of 0.84μm and 0.037μm selected based on ranking m (given by tabular grains with 1001 major faces). The selected tabular grain population has an average aspect ratio (ECD/t) of 23 and 65 It had an average tabular deformity (ECD/'t2) of 7. Main of selected tabular grains The face edge length ratio was 1.4. 72% of the total particle projected area is (1001 principal surface and tabular grains having an aspect ratio of at least 7.5. these The tabular grains have an average ECD of 0.75 μm, an average thickness of 0.045 μm, 18. It had an average aspect ratio of 6 and an average tabular deformity of 488.

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

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

This emulsion was similar to Preparation I except that no iodide was intentionally added. I set it.

The resulting emulsion mainly consists of uprights with edge lengths in the size range of approximately 0.1-0.5 μm. It consists of cubic and rectangular parallelepiped particles with a very small aspect ratio. few big Rods and high aspect ratio (1001 tabular grains were present, but did not constitute a useful amount.

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

The color photographic elements of this invention consist of a single radiation-sensitive emulsion layer on a support. good. This element also includes a radiation-sensitive layer applied to each dome of the support. It includes a so-called duplicated format. It's okay. However, particularly useful embodiments include red light sensitizing units, green light sensitizing units, radiation-sensitive silver halide emulsion in each unit. a multicolor multilayer element comprising at least one dye-forming compound in reactive association with be.

If desired, color photographic elements of the invention can be made from the Kenneth & Iason Pub. lications, Ltd,, Dudley Annex, 12a Nort h　5treet, Emsworth.

Hampshire POIO7DQ, Re5earch published from the UK Disclosure.

Applied magnetism as described in November 1992, [tem 34390] Can be used with a sexual layer.

Some preferred layer sequences for multicolor elements of the invention are as follows.

Antihalation layers applied immediately adjacent to the support on either side of these Not shown in the format. Also, gelatin, pigments, ultraviolet absorbers, polymers, etc. -beads, etc., and a protective coating applied over the topmost dye-image-forming unit. The bar coat layer is also not shown.

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

middle class middle class /////Support ///// Structure■ In the above structure, the red-sensitized cyan dye image-forming silver halide emulsion unit is placed closest to the support, next in order is the green sensitizing macenta dye image-forming halogen a silver emulsion unit followed by a blue-sensitized yellow dye image-forming halogen. There is a silver emulsion unit. The imageable unit is typically an intermediate layer as described above. are separated from each other by.

Each of the imageable units includes a single radiation-sensitive silver halide emulsion layer. It may be In addition, each unit has an independent order of increasing radiation sensitivity. In the introduction, there are two different sensitivities: low sensitivity, high sensitivity, or low sensitivity, medium sensitivity, and high sensitivity, respectively. or three layers may be included. In carrying out the present invention, (1001 main surface a dye image-forming compound and a PUG-releasing compound; The tabular silver chloride emulsion in reactive association is the only blue-sensitized silver halide emulsion unit. or it may be included in each of the silver halide emulsion units. It's fine. If the unit contains more than one radiation-sensitive layer, this plate The silver chloride emulsion may be in the lowest speed layer (low speed layer) or it may be in the unit It may be present in other emulsion layers or in all emulsion layers.

Other useful multicolor multilayer formats for elements of the invention are represented by the structure ■ This is the so-called reverse layer order.

middle class middle class /////Support ///// Structure■ In the above structure, a blue sensitized yellow dye image-forming silver halide emulsion unit is placed closest to the support, followed by the red-sensitized cyan dye image-forming unit. and on top is a green sensitized magenta dye image-forming unit. As described above Individual units are typically separated from each other by intermediate layers.

As mentioned above for Structure ■, each of the imageable units is a single radiation-sensitive It may consist of two layers, each with independently different sensitivities (low sensitivity, high sensitivity). Contains three silver halide emulsion layers (low sensitivity, medium sensitivity, high sensitivity) It's okay to stay. In addition, as described above for structure I, A tabular silver chloride emulsion containing grains is placed only in the blue-sensitized silver halide emulsion unit. or it may be located in each of the units.

When the unit consists of two or more radiation-sensitive layers, this tabular silver chloride emulsion is May be in the lower sensitivity layer or in other or all layers of the unit. It's fine.

Other suitable layer sequences for practicing the present invention are described by structure 1.

middle class middle class middle class middle class Structure■ In the above structure, the lower sensitivity red-sensitizing halogen of the cyan dye image-forming unit The silver emulsion layer is placed closest to the support and the next in order is magenta dye imaging. Lower sensitivity green sensitized silver halide emulsion layer of the color unit, cyan dye image forming unit of a high-speed red-sensitized silver halide emulsion layer and a magenta dye image-forming unit. This is a high-sensitivity green-sensitized silver halide emulsion layer. Consists of 1, 2 or 3 emulsion layers. The blue-sensitized yellow dye image-forming silver halide emulsion unit is on the top. be. Similar to the previous structure, the imageable units are typically interconnected by an interlayer. It is separated from the Elements of the invention having the layer order shown in structure - in the lower speed emulsion layer of the dye image-forming unit as well as in the higher sensitivity of this unit. In the emulsion layer of (a tabular silver chloride emulsion having grains bonded by +001 principal planes) May be included. Tabular silver halide emulsions can also be green- and/or red-sensitized emulsions. in the lowest light-sensitive layer of the unit as well as in all other radiation-sensitive layers of this element. It can also be used.

Yet another useful format for color elements of the invention is shown by structure IVa. represent.

middle class middle class middle class middle class /////Support ///// Structure IVa In the above structure, the lower sensitivity of the red sensitized emulsion unit and the green sensitized emulsion unit The silver halide emulsion layer consists of one of the high-sensitivity silver halide grain layers of these units. , separated by a blue sensitized emulsion unit which may consist of two or three emulsion layers. ing. According to the present invention, silver halide grains having silver halide grains bonded by +1001 principal planes The emulsions are placed in the upper high-speed layer in the green- and red-sensitized silver halide emulsion units. It can also be used in red sensitized silver halide emulsion units or required. It can be used for all basic radiation-sensitive layers.

A variation of structure IVa is structure IVb (not shown), in which lower Sensitivity and high sensitivity The location of the silver halide emulsion layer is the red sensitized emulsion unit and the green sensitized emulsion unit. Both units have been moved. That is, a lower sensitivity green sensitized emulsion layer and a higher sensitivity green sensitized emulsion layer. The positions with the emulsion layers are reversed from their positions in structure IVa, and the red-sensitized milk The same applies to the position of the agent layer. In structure IVb, tabular (1001-sided silver chloride grains) Green- and red-sensitized silver halide emulsions with lower sensitivity of the upper layer in the unit or they can be used in all of the radiation-sensitive layers of the element. can be done.

Other suitable layer sequences for multicolor elements of the present invention are Re5earchDis closure, January 1983, Item 22534, pages 35-37. It is listed.

The invention can be better appreciated by reference to the following examples. the below described In each of the examples, color photographic elements exhibit unexpectedly high levels of image sharpness. Ta. It is sufficient that this image sharpness is evident from simple observation of the processed element. This is noticeable. Such sharpness depends on the refractive index value of the dispersion medium present in the emulsion layer. Tabular (unique shape of 1001 silver halide grains) gives very similar refractive index values It seems that this can be attributed to the feeling.

example! - Manufacture and description of silver halide emulsions Control silver halide emulsions and according to the invention ++00) A tabular silver chloride emulsion bonded by main surfaces was produced as follows. Sensitized. A summary of the emulsions and their properties are listed in Table 5.

The grains were primarily (cubic silver chloride control emulsion with 1001 faces) as described in U.S. Pat. No. 952.491 and Re5search Disclosure, Item 3 08119゜According to the method described in Section I of December 1989. It was manufactured.

These emulsions were sensitized to green, blue or red light by methods known in the art. .

Re5search the cubic silver iodobromide emulsion Disclosure, Item 308119. According to the method contained in 5section I of December 1989. Manufactured by Sensitization was performed by methods known in the art.

A tabular silver iodobromide emulsion was manufactured using U.S. Patent No. 4.439.520, Re5earchD. isclosure, Item 22534. January 1983 and Re5ea rch Disclosure.

[tem 308119. Manufactured by the method described in December 1989 , sensitized.

Tabular silver chloride emulsions bound by (100) major surfaces useful in the practice of the present invention An exemplary manufacturing method is as follows.

Table 5 Characteristics of typical silver halide emulsions Emulsion ID Characteristics Sensitization Eλ1-2C control Cubic Al1C 1 line average edge length 0.6 μm EM-9c Control cubic AgC1 blue average edge length 0.28 μm A. Preparation of emulsions Elil-4, EM-7 and EM-10 Six solutions were prepared as follows. It was manufactured in this way.

solution l Gelatin (bone) 105g NaC11.96g Distilled water 5798g Solution 2 Kl O, 36g distilled water isog solution 3 NaC1199g Distilled water 6760mL solution 4 AgNOz 5.722 molar concentration 510g Add distilled water to make total volume 6300m Solution 5 to L Gelatin (phthalated) +00g Distilled water 1000g Solution 6 80g gelatin (bone) Distilled water 1000g Solution 1 was placed in a reaction vessel equipped with a solution machine. Add solution 2 to this reaction vessel Ta. While stirring the mixture at a pH of 6.0 and a temperature of 40 °C, solutions 3 and and Solution 4 were added for 0.5 minutes at 80 ml/min. Adjust VAg to 175 mV, The mixture was held for 10 minutes. Following this hold, solutions 3 and 4 were simultaneously added for 24 hours. mL/min for 40 min, then VAg at 175 mV 1 m24. This flow was linearly accelerated from 24 mL/min to 48 mL/min over 130 min. Ta. Solution 5 was added and stirred for 5 minutes. The pH was then adjusted to 3.8 and the temperature to 15 The gelatin was precipitated while lowering to °C. Decant the liquid layer and evaporate the reduced volume. I restored it with water. The pH was adjusted to 4.5 and the mixture was held at 40 °C for 5 min. The pH was then adjusted to 3.8 and the precipitation and decanting steps were repeated. Add solution 6 , pH and VAg were adjusted to 5.6 and 130 mV, respectively.

The resulting emulsion mainly has (100) planes and an average equivalent circular diameter (EC) of 1.2 μm. D) and tabular silver chloride grains having an average thickness of 0.12 μm.

The emulsion thus prepared was treated by treating it with 1% NaBr and holding for 5 minutes; Add spectral sensitizing dyes 5S-22 and 5S-26 in a 3:1 ratio, hold for 10 minutes, 1. Na2S 2035H20. -0 mg 1 mol and KAuCl, 1.3 against green light by adding 1 mg mol and heating at 60°C for 10 minutes. It was sensitized to produce a green light sensitized emulsion, EM-1. Similarly, spectral sensitizing dye 5 Red light sensitized emulsion E&I-7 was obtained using S-25 and 5S-23 in a 1.2 ratio. Blue light sensitized emulsion EM-10 was obtained using photosensitizing dye 5S-1.

B Emulsion Snake 1-5. Prepare 8 solutions of E91-8 and E1-11 as follows. It was manufactured as follows.

solution l Gelatin (bone) 211g NaCl 1.96g Distilled water 5800g Distilled water 90g solution 3 NaC1207g Distilled water 7000mL solution 4 NaC113.1g Distilled water 108mL solution 5 AgNOz 5.722 molar concentration 69.8 g Distilled water 5425 g Solution 6 AgN035.722Molar concentration 69.8g Distilled water 73.7g solution 7 Gelatin (phthalated) +oog Distilled water 1000g solution 8 Gelatin (bone) 80g Distilled water 1000g Solution 1 was placed in a reactor equipped with a stirrer at 40°C. Add solution 2 to this reaction vessel. was added to adjust the pH to 5.7. While stirring this mixture vigorously, add solution 4. and Solution 6 were added at 180 mL/min for 30 seconds. The reaction mixture was then stirred for 10 min. held. Following this hold, add solution 3 and solution while maintaining pct at 1.91. Solution 5 was simultaneously added at 24 mL/min for 40 minutes. Next, maintain this speed for 130 minutes. and accelerated to 48 mL/min.

The mixture was cooled to 40°C, solution 7 was added and the mixture was stirred for 5 minutes. next The gelatin was precipitated while adjusting the pH to 3.8 and reducing the temperature to 15 °C. Ta. The liquid layer was decanted and the reduced volume was restored with distilled water. Adjust pH to 4.5 , the mixture was kept at 40 °C for 20 min, then the pH was adjusted to 3.8, and the precipitation and The decanting process was repeated. Solution 8 was added to bring the pH and pCl to 5.6 and 1.6, respectively. Adjusted to 6.

The obtained emulsion mainly has (1001 sides, 1.4 μm average equivalent circle) The emulsion prepared by NatS-22 and 5S-26 were added in a 3:l ratio and held for 10 minutes. 0i5H20 was added at 1.0 mg 1 mol and KAuCl4 was added at 1.3 mg 1 mol. and sensitized to green light by heating at 60″C for 10 minutes to I made 5. Similarly, spectral sensitizing dyes 5S-25 and 5S-23 were added in a l:2 ratio. to obtain red light sensitized emulsion EM-8 and blue light sensitization using spectral sensitizing dye 5S-1. Emulsion EM-I+ was obtained.

Production of C0 large tabular silver chloride emulsion Typical method for producing large (ECD greater than 2 μm) tabular silver halide emulsions is as follows.

Bone gelatin 1.77% by weight, sodium chloride 0.0 at 55°C and pH 6.5 2945 mL of a solution containing 56M potassium iodide 1.86x IO''M was added. In a stirred reaction vessel, add 15 mL of 4.0 M silver nitrate solution and 4.0 M sodium chloride. 15 mL of solution was added simultaneously at a rate of 30 mL/min.

The mixture was then held for 5 minutes, 7000 ml of distilled water was added and the pci was increased to 2. The temperature was increased to 65°C while adjusting the pH to 6.5. following retention , through growth using a dual-zone process. The size of the resulting particles was increased. In this method, a total volume of 30 m1 was grown. In a well-stirred continuous reactor, a solution of 0.67 M silver nitrate was added to a solution of sodium chloride. Premixed with a 0.67M solution and a 0.5% by weight solution of bone gelatin at a pH of 6.5. Ta. The effluent from this premix reactor is then used as a growth reactor during this step. Added to the original functioning reaction vessel. During the growth process, the microcrystals from the continuous reactor are Aged onto the original crystals using Stowald aging. During this growth process the growth reactor The total suspension volume was kept constant at 13.5 L using ultrafiltration.

The flow rates of 0.67M silver nitrate solution and 0.67M sodium chloride solution were adjusted at 25 minute intervals. linearly from 20 mL/min to somL/min, 150 mL/min and 240 mL/min increased to The flow rate of the 0.5 wt% gelatin reagent was kept constant at 500 mL/min. I held it. A continuous reactor in which these reactants were premixed was heated to 30°C and a pC of 2.45. 1, while the growth reactor was heated to a temperature of 65°C, a pct of 2.15 and a pct of 6.5 Maintained pH.

The result of this operation is a high aspect ratio tabular grain iodide containing 0.01 mol% iodide. 6 moles of compound emulsion were obtained. More than 90% of the total projected grain area is on the (+001 principal surface) , tabular grains having an average ECD of 2.55 μm and an average thickness of 0.165 μm. given by. Therefore, this tabular grain population has an average aspect ratio of 15.5. and had an average tabular deformity of 93.7.

This emulsion was prepared by treating it with 1% NaBr, holding for 5 minutes, and spectral sensitizing dye (SS -25 and 5S-23, 2:1 ratio) and held for 10 minutes, Na2 1.0 mg 1 mol of S20 x 5H20 and 1.3 mg 1 mol KAuCl4 sensitized to red light by adding 1000 ml and heating at 60°C for 10 min. .

Sample lots were prepared by applying the following layers to a transparent support in the order listed: . Quantities of components are given in g/m''.

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

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

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

These layers further contain α-4-nonylphenyl-ω-hydroxy as a surfactant. Sea-poly(oxy-(2-hydroxy-1,3-propanediyl)) and (rose) -monoctylphenyl)-di(oxy-1,2-ethanediyl)sulfonate Consisting of

This film was treated with 2% by weight of bis-vinylsulfonylmethane based on the total gelatin. It was hardened at the time of casing.

Same as sample 101 except that emulsion EM-1c was replaced with an equal amount of emulsion EM-2c. Sample 102 was manufactured in the following manner.

Same as sample lot except that emulsion EM-1c was replaced with an equal amount of emulsion EM-3c. Sample +03 was manufactured in the same manner.

Same as sample 101 except that emulsion EM-1c was replaced with an equal amount of emulsion EM-4 Sample +04 was produced.

Same as sample 101 except that emulsion EM-1c was replaced with an equal amount of emulsion EM-5. Sample +05 was produced.

Image dye-forming coupler C-1 was combined with 0.32 g of image dye-forming coupler C-2. Sample +06 was manufactured in the same manner as sample 105 except that the sample was replaced.

Same as sample 101 except that emulsion EM-1c was replaced with an equal amount of emulsion EM-6c. Sample +07 was produced.

Same as sample 101 except that emulsion EM-1c was replaced with an equal amount of emulsion EM (-7) Sample +08 was produced.

Same as sample 101 except that emulsion EλI-1c was replaced with an equal amount of emulsion EM-8. Sample 109 was manufactured in the following manner.

Emulsion EM-1c was replaced with an equal amount of emulsion EM-9c, and the image dye-forming coupler - Sample except that C-1 was replaced with 1.08 g of image dye-forming coupler C-3. Sample +10 was produced in the same manner as Sample 101.

Same as sample 110 except that emulsion EM-9c was replaced with an equal amount of emulsion EM-10. A sample ill was prepared.

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

Coupler C-t is a cyan image dye-forming coupler and C-2 is a magenta colored coupler. C-3 is a dye-forming coupler and C-3 is a yellow image dye-forming coupler. Ru. These couplers are prepared as photographic coupler dispersions as known in the art. Gave.

Samples 101 to 112 were measured using graduated concentration test objects. exposure to white light through a site test object) and Developed using C-41 processing. This process uses propylene amines in the bleaching solution. It was changed in that it consisted of ferric tetraacetate.

Photographic sensitivity allows for Status M density, which is 0.15 higher than Dmin after processing. It was measured as the exposure required to achieve this. Status M concentration at Dmax value is also measured. Established.

Table 6 below shows, for each sample, emulsion name: surface area per grain; color sensitization of one color. Elementary image-forming couplers: Experimentally observed relative sensitivities: for spectrally sensitized emulsions. The expected relative photosensitivity assuming that photosensitivity is a linear function of particle surface area is: and g/m of silver for each sample! D per 27 m2 of coated coupler The status M dye density formed at max, that is, the standardized dye density gain rate (norm alized dye density yield) (DDY).

Table 6: Photosensitivity and dye yield in color development processing 101 E+c Green C- 10,471,001, Ox 7.41 Control 102 Ell-2c Green C-1 2,161,29x 4.6x 5.69 Control 103 EM-3c Green C-1 5,591,95x 11.8x 3.61 Control 104 EM-4 Green C-12 ,716,91x 5.8x 5.85 Invention 105 EM-5 Green C-13, 6914, I2x 7.8x 5.50 This invention! 06 EM-5 Green C-23, 6919,05x 7.8x 13.66 Invention 107 EM-6c Red C- 10,471,00x 1. Ox 7.12 Control 108 E 1-7 Red C- 12,716,45x 5.8x 5.50 Invention 109 EM-8 Red C-1 3,698,51x 7.8x 5.17 Invention +1 OEM-9c Blue C-3 0,471,00x 1. Ox 3.01 Control Ill EM-101F C-3 2,7116,59x 5.8X 3.35 Invention 112 EM-11 Blue C- 33,6921,41x 7.8x 3.27 Invention control sample 101.102 and The results obtained with 103 and 103 showed high photographic effect with cubic shape + 100 lAgC1 particles. This shows the difficulty in obtaining high values of dye density or dye density yield. Particle size (and When dye density gain decreases dramatically, photographic speed decreases Almost no increase. For spectrally sensitized emulsions, photographic speed is measured by surface area per grain. is expected to increase directly as a function of It wasn't done. Conversely, samples 104 and 105 of the present invention have The photographic sensitivity far exceeded what was expected. In addition, these The dye density gains obtained are similar to those obtained from smaller photographically sensitive control samples. It was beyond anything.

The results from inventive sample 106 show that a lower stoichiometric amount is required for pigment formation. Image dye-forming couplers that require oxidized developing agents (Coupler C-2 is a 2-equivalent image forming coupler) image coupler and coupler C-1 is a 4-equivalent image coupler). or by selecting image couplers that form high extinction image dyes. It shows that both luminous intensity and dye density yield can be further improved.

The results from samples 107 to +09 and the results from samples 110 to 112 are based on these results. It has been shown that advantageous effects were also obtained from samples of the invention that are sensitive to red and blue light, respectively. It shows.

As can be easily seen, the photographic samples according to the invention are Not only does it provide greatly improved photographic sensitivity, but also a surprisingly Gives high pigment density formation.

The above sample was exposed to white light through a graduated density test object and 1 using the color photographic paper developing agent described in Patent No. 4.892.804. Developing was performed for 95 seconds. Results similar to those shown in Table 1 were obtained.

Exposure and development using Kogutsu C-41 processing as described above were carried out for 1 minute and 2 minutes. Samples 101-112 were repeated using development times of , 3 minutes, 4 minutes, and 5 minutes. versus The improved performance of the inventive element compared to that of the control sample is again observed in all cases. It was done.

Changing the contact time of the photographic material and the processing solution can be controlled by changing the temperature or the concentration of components in the processing solution. is typically used by those skilled in the art to approximate the effects of changes in

Thus, longer processing times may be a result of increased component concentrations or elevated temperatures or both. approximating the effects of the other, a shorter treatment time may result in reduced component concentrations or lowered temperatures or both. Approximate the direction. These effects are well known to those skilled in the field of photographic technology, and A person skilled in the art can use the elements of the invention to obtain the desired results for a particular application. Treatment compositions and temperatures can be selected.

Example 3 - Photographic element containing a PUG-releasing compound that releases a development inhibitor. Samples 201-205 were prepared by application to transparent supports in the order listed.

The amounts of components are given in g/m2.

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

Layer 2 (g photosensitive layer): 0.54H EM-13c, 0.54g image dye formation Coupler C-1, 1, 54 g of gelatin and various DIR compounds listed in Table 7 consists of the amount of

IW3 (protected H'): Consists of 2.15 g of gelatin.

These layers further contain α-4-nonylphenyl-6)-hydrocarbon as a surfactant. xo-poly(oxy-(2-hydroxy-1,3-propanediyl)) and monooctylphenyl)-di(oxy-1,2-ethanediyl)sulfone It consists of

This film was treated with 2% by weight of bis-vinylsulfonylmethane based on the total gelatin. It was hardened at the time of application.

Sample 201 except that emulsion EM-+3c was replaced with an equal weight of emulsion Eλl-14c. Control sample 206-2+1 was prepared similarly to ~205.

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

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

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

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

Samples 201 to 20 except that emulsion Eλl-13c was replaced with an equal weight of emulsion crucible-4. Control samples 316 to 321 were produced in the same manner as in Example 5.

Samples 201-20 except that emulsion EM-13c was replaced with an equal weight of emulsion EM-5. Samples 322 to 329 were manufactured in the same manner as in Example 5.

B Effect of PIG-releasing compounds that release development inhibitors on processed elements Samples 201-329 are exposed to light through a graduated density test object, and It was developed as a color negative film using Kogutsu C-41 processing. This process was modified in that the bleaching solution consisted of ferric propylene diaminetetraacetate.

The useful latitude for each sample is 0.0.0 from Dmin for each sample. lO big space 0.10 less than the exposure and Dmax required to allow status M density Quantified by measuring the exposure required to allow Status M density did. The greater the difference in exposure, the greater the useful latitude of the sample. Become. Emulsions and development inhibitor releasing (DIR) that allow for large increases in latitude ) compounds are particularly useful. Furthermore, the photographic gamma of each sample is exposure value towards the center of the latitude obtained after processing as a function of logarithmic exposure. It was quantified as the rate of change in Status M concentration. Significant decrease in gamma Also particularly useful are combinations of emulsions and DIR compounds that allow.

Table 7 below shows the emulsion name, DIR compound name and amount (g/m2) for each sample; The relative gamma of the treated elements (in each case the corresponding counterpart made without DIR compound) normalized to the control sample); and the relative latitude of the treated sample (in each case , normalized to a corresponding control sample prepared without DIR compound).

Samples 201-211 include those typically used in combination with DIR compounds. Either similar cubic silver iodobromide emulsions or tabular silver iodobromide emulsions are included.

These results demonstrate the large increase in latitude made possible by these combinations. and a large decrease in gamma. Thus, a specific amount and type of DIR The compounds can be combined with silver iodobromide emulsions to form various latitudes needed for specific applications. Obtaining the de and gamma positions is well within the skill of the skilled photographer.

Samples 301-315 contained cubic silver chloride emulsions known in the art. Ru. These results demonstrate that the combination of these cubic silver chloride emulsions with various DIR compounds Typically, at best, there is very little increase in useful latitude and It has been shown that it leads to less decline. In some cases, latitude reaches a plateau. , while in other cases the gamma increased. This property applies to all encountered in these combinations. It may be related to loss of body sensitivity or to changes in Dmin.

Samples 317-321 and 323-329 C, flat plate according to the present invention +100) A combination of surface AgCl crystals and DIR compounds is shown.

Table 7. Effect of DIR compounds on gamma and latitude 201 control EM-13 c None 100.0 100.0 (Ag[Br cube) 202 Control EAI-+3c D-2 (0,032) 30.5 4.57.0 203 Control EAI-13c D-1 (0,029) 79.0 339.02 04 Control EM-13c D-3 (0,03+) 80.0 240.0205 Control EAI-13c D-4 (0,037) 79.0 427.0206 pairs Teru EM-14c None 100.0 100.0 (AglBr flat plate) 207 Control EM-14c D-2 (0,032) 40.9 776.020 8 Control Elt+-14CD-1 (0,058) 81.3 331.0209 Control ENl-14c D-4 (0,074) 52.3 550.0210 pairs Teru EM-14c D-6 (0,061) 77.3 537.0211 Control EM-14c D-7 (0,081) 79.5 219.0301 Control E! J-6c None 100.0 100.0 (AgC1 cube) 302 control EM-6CD-1 (0,043) 89.5 96.6303 control EM-6c D-2 (0,043) 107.2 106.8304 Control E M-9c None ioo, o ioo.

(AgC1 cube) 305 Control EM-9c D-1 (0,058) 110.0 132.030 6 Control EM-9c D-2 (0,032)! 69.0 50.0307 control EM-12c None 100.0 100.0 (AgC1 cube) 308 Control EM-12c D-1 (0,058) 96.0 132.030 9 Control EM-+2c D-2 (0,032) 109.5 112.0310 Control EM-12c D-3 (0,031) 104.8 112.0311 pairs Teru EAI-12c D-4 (0,037) 89.7 120.0312 Control EM-3c None 100.0 100.0 (AgCl cube) 313 Control EAI-3c D-2 (0,032) +04.3 181.03 14 Control εM-3c D-1 (0,058) 108.6 178.0315 Control EM-3c D-4 (0,073) 87.0 100.0316 Control E Without M-4 100.0 100.0 (AgCI (+001 flat plate) 317 Present invention EM-40-2 (0,032) 73.6 281.8318 pieces Invention EM-40-1 (0,058) 54.9 288.4319 Invention E M-40-3 (0,031) 73.6 302.0320 Invention EAI-4 0-4 (0,037) 58.2 316.0321 Present invention Ell-4D-5 (0,027) 89.0 174.0323 Present invention EM-5D-2 (0,0 32) 73.3 525.0324 Present invention EM-5D-1 (0,058) 61.4 1072.0325 Present invention ENf-5D-4 (0,073) 52 ．． 3' 575.0326 Invention EM-5D-6 (0,055) 59.6 '355.0327 Present invention EAI-5D-7 (0,081) 90.4 468.0328 Present invention EM-5D-3 (0,031) 86.8 218. 0329 Present invention EAI-5D-5 (0,032) 75.0 121.0 units Photosensitivity due to light +100) From the combination of face plate-shaped silver chloride emulsion and DIR compound The sample makes a useful decrease in gamma accompanied by a large increase in latitude at the same time. This will be easily recognized. These results are based on the well-known (too Silver chloride emulsions typically exhibit increased galvanicity when used in combination with DIR compounds. It is highly unlikely that the This is a surprising thing. Elements of the invention have been described by many persons skilled in the photographic arts. The combination of emulsions and DIR compounds that have been optimized over many years enables allows for both greater latitude increase and greater gamma suppression at the same time than is particularly noteworthy.

Processing process using exposure and Kogutsuku C-41 processing and the salmon folding of the above data. Samples 201-211 and and 301-329. Elements of the invention compared to control samples The latitude improvements and gamma reductions previously observed were maintained.

As mentioned above in Example 2, varying the contact time of the photographic material with the processing solution can be is used in the art of photography to approximate the effects of changes in the concentration of components in processing solutions. Typically used by people. By such means, skilled photographers can , processing times and compositions, DIR compounds, dyes for specific applications, according to the present invention. Forming compounds and sensitization (1001-sided silver chloride tabular grain emulsions can be selected) Samples 901-969 were prepared generally as described for sample 101 in Example 2. Manufactured. All of these samples were coated on transparent supports.

Samples 970-972 were coated on reflective supports. All of these elements are included in the present invention. represents another example of the implementation of. Type and amount of silver halide emulsion used in each sample and types of image dye-forming coupler compounds and PUG-releasing coupler compounds and The amounts are shown in Table 8 below.

B. Dye density gain sample from the processed element was measured using a graduated density test object. Exposure to clear light and processing using the Kogutsuku C-41 process. this The treatment was varied in that the bleach solution consisted of ferric propylene diaminetetraacetate. in each case , status in the red, green or front band corresponding to the maximum absorption wavelength exhibited by the sample M concentration was used. Transmission density was measured for samples 901 to 969, and sample 970 Reflection density was measured for ~972.

Table 8 shows the types and amounts of emulsions and coupler compounds used in each element. for each sample Standardized dye density yield (DDY) observed for Or B) is also shown.

901E included 1-5 (0,538) C-5 (0,646) 7.20R902 EM-5 (0,538) C-6 (0,646) 4.95R903E8l-5 (0,538) C-7 (0,646) 5.03R904E8 I-5 (0,5 38) C-8 (0,646) 6.15R905E Milk 1-5 (0,538) C-31 (0,646) 5.37R906Elf-5 (0,538) C- 10 (0,646) 4.0IR9071JI-5 (0,538) C-12 ( 0,646) 7.00R908EM-5 (0,538) B-1 (0,646 ) 6.54R912EλI-5 (0,538) C-41 (0,215) 3 ．． 56R913EλI-5 (0,538), C-42 (0,215) 4.1 7R914EM-5 (0,538) C-13 (0,646) 3.64G91 5 To E l-5 (0,538) C-14 (0,646) 8.61G916 EM-5 (0,538) C-26 (0,646) 3.678917 EM- 5 (0,538) B~32 (0,646) 4.70B918 EM-5 (0 ,538) C-3(0,646)+D-t8(0,o65)+3-t( 0,oo5) 4. t7B919 EM-5 (0,538) C-2 (0,64 6) +D-18 (0,065) +8-1 (0,005) 7.11G92 0E8 f-5 (0,538) C-31 (0,646) +D-+8 (0,06 5) +8-1 (0, o05) 5.58R921EM-5 (0,538) C-17 (0,646) 7.950922 EM-5 (0,538) C-3 1 (0,646) +B-1 (0,054) 4.97R923Eλ! −5(0 ,538) C-31 (0,646) +B-1 (0,054) +D-26( 0,054) 4.96R924EλI-5 (0,538) C-31 (0,6 46) +B-6 (0, o54) +D-26 (0,054) 4.68R92 5EM-5 (0,538) C-31 (0,646) +D-19 (0,o54 ) 5.66R926EM-5 (0,538) C-31 (0,646) +D -19 (0,054) +C-41 (0,054) 4.89R927EM-5 (0,538) C-31 (0,646) + D-25 (0, o54) 5.2 4R9281JI-5 (0,538) C-31 (0,646) +D-27 ( 0,054) 5.23R929E8! -5 (0,538) C-31 (0,6 46) +B-1 (0,054) +D-3 (0,054) 4.83R932 EM-10 (0,430) C-1 (0,323) +D-28 (0,054) 7.15R933EM-10 (0,430) C-1 (0,323) +C- 45 (0,108) 6.37R9341JI-10 (0,430) C-1 ( 0,323) +D-20(0,054)? , 89R935EM-10 (0, 430) C-1 (0,323) +D-3 (0, o54) 7.77R936 EM-10 (0,430) C-1 (0,323) +D-1 (0,054) 6.48R937EM-1o (0,430) C-1 (o, 323) +C-4 6 (0,054) 6.79R938Ell(-10(0,430) C-1( 0,323) +C-47 (0,054) 7.27R939EM-10 (0, 430) C-1 (0,323) +8-1 (0,054) +D-1 (0, 054) 5.88R940Ell-10 (0,430) C-1 (0,32 3) +8-1 (0,054) +D-20 (0,054) 7.12R94 1EM-10 (0,430) C-1 (0,323) 10B-1 (0,054) +D-3 (0,054) 6.86R942ENl-10 (0,430) C -1 (0,323) +D-29 (0,108) 5.45R943EM-10 (0,430) C-1 (0,323) +C-49 (0,005) 7.98 R944EM-10 (0,430) C-1 (0,323) +C-50 (0, 005) 7.98R945E8l-10 (0,430) C-1 (0,323 ) +C-51 (0,005) 7.99R946EM-11 (0,538) C-27 (1,078) 4.04B947E8l-11 (0,538) C- 3 (0,8o7) +C-27 (0,269) 3.33B948Enl-11 (0,538) C-29 (1,078) 3.0889496M-11 (0, 538) C-28 (1,078) 2.588950E8l-11 (0,53 8) C-25 (1,078) 1.298951 ENl-11 (0,538 ) C-37 (1,078) 4.39B952E8l-11 (0,538) C-38 (1,078) 4.708953E8l-11 (0,538) C- 3 (1,078) +D-30 (0,054) 3.49B9541JI-11 (0,538) C-3 (1,078) + D-19 (0,054) 3.73 8955 EM-11 (0,538) C-3 (1,078) +8-1 (0 ,054) 3.47B956 EM-4 (0,538) C-18 (0,43 0) 5.06G957E9l-4 (0,538) C-15 (0,430) 8.08G9586kl-4 (0,538) C-33 (0,430) 8.5 6G959E 1-4 (0,538) C-16 (0,430) 11.59 G960E included 1-4 (0,538) C-16 (o, 323) +C-15 ( 0, +o7) 9.55G961 EM-4 (0,538) C-34 (0,4 30) 11.67G9622M-4 (0,538) C-36 (0,430) 6.530963El-4' (0,538) C-22 (0,430) 6 ．． 0IG964E included 1-4 (0,538) C-40 (0,430) 5.5 8G965 E too! -4 (0,538) C-15 (0,430) 10B-1 ( 0,032) 7.95G966 EM-4 (0,538) C-15 (0,4 30) +D-30 (0,032) 8.0OG967 Eλ+-4 (0,53 8) C-15 (0,430) + D-16 (0,032) 7. '56096 86M-4 (0,538) C-15 (0,430) +C-40 (0,032 ) 7.48G969 EM-4 (0,538) C-15 (0,430) + C-39 (0,032) 7.28G970 EM-4 (0,538) C-5 (0,430) 10.54R971EλI-4 (0,538) C-20 (0 ,430) 11.32G972 Elf-4 (0,538) C-25 (0, 430) 4.29B The above results were demonstrated when combined with various PUG-releasing coupler compounds. Combined, +1001 plane silver chloride tabular grain emulsions and a wide variety of dye imaging This shows that excellent dye density yields were obtained with the neutral coupler compounds.

Samples 901-969 were exposed to white light through a graduated density test object and 45 seconds in the color photographic paper developer described in Patent No. 4.892.804. Developed, then bleached and fixed. Again good pigment density formation from these elements was observed.

Example 5 The following layers containing one and the same development inhibitor-releasing (DIR) coupler compound: Samples 401-412 were prepared by applying to a transparent support in the order listed. . The amounts of components are given in g/m2.

Layer 1 (/anti-lusion layer): consists of gray silver and gelatin.

Layer 2 (photosensitive layer): 0.33g tJl-5, 1,82g gelatin, image dye It consisted of a forming coupler (0.54 g) and the DIR compounds listed in Table 9 below.

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

These layers further contain α-4-nonylphenyl-lopandiyl as a surfactant. )) and (octylphenyl)-di(oxo-1,2-ethanediyl) ) consists of sulfonates.

This film was mixed with 2% by weight of bis-vinylsulfonylmethane based on total seratin. B. Influence of DIR coupler compounds on the resolution of processed elements Measuring modulation transfer function (NIFT)/percent response as a function of spatial frequency Samples 401-412 were exposed to a sinusoidal turn of white light in order to obtain the desired results. next The sample was then processed using the Koda Tsuku C-41 process. Bleaching used for processing 1. It was changed to consist of 3-propylenediaminetetraacetic acid. exposed and processed The MFT/centre response is measured as a function of the spatial frequency in the film plane. The specific details of this exposure-evaluation cycle can be found in Jo urnalof Applied Photographic Engineer ring, volume 6, pages 1-8. February 1980 R1 ambert S and F ．． C. Eisen. “A System for the Automati cEvaluation of Alodulation Transfer Functions of Photographic Materials'' Are listed.

The MTF percent response of the photosensitive layer of these samples was monitored at several spatial frequencies. I tarred. Higher values of MTF percent response indicate sharper images. Furthermore, Spatial frequency at which the MTF percent response drops to 70%, a measure of resolution The number was measured. Higher spatial frequencies indicate films with better resolution. child The results of the test are also shown in Table 9.

Table 9: λITF Percent Response and Resolution 401 Without C-1 90% 82% 86% 61% 38 c/mm402 C-I D-298% 90% 1 01% 79% 60 c/mm (0,032) 403 C-I D-198% 93% 104% 79% 70 c/mm ( 0,058) 404 C-I D-3100% 90% 97% 74% 58 c/mm ( 0,031) 405 C-I D-4100% 95% 102% 78% 72 c10+ m (0,037) 406 C-I D-691% 85% 92% 70% 52 c/mm (0 ,058) 407 C-I D-7103% 93% 94% 67% 38 c/mm ( 0,081) 408 C-20-31 105% 108% 105% 82% 61 c/m m (0,058) 409 C-20-397% 97% 100% 79% 61 c/mo+( 0,027) 410 C-20-498% 98% 103% 80% 86 c/mm (0 ,032) 411 C-2D-3298% 100% 108% 89% 78 c/mm (0,030) 412 C-2D-3390% 92% 90% 69% 49 c/mm (0 ,037) As can be seen, elements of the invention containing various DIR compounds all improved. It showed sharpness and generally improved resolution. Dye image-forming coupler compounds and and DIR coupler compound selection, the specific spatial frequencies increased and the degree of enhancement It's changing. Suitable combinations for a particular application will be readily ascertained by those skilled in the art. Ru.

Example 6 - Preparation and Development Processing of Elements Containing Development Accelerator-Releasing Compounds The following layers are described. Samples 501-504 were prepared by applying them to transparent supports in the order listed. Growth The amount is g/m! Indicated by

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

Layer 2 (photosensitive layer): E! of 0.43H! 11-10.1.82 g gelatin, 0 ．． 54 g of image dye-forming coupler C-1 and the development accelerator described in Table 1O below. It consists of a release type (DAR) compound.

1'i3 (protective layer), consisting of 2.15 g of gelatin.

These layers further contain α-4-nonylphenyl-ω-hydroxy as a surfactant. Sea-poly(oxy-(2-hydroxy-1,3-propanediyl)) and (para -t-octylphenyl)-di(oxy-1,2-ethanediyl)sulfonate Consisting of

This film was treated with 2% by weight of bis-vinylsulfonylmethane based on total seratin. It was hardened at the time of application.

B Effect of development accelerator releasing (DAR) compound on photosensitivity of element Samples 501-5 04 to white light through a graduated density test object, and then Kogutsu C- 41 processing was used for development processing. The bleaching solution used for processing is 1,3-propylene. It was changed to consist of diaminetetraacetic acid. Then, with a normalized gamma of 1.0, Dm Test by measuring the exposure required to make a density 0.15 higher than in. The relative photographic sensitivity of the materials was evaluated.

These values are listed in Table 10.

Table: Impact on photographic sensitivity caused by IO development accelerator-releasing (DAR) compounds 501 Without C-1 100.0% 502 C-I C-49 (0,005) 102°3% 503 C-I C- 50 (0,005) 177.8% 504 C-I C-51 (0,005) 198.5% As can be seen, all DAR compounds are increased within the elements of this invention. Added photographic sensitivity. Of course, the amount of increased photosensitivity depends on the dye image-forming compound and and the selection and amount of DAR compound. The combination suitable for a particular application is Easily confirmed by the vendor. DAR compounds are also described elsewhere herein. It can be used in combination with other PUG-releasing compounds.

The amounts and types of bleach accelerator releasing (BAR) compounds shown in Table 11 were added to the photosensitive layer. The test was carried out in a manner similar to that used to prepare Sample 501 of Example 6, except that Materials 505 to 511 were produced. To further demonstrate the practice of the invention, development inhibitor release Type (DIR) compounds were also added to some samples.

B. Bleach accelerator releasing (BAR) compound affected samples 501 and 505-511. Exposure to white light through a graduated density test object with tin removal from the treated element. , then developed using the method described in U.S. Pat. No. 4,892.804. Processed. The amount of metallic silver (g/m2) remaining in the treated elements was determined by X-ray fluorescence. was measured. These values are listed in Table II.

Table I + Impact on tin removal caused by bleach accelerator releasing (BAR) compounds 501 C-1 None None 0.038505 C-I D-28 (0,054) None 0.008506 No C-1 D-20 (0,054) 0.21450 7 C-I B-1 (0,054) D-20 (0,054) 0.06750 8 C-1 No L D-3 (0,054) 0.250509 C-I B-1 ( 0,054) D-3 (0,054) 0.076510 Without C-1 D-1 (0,054) 0.025511 C-I B-1 (0,054) D-1 ( 0,054) 0.003 As can be seen, BAR compounds greatly reduces the color quality of images made visible or printed from functions to promote the removal of metallic silver deposits. What is particularly noteworthy is that DIR typically leaves a large amount of metallic silver in the processed element. The ability of BAR compounds to remove silver from elements of the invention that also contain the compounds.

The amounts and types of competitive coupler releasing (CCR) compounds shown in Table 12 were added to the photosensitive layer. A method similar to that used to prepare sample 501 of Example 6, except that Samples 512 and 513 were produced.

Samples 501, 512 and 513 were exposed to white light through a graduated density test object. The film was exposed to light and then developed using Kogutsu C-41 processing.

The bleaching solution used in the treatment was changed to consist of 1,3-propylenediaminetetraacetic acid. Ta. The relative photographic speed, gamma and maximum density of the processed elements were determined. these values are listed in Table 12.

501 No C-1 100.0% 100.0% ioo, o% 512 C -I C-46 (0,054) 97.7% 94.4% 97.3%513 C-I C-47 (0,054) 95.5% 86.0% 89.4% Above As can be seen from the results, the CCR compound reacts competitively with the oxidized developing agent and This reduces the sensitivity, density and gamma of the elements of the invention. Of course, these influences The size of the image-forming compound and CCR compound depend on the selection of the image-forming compound and the amount of each used. Depends on. Suitable combinations for a particular application will be readily ascertained by those skilled in the art. C.C. The R compounds may also be combined with other PUG-releasing compounds described elsewhere herein. Can be used together.

Samples 514 and 515 were prepared by applying the following layers to a transparent support in the order listed. was manufactured. The amount of components is shown in 27 m2.

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

Layer 2 (photosensitive layer): 0.538 g EM-5, 1, 82 g gelatin, 0. 646g of image dye-forming coupler C-31, 0,054g of DIR compound Riichi 3 and 0.054 g of compound B-1, and in sample 515, 0.032 g of electron transfer agent releasing (ETAR) compound.

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

These layers further contain α-4-nonylphenyl-ω-hydroxy as a surfactant. Sea-poly(oxy-(2-hydroxy-1,3-propanediyl)) and (para -t-octylphenyl)-di(oxy-1,2-ethanediyl)sulfonate Consisting of

This film was treated with 2% by weight of bis-vinylsulfonylmethane based on the total gelatin. It was hardened at the time of casing.

Samples 514 and 515 were exposed to white light through a graduated density test object and then The film was developed using Kogutsu C-41 processing. 1 bleach solution used for treatment , 3-propylenediaminetetraacetic acid. Relativeness of processed elements Luminous intensity, gamma and maximum density were measured. These values are shown in Table 13.

514 Without C-31 100.0% 100.0% 100.0% 515 C -3I C-52 (0,032) 407.4% 115.1% 113.8% As can be seen, the ETAR compound increases the photosensitivity of the elements of the invention containing it. , density and gamma were improved. As shown in this example, ETAR compounds are also used in the present invention. For use in combination with other PLIG-releasing compounds listed elsewhere in the specification. can be done.

Except that the amounts and types of bleach inhibitor-releasing compounds shown in Table 14 were added to the photosensitive layer. Sample 516 was prepared in a manner similar to that used to produce sample 501 of Example 6. Manufactured.

Samples 501 and 516 were exposed to white light (measured through a graduated concentration test object). Ta. These values are listed in Table 14.

``Groups of snoring and snoring 11 views of 11 levels of groan suppressant-releasing (BIR) compounds. influence 501 Without C-1 0.02 0.038516 C-L D-29 (0,1 08) 0.35 0.350 As you can see, BIR compounds contain this Prevents bleaching of treated elements, thereby making them look like movie soundtracks IR-readable density images (quadrant formation) that can be used for applications such as enable. BIR compounds also include other PUG-releasing compounds described herein. Can be used in combination with objects.

Example 11 - Preparation and Testing of Multicolor Multilayer Photographic Elements A, Preparation of Elements Apply the following layers to the cellulose triacetate transparent support in the order listed. A color photographic element, sample ML-101, was prepared by. Amount of silver halide is expressed in g/m2 of silver. The amounts of other substances are given in g/m2.

Both organic compounds are commonly used in the art (2. Coupler It was used as an emulsion containing a solvent, a surfactant and a stabilizer, or as a solution. The coupler solvents used in the photographic samples (this 1, 1) cresyl phosphate, di -n-butyl phthalate, N, N-di-n-ethyllaurinamide, N, N- Di-Δ-butyllaurinamide, 2,4-di-t-amylphenol, N-butyl -N-phenylacetamide and 1,4-cyclohexylene dimethylene bis- (2-ethoxyhexanoate). Mixtures of compounds are known in the art. They were used as individual dispersions or as co-dispersions, as is common practice. child The sample also contains sodium hexametaphosphate, 3,5-disulfocatecol di- Consisting of thorium, gold sulfide, propargyl-aminobenzoxazole, etc. there was. The silver halide emulsion is 4-hydroxy-6-methyl-1,3,3a,7-te Stabilized with traazaindene.

Layer + (L/-'/a anti-layer 1 knee 0.043g DYE-1; 0.0 21g DYE-2: 0.065g DYE-6; 0.215g DYE-6; 2.15g of gelatin.

Layer 2 (lowest sensitivity red sensitized layer 1: red sensitized silver chloride cubic emulsion at 0.215 g, Average edge length 0.28 μm; 0.592 g red sensitized silver chloride (1001 plane plane) Tabular emulsion, average equivalent circular diameter 1.2 μm, average grain thickness 0.14 μm.

0.70g TC-1; 0.075g Tegelatin: 2.04g Tegelatin.

Layer 3 (highest sensitivity red sensitized layer): 0.538g red sensitized silver chloride (1001 side Tabular emulsion, average equivalent circular diameter 1.4 μm, average grain thickness 0.14 μm.

0.129g C-1; 0.032g D-+5; 2.15g gelatin.

Layer 4 (middle layer) - Gelatin 1.29g.

Layer 5 (highest sensitivity blue sensitized layer 1: 0.215 g of green sensitized silver chloride cubic emulsion, Average edge length 0.28 μm; 0.592 g green sensitized silver chloride (1001 plane plane) Platy emulsion, average equivalent circular diameter 1.2 μm, average grain thickness 0.14 μm: 0, 323 g C-2; 0.022 g D-17; 1.72 g gelatin.

Tabular emulsion, average equivalent circular diameter 1.4 μm, average grain thickness 0.14 μm20.08 6 g C-2; 0.011 g D-16; 1.72 g gelatin.

Layer 7 (middle layer): 1.29 g of gelatin.

Layer 8 (lowest sensitivity blue sensitized layer): 0.215g blue sensitized silver chloride cubic emulsion, Average edge length 0.28μm; Blue sensitized silver chloride (100) surface at 0.215g Platy emulsion, average equivalent circular diameter 1.2 μm, average grain thickness 0.12 μm: 1.08 g C-3; D-18 at 0.065 g; Gelatin at 1.72 g.

Layer 9 (highest sensitivity blue sensitized layer): 0.323g blue sensitized silver chloride (100) surface Platylet emulsion, average equivalent circular diameter 1.4 μm, average grain thickness 0.14 μm; 0.12 C-3 for 9g; D-18 for 0.043g; Gelatin for 1.72g.

Lippmann emulsion; 0.026g silicone lubricant; tetraethylammonium Perfluorooctane sulfonate; -octylphenoxyethoxyethyls Sodium sulfonate salt, 0.0538g anti-matting polymethyl methacrylate Beads; 1.61g gelatin.

This film was treated with 2% by weight of bis-vinylsulfonylmethane based on the total gelatin. It was hardened at the time of application. surfactants, as commonly practiced in the art; Coating aids, scavengers, soluble absorbent dyes and stabilizers were added to the various layers of this sample. added to. The total dry thickness of the photosensitized layer is approximately 13,7 μm, and the total dry thickness of the applied layer is The dry thickness was approximately 19.5 μm.

Sample tag-102 is the same except that 0.043 g of compound B-1 was added to l1i2. It was the same as sample ML-101.

Sample Sanification-103 was prepared by adding 0.065 g of compound C-42 to layer 2 and adding 0.043 g of compound C-42 to layer 2. and 0.065 g of compound C-40 to layer 5 and 0.065 g of compound C-40 to layer 5. Sample ML-102 was the same as sample ML-102 except that 043 g was added to layer 6.

Sample ML-104 contains compounds D-3, D-15, D-16, D-17 and D-1 8 was removed, and the following compounds were added in its place. That is, layer 2 contains 0.0 of D-4. Layer 3i: 0.032 g of D-1 was added, and 0.03 g of D-1 was added to layer 5. 0.032 g of D-1 was added to layer 6, and 0.011 g of D-7 was added to layer 8. 065g was added and layer 91. :The test except that 0.043g of D-7 was added. It was the same as that of the chemical compound-101.

Sample ML-105 was tested except that 0.043 g of compound B-1 was added to layer 2. It was the same as the sample ML-104.

Sample ML-107 had layer 2. 3. Double the amount of silver chloride emulsion in 5 and 6, Sample ML-10 except that the amounts of compounds D-1 and D-4 in these layers were also doubled. It was similar to 4.

The sample layer 108 is layer 2. 3. Double the amount of silver chloride emulsion in 5 and 6, The amounts of compounds D-3, D-15, D-16 and D-17 in these layers were also doubled. Other than that, it was the same as sample Heka-101. This change increases the film thickness by approximately 1 ．． 0 μm was added.

For samples ML-201 to 205 and ridges-207 to 208, silver chloride emulsions were prepared as follows. A sensitized silver iodobromide emulsion containing about 3.7 mol % iodide is used in the photosensitive layer. Same as samples &lL-101-105 and &lL-107 to +08 except that It was manufactured as follows.

Layer 2: 0.2] 5 g 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 Particle thickness 0.09μm0 In layer 3 (N-201-205 and ML-207-208) 0.538g Red sensitized silver iodobromide emulsion, average equivalent circular diameter 1.2 μm, average grain thickness 0.13 μm0 In layer 5: 0.215 g of green sensitized silver iodobromide emulsion, average equivalent circular diameter 0.5 μm, flat Average grain thickness 0.09 μm; 0.592 g green sensitized silver iodobromide emulsion, average equivalent circle Diameter 10μm, average particle thickness 0.09μm0 layer 6: 0.538g green sensitized iodine Silver bromide emulsion, average equivalent circular diameter 1.2 μm, average grain thickness 0.13 μm0 In layer 8: 0.215g blue sensitized silver iodobromide emulsion, average equivalent circular diameter 0.5μm, flat Average grain thickness 0.08μm; 0.215g blue sensitized silver iodobromide emulsion, average equivalent circle Diameter 1.05 μm, average particle thickness 0.11 μm.

In layer 9, 20.323 g of blue sensitized silver iodobromide emulsion, average equivalent circular diameter l, 35 μm, flat Uniform particle thickness 0.13μm0 B. Pass the density measurement sample of the exposed and developed element through a graduated density test object. The film was exposed to white light and then processed using the Kogutsu C-41 process. process The bleaching solution used was changed to consist of 1,3-propylenediaminetetraacetic acid.

The status Ma generated in the unexposed and undeveloped areas of each sample was measured after processing. . ISO Speed - Exposure level 10 stops higher than point (i.e. 3.01 The Status M concentration produced after treatment with agE) was measured. ISO Speed Port Int is the exposure required to create Status M density 0.15 higher than Dmin. be. The difference in concentration production was calculated by subtraction. This difference represents the concentration production of each sample. vinegar. This value is shown in Table 15.

Table 15 = Status M concentration generation ML-101 Invention 2.27 2.23 2.00 ML-201 Control 1.3 7 1.88 2.53ML-102 Present invention 2.33 2.26 1.95M L-202 control 1.67 2.01 2.709 IL-103 present invention 2. 43 2.31 1.64 ML -203 control 1.74 2.01 2.38 ML-104 Invention 1.87 2.21 2.54 ML-204 Control 1.4 5 2.07 2.78 Adhesive-105 Invention 1.93 2.27 2.59ML -205 Control 1.60 2.17 2.74 Octa-107 Invention 2.17 2.17 2.78ML-207 control 1.60 2.27 Changed to 2.89- 108 Invention 2.81 2.19 2.69 ML-208 Control 1.33 1 ．． 87 As can be seen from 2.3, the density generation ability of the multilayer multicolor element of the present invention is Generally equivalent to that of an otherwise similar control sample containing a silver iodobromide emulsion or exceed it. Furthermore, the elements produced according to the invention are not as good as those obtained in the control sample. This produced a more uniform density production in the three color records than the one above. in concentration generation This greater uniformity is likely due to the lower uniformity in the elements of the invention compared to that in the control elements. This can be attributed to improved development in the red sensitized layer in the layer. to the position of this layer of elements This reduced dependence of dye concentration formation in a particular layer is an important advantage of the present invention. Ru.

C1 Photo-ablation and pressure desensitization effect measurement sample ML The pressure and wear sensitivity of -101 to 105 and Iriyama -207 to 208 were determined for each sample. Approximately 42 mm with a roller device equipped with sandblasted steel wheels. The evaluation was made by applying a pressure of psi (2,9xlO'Pascal). sand The recesses and ridges of blasted wheels can be removed, for example, from the film transport of a camera. Imitating dirt particles or other defects on the mechanism, etc.

Both the pressurized and non-pressurized parts of each sample are tested using a graduated concentration test object. The film was exposed to transparent white light and then processed using Kogutsu C-41 processing.

The bleaching solution used for treatment is 1. Modified to consist of 3-propylenediaminetetraacetic acid I got it.

The magnitude of the pressure force effect is determined by the blue status M Dmi of the non-pressurized part of each sample. n was quantified by comparing with that of a pressurized section of the same sample. Polishing ho The increase in density caused by eel is pressure abrasion or light abrasion. pressure force The smaller the value of Dust or imperfections in the transfer equipment can cause unsightly marks and imperfections to form. It is excellent in that it shows how difficult it can be. This means that a color fill like this The improved quality of the prints made from the system is shown.

In related tests, a roller rig fitted with a wheel that polished a portion of each sample was used. By subjecting the sample to a pressure of approximately 25 psi (1,7 x lo' Pascals) at were evaluated separately for pressure desensitization. These samples were prepared as just described. Blue status M density between exposed, developed, pressurized and non-pressurized samples The maximum difference is noted. Pressure from an abrasive wheel can e.g. During winding or tightly rolling the It mimics the effect of pressure on the film sample as it occurs during transport. The pressure is Tends to cause emulsion desensitization or density loss. Large density in photographic film The loss is that prints made from such films have unsightly marks and defects. It should be avoided if possible. For this reason small values of pressure desensitization are desirable. .

The results of these photoabrasion and pressure desensitization tests are shown in Table 16.

Table 16: Photoabrasion and pressure desensitization results Blue status M Change in Dmin ML-101 Invention +0.06 -0 ．． 04 Emulsification-201 Control +0.19 -0.02λIL-102 Present invention +0 ．． 05 -0.02ML-202 control +0.20 -0.02ML-103 bottles Invention +0.04 -0.02ML-203 control +0.15 -0.03N+ L-104 Invention +0.06 -0.02 ML-204 Control +0.12 - 0.04ML-105 Invention +0.06 -0.02ML-205 Control +0 ．． 12 -0.02 in IL-107 Present invention +0.05 -0.02 in IL-2 07 Control +0.14 -0.02ML-108 Invention +0.04 -0.0 2NIL-208 control +0.16 -0.04 As can be seen, the present invention The samples prepared by When exposed, it exhibits less pressure desensitization and significantly improved resistance to photoabrasion. Ta.

D. Measurement of effectiveness of masking coupler 1. Use of cyan dye-forming, preformed magenta dye-releasing couplers Photographic samples ML-102 and Kyuka-103 were tested using a graduated concentration test object and Kodak. Exposure to light passed through a Klatten 29 filter. This arrangement allows for red light separation exposure. make it possible. This sample was then developed using Kogutsu C-41 processing. place 1. Changed to consist of 3-propylenediaminetetraacetic acid Ta. As the effect of red light exposure, the difference between Dmin and Dmax at green status M density is Changes between the two were measured. This change in green density is shown in Table 17.

Table 17: Change in green density as a function of red light exposure Sample masking coupler No change in green density ML-102 10.39 ML-103C-42〇, +5 Sample ML-10,3 containing the masking coupler showed improved color separation properties; Undesirable green density associated with exposure and development of the red light sensitized layer was observed in sample ML-103. was reduced by the presence of skinning coupler C-42.

2. Use of magenta dye-forming, preformed yellow dye-releasing couplers Photographic samples ML-102 and ML-103 were measured using a graduated concentration test object and Kodak. Exposure to light passed through a Klatten 74 filter. This arrangement allows green light separation exposure. make it possible. This sample was then developed using Kogutsu C-41 processing. place The bleaching solution used for cleaning was changed to one consisting of 1,3-propylenediaminetetraacetic acid. . As the effect of green light exposure, the difference between Dmin and Dmax at blue status Ma degree is Changes between the two were measured. This change in blue density is shown in Table 18.

Table 18: Change in blue density as a function of green light exposure Sample masking coupler No change in blue density ML-102 +0.44 ML-103C-40+0.15 Sample ML-103 containing the masking coupler showed improved color separation properties, with green Undesirable blue density associated with exposure and development of the photosensitized layer was masked in sample ML-103. was reduced by the presence of King coupler C-40.

E. Color reversal development processing Photographic sample ML-101 was exposed to white light through a graduated density test object and then The film was developed according to the Kodak E-6 reversal film process.

An inverted image suitable for direct viewing was formed.

Apply the following layers to the cellulose triacetate transparent support in the order listed. A color photographic element, sample λ-301, was produced by the following steps. Amount of silver halide is expressed in g/m2 of silver. The amounts of other substances are given in g/m2.

The organic compound is a coupler solvent, both as commonly used in the art. , used as an emulsion containing surfactants and stabilizers or as a solution. This photo test Coupler solvents used in the sample include tricresyl phosphate, di-n-butyl Phthalate, N,N-di-n-ethyllaurinamide, N,N-di-n-butyl Laurinamide, 2,4-di-t-amylphenol, N-butyl-N-phenylene Ruacetamide and 1. 4-cyclohexylene dimethylene bis-(2-ethoxy cyhexanoate). Mixtures of compounds are commonly practiced in the art. 'Used as individual dispersions or as co-dispersions. This sample is , sodium hexametaphosphate, 3.5-disulfonic acidol disodium, It consisted of gold sulfide, propargyl-aminobenzoxazole, etc. Halo The silver genenide emulsion contains 2 g of 4-hydroxy-6-methyl-], 3.3 g per mole of silver. a, stabilized with 7-chitraazaindene.

Layer 1 (/anti-lusion layer 1: 0.323g gray silver; 2.44g gelatin) Chin.

Layer 2 (lowest sensitivity red sensitized layer 1: 0.269g red sensitized silver iodobromide emulsion, iodide about 4 mol%, average equivalent circular diameter 0.5 μm, average particle thickness 0.08 μm: 0 ．． 538g red sensitized silver iodobromide emulsion, approximately 3.7 mol% iodide, average equivalent circular diameter 1. 0 μm, average particle thickness 0.09 μm: C-l at 0.70 g; at 0.075 g D-3; Gelatin at 2.04g.

Layer 3 (highest sensitivity red sensitized layer): 0.538g red sensitized silver iodobromide emulsion, iodide Approximately 3.7 mol%, average equivalent circular diameter 1.2 μm, average particle thickness 0.12 μm; C-1 at 0.129g, D-3 at 0,065g; gelatin at 2.15g.

Layer 4 (middle layer): 1.29 g of gelatin.

Layer 5 (highest sensitivity blue sensitized layer 1: 0.269g green sensitized silver iodobromide emulsion, iodide about 4 mol%, average equivalent circular diameter 0.5 μm, average particle thickness 0.08 μm; 0 ．． 538g green sensitized silver iodobromide emulsion, approximately 3.7 mol% iodide, average equivalent circular diameter 1. 0 μm, average particle thickness 0.09 μm; 0.323 g TeC-2, 0. l0 8g of D-2: 2.15g of gelatin.

Layer 6 (Highest sensitivity blue sensitized layer 1: 0.538g green sensitized silver iodobromide emulsion, iodide Approximately 3.7 mol%, average equivalent circular diameter 1.2 μm, average particle thickness 0.12 μm; C-2 at 0.086g; DIR compound D-16 at 0.065g 1.72g and gelatin.

17 (medium flJ [tl]: Seyfn 1.29g.

Layer 8 (lowest sensitivity blue sensitized layer): 0.161g blue sensitized silver iodobromide emulsion, iodide about 4 mol%, average equivalent circular diameter 0.5 μm, average particle thickness 0.08 μm + 0 ．． 269g blue sensitized silver iodobromide emulsion, approximately 3.7 mol% iodide, average equivalent circular diameter 0. 72μm, average particle thickness 0.09μm; 1.08g Tec-3: 0.065 D-8 in g: Gelatin in 1.72 g.

Layer 9 (Highest sensitivity blue sensitized layer 1: 0.646g blue sensitized silver iodobromide emulsion, iodide About 9 mol%, average equivalent circular diameter 1.3 μm; c-320 at 0.129 g. 043 g D-8; 1.72 g gelatin.

Layer 10 (protection 1i-11 + 0.108g DYE-8: 0.161g DYE-8) Yε-92 0.108g unsensitized silver bromide Lippmann emulsion; N,N,N-trimethylene -N-(2-perfluorooctylsulfonamido-ethyl)ammonium iodine -Dite; Sodium triisopropylnaphthalene sulfonate, 0.54g gelatin.

Layer 11 (protective layer-21: silicone lubricant: tetraethylammo at 0.026 g) perfluorooctane sulfonate; -octylphenoquine ethoxye Anti-matting polymethyl methacrylic acid sodium salt, 0.0538g Relate beads; 0.54g gelatin.

This film was mixed with 2'M% bis-vinylsulfonylmethane based on the total gelatin. It was hardened at the time of application. Surfactants, as commonly practiced in the art. , coating aids, scavengers, soluble absorber dyes and stabilizers were added to the various formulations of this sample. added to the layer. The total dry thickness of the photosensitized layer was approximately 16.4 μm, and The total dry thickness of the gold plate was approximately 21.7 μm.

Sample ML-302 was prepared by removing the silver iodobromide emulsion from layers 8 and 9, etc. as follows. Sample ML-301 was the same except that the weight of the silver chloride emulsion was replaced.

Cubic blue sensitized silver chloride emulsion at +0.43 g in layer 8, average edge length 0.28 μm.

In layer 9: 0.646g cubic blue sensitized silver chloride emulsion, average edge length 0.6μm 0 Photographic sample ML-303 was prepared by removing the silver iodobromide emulsion from layers 8 and 9 as follows: The photographic sample was the same as 301 except that the same weight of silver chloride emulsion was used. .

In layer 8: 0.43 g (1001 plane tabular blue sensitized silver chloride emulsion, average equivalent circular diameter 1 ．． 2 μm, average particle thickness 0.14 μm.

In layer 9: 0.646 g (1001 plane tabular blue sensitized silver chloride emulsion, average equivalent circular diameter 1.4 μm, average grain thickness 0.14 μm 0B, filtration in the lower layer of the treated element. Modulation transfer function (MFT) as a function of spatial frequency in the film plane Samples ML-301, 9 IL-302 and &1L to measure percent response -303 was exposed to white light in a sinusoidal pattern. Then, the sample was 41 processing was used for development processing. The bleaching solution used for processing was mixed with 1°3-propylene. It was changed to consist of diaminetetraacetic acid. The exposed and processed elements are was evaluated to measure the MFT percent response as a function of inter-frequency frequency. this dew Specific details of the light-evaluation cycle can be found in the Journal of Applie d Photographic Engineering.

Volume 6, pages 1-8, February 1980, R. Amberts and F. C. Eis. en, -ASystem for the Automatic Evalu ation of Modulation Transfer Function Described in s of Photographic Materials- . A more general description of the measurement and meaning of &lTF percent response curves can be found in this document. It is stated in the paper cited in .

Monitor the MTF percent response of the green and red light sensitizing layers of these multilayer multicolor films. - and the spatial frequency at which the &ITF percent response drops to 50% was recorded. . Higher spatial frequencies indicate films with better resolution. combined red and the average MTF percent response of the green records. Table 19 shows the results of this test. Shown below.

&1L-301 Tabular Ag1Br 58 42 114% 112% ML-30 2 cubic AgC14338113% 108% sample ML-301 to ML-303 are the same except for the form and content of the emulsion contained in the blue light sensitized layer. these In examples, the blue light sensitizing layer is closer to the exposure source than the green light sensitizing layer or the red light sensitizing layer. Main departure The blue-light sensitized layer was sensitized according to By this, the upper blue light sensitized layer contains a cubic silver chloride emulsion or a tabular silver iodobromide emulsion. The resolution of the lower layer, as seen by comparing the results from the control element has been greatly improved. MTF percent response at low spatial frequencies is also significantly improved. It is.

Apply the following layers to the cellulose triacetate transparent support in the order listed. A color photographic element, sample &IL-401, was prepared by. silver halide The amount is shown in 27 m2 of silver. The amounts of other substances are given in g/m2.

The organic compound is a coupler solvent, both as commonly used in the art. , used as an emulsion containing surfactants and stabilizers or as a solution. This photo test Coupler solvents used in the sample include tricresyl phosphate, di-n-butyl Phthalate, N, N-di-n-ethyllaurinamide, N, N-di-n-buty Lulaurinamide, 2,4-di-t-amylphenol, N-butyl-N-phene Nyl acetamide and 1,4-cyclohexylene dimethylene bis-(2-ethoxy cyhexanoate). Mixtures of compounds are commonly practiced in the art. They were used as individual dispersions or as co-dispersions as described above. This sample is further , sodium hexametaphosphate, 3,5-disulfonic acidol disodium, sulfur It consisted of gold oxide, propargyl-aminobenzoxazole, etc. /)B The silver germide emulsion contains 2 g of 4-hydroxy-6-methyl-1,3,3 per mole of silver. a, stabilized with 7-tetraazaindene.

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

Layer 2-(SY) (lowest sensitivity blue sensitized layer 1: 0.43 g of blue sensitized silver chloride (100 One-sided tabular emulsion, average equivalent circular diameter 1.2 μm, average grain thickness 0.12 μm; Yellow dye-forming image coupler C-3 at 1.08 g: D-18 at 0.108 g ; 1.72g of gelatin.

Layer 3-(FY) (Highest sensitivity blue sensitized layer 1: Blue sensitized silver chloride (1 001 plane tabular emulsion, average equivalent circular diameter 1.4 μm, average grain thickness 0.14 μm; Yellow dye-forming image coupler C-3 at 0.129g; D at 0.086g -18: Gelatin at 1.72g.

Layer 4-(IL) (intermediate layer): Gelatin 1.29g0 Layer 5-(SC) (lowest sensitivity Red sensitized layer 1: 0.807g red sensitized silver chloride + 1001 tabular emulsion, average etc. Value circle diameter 1.2μm, average particle thickness 0.12μm; cyan dye formation at 0.70g Image coupler C-1; D-15 at 0.043 g; gelatin at 1.08 g.

Layer 6-(FC)f highest sensitivity red sensitized layer): Red sensitized silver chloride +1 at 0.538g 001 plane tabular emulsion, average equivalent circular diameter 1.4 μm 1 average grain thickness 0.14 μm: Cyan dye-forming image coupler C-1 at 0.129 g; D- at 0.048 g 15; 1.08g of gelatin.

Layer 7-(IL) (intermediate layer): 1.29 g of gelatin.

Layer 8- (SM) (Highest sensitivity blue sensitized layer 1: Green sensitized silver chloride at 0.807g (1001-plane tabular emulsion, average equivalent circular diameter 1.2 μm, average grain thickness 0.12 μm Magenta dye-forming image coupler C-2 at m + 0.323g; 0.065 g D-17: 2.15 g gelatin.

Layer 9- (Fit) (Highest sensitivity blue sensitized layer 1: Green sensitized chloride at 0.538g Silver + 1001 plane tabular emulsion, average equivalent circular diameter 1.4 μm, average grain thickness 0.14 μm; 0.086g Magenta dye-forming image coupler C-2; 0.03 D-16 for 2g; Gelatin for 1.72g.

Layer 1 O-(QC) (Protective layer 1: 0.108 g and DYE-8: O, 118 g DYE-9; 0. 108g unsensitized silver bromide Lippmann emulsion, 0.026g Silicone lubricant; tetraethylammonium perfluorooctane sulfonate , -octylphenoxyethoxyethylsulfonic acid thorium salt; 0.053 8g anti-matting polymethyl methacrylate beads; 1.99g gelatin.

This film was treated with 2% by weight of bis-vinylsulfonylmethane based on the total gelatin. It was hardened at the time of application. surfactants, as commonly practiced in the art; Coating aids, scavengers, soluble absorber dyes and stabilizers were added to the various layers of this sample. added to. The total dry thickness of the photosensitized layer was approximately 10.5 μm, and the applied The total dry thickness was approximately 16.8 μm. Therefore, the layer order of sample ML-401 is , support, AHU, SY, FY, IL, SC, FC, IL, SM, F M, it was QC.

Test RML-402 lit Compound C-40 8- (SLI) d 0.065 Sample ML-4 except that 0.043 g was added to layer 9-(FM). It was the same as 01.

Sample ML-403 has compound C-43 added to layer 8-(SM) at 0.091 g. , Same as sample ML-401 except that 0.059 g was added to layer 9-(FM). It was like that. The amount of C-43 is equimolar to the amount of C-40 used in ML-402. It was.

Sample ML-404 combines the layers used in sample ML-401 as follows in the order AH Supported by U, SC, FC, IL, SM, Decoy, II, SY, FY, QC. It was manufactured by applying it to a carrier.

Layer 1- (AHU) (antihalation layer): DYE-1 at 0.043g , DYE-2 at 0,021g; C-39 at 0.065g; D at 0.215g YE-6: Gelatin at 2.15g.

1ii2-(SC) (lowest sensitivity red sensitized layer 1: red sensitized silver chloride at 0.807g (1001 tabular emulsion, average equivalent circular diameter 1.2 μm, average grain thickness 0.12 μm cyan dye-forming image coupler C-1 at 0.70 g; D-1 at 0.043 g 5; 1.08g of gelatin.

Layer 3-(PC) (Highest sensitivity red sensitized layer 1: Red sensitized silver chloride +1 at 0.538g 001 plane tabular emulsion, average equivalent circular diameter 1.4 μm, average grain thickness 0.14 μm: Cyan dye-forming image coupler C-1°0 at 0.129g, D at 048g -15, 1,08g of gelatin.

Layer 4-(IL) (intermediate layer) - 1.29 g of gelatin.

Layer 5- (SKI) f Highest sensitivity blue sensitized layer 1: Green sensitized chloride at 0.807g Silver + 1001 plane tabular emulsion, average equivalent circular diameter 1.2 μm, average grain thickness 0.12 μm; 0.323g magenta dye-forming image coupler C-2; 0.06 5g of D-17: 2.15g of gelatin.

Layer 6-(FLI) (highest sensitivity blue sensitized layer): 0.538g green sensitized silver chloride + 1001 plane tabular emulsion, average equivalent circular diameter 1.4 μm, average grain thickness 0°14 μm Magenta dye-forming image coupler C-2 at 0.086g; 0.032g D-+6; 1.72g of gelatin.

[7-(IL) (intermediate layer): 1.29 g of gelatin.

Layer 8-(SY) (lowest sensitivity blue sensitized layer): 0.43g of blue sensitized silver chloride (100 One-sided tabular emulsion, average equivalent circular diameter 1.2 μm, average grain thickness 0.12 μm; Yellow dye-forming image coupler c-3 at 1.08g; 0, D-18 at 108g ; 1.72g of gelatin.

Layer 9-(FY) (highest sensitivity blue sensitized layer): 0.646g of blue sensitized silver chloride [0 01 plane tabular emulsion, average equivalent circular diameter 1.4 μm, average grain thickness 0.14 μm; Yellow dye-forming image coupler C-3 at 0.129g; D- at 0.086g 18: Gelatin at 1.72g.

Layer 10- (QC) (protective layer): O, l08g"II' DYE-8,0 , l18g DYE-9; 0.108g unsensitized silver bromide Lippmann emulsion; 0 ．． 026g silicone lubricant, tetraethylammonium perfluorooctane Sulfonate; -octylphenoxyethoxyethylsulfonic acid sodium salt ; 0.0538 g anti-matting polymethyl methacrylate beads; 1.9 9g of gelatin.

Layer 2- (SC) t: 0.065 g of Compound C-42 as a sample Layer 3- (FC) i,: Added at 0.043 g and added compound C-40. Layer 5-(sλ1) was added at 0.065 g, layer 6-(FM) was added at 0.043 g. The sample was the same as Heda-404 except that it was added in g.

B Measurement of masking coupler effect Two different magenta dye-forming masking couplers: preformed yellow - One containing a dye (C-40) and a protected color that turns yellow only after processing. A comparison of the results from the other (C-43) containing element was made.

Photographic samples ML-401-&IL-403 were added to the scaled concentration test object and Kodak. Exposure to light passed through a Klatten 74 filter. This arrangement allows green light separation exposure. make it possible. This sample was then developed using Kogutsu C-41 processing. place The bleaching solution used for cleaning was changed to one consisting of 1,3-propylenediaminetetraacetic acid. . As the effect of green light exposure, Dmin and Dmax at blue status M11 degrees Changes between the two were measured.

This change in blue density is shown in Table 20 below. Furthermore, these samples are calibrated. Expose to white light through the concentration test object and monitor the relative blue light sensitivity of the blue light sensitizing layer did. These values are also shown in Table 20.

Table 20. Changes in blue density as a function of green light exposure and as a function of white light exposure Changes in blue sensitivity Compared to -401 +0.31 100.0% 8 to L-402' C-40+0 ．． 15 38.9%9 IL-403C-43+0.14 61.7% Masking Samples AIL-402 and ML-403 containing couplers showed improved color separation properties. The undesirable blue density associated with exposure and development of the green light-sensitive layer is shown in the sample. Presence of masking coupler C-40 in 02 and C-4 in sample AIL-403 Decreased by the presence of 3. Blue light sensitivity is reduced by the protected shield provided by C-43. The enhanced masking capabilities of the conventional masking machine provided by the C-40 It is also clear that it has been substantially improved compared to Noh. So ML-403 has a blue feel. A more desirable combination of luminous intensity and color reproduction is shown.

Effect of layer order on film optics of C lower red-sensitized layer Sample ML-401-Kuuka-4 In No. 05, all of the photosensitive layers contained a (1001-plane tabular silver iodobromide emulsion).

Samples ML-404 and ML-405 are standards for color films containing silver iodobromide emulsions. It has a layer order. That is, the blue light sensitized layer is closer to the exposure source than the green or red sensitized layer.

This layer order ensures that the silver iodobromide emulsions are all sensitive to blue light and have a yellow coloration. interposed between the layers spectrally sensitized to green or red light and the exposure source. For silver iodobromide emulsion films, good color separation is best obtained when It is standard. The layer intended to be exposed by blue light is then filtered through a yellow filter. – placed closer to the exposure source than the other layers. Silver chloride emulsions have a small inherent sensitivity to blue light. , this layer order is no longer necessary. For samples, -401-411 -403, the emulsion layer spectrally sensitized to blue light is spectrally sensitized to green or red light. A reverse layer order is used, with the sensitized emulsion layer located further from the exposure source. . The resolution of the red light sensitized layer is determined by the light accompanying the blue light sensitized layer from the exposure optical path for the red light sensitized layer. Improved by removing scattering film components. This is shown below.

Modulation Transfer Function (&!FT) Percent Response as a Function of Spatial Frequency in the Film Plane In order to measure the response, the samples were converted to white in a sinusoidal pattern. Exposure to colored light. The samples were then processed using Kogutsu C-41 processing.

The bleaching solution used for treatment is 1. Modified to consist of 3-propylenediaminetetrafluoric acid I got it. AIFT pattern of exposed and processed elements as a function of spatial frequency in the plane of the film. - evaluated to measure cent response. Special details of this exposure-evaluation cycle The fact is that in the above-mentioned report by R1 Amberts and F. C. Eisen. Are listed.

The &lTF percent response of the red light sensitized layer of these multicolor multilayer films was monitored. , the spatial frequency at which the MTF percent response decreased to 50% was recorded. Than High spatial frequencies indicate films with good resolution. Table 2 shows the results of this test. Shown in 1.

K-401 reverse 50 ML-402 reverse 52 ML-403 reverse 51 8IL-404 Standard 32 -405 standard 38 As readily apparent, the film samples with reversed layer order exhibited superior resolution. .

D. Measurement of photoabrasion effect Samples ML-401-ML-405 were subjected to pressure bridging as described above in Example 11-C. Or the photoabrasion photosensitivity was evaluated.

The results of this evaluation are shown in Table 22 below. Smaller values of light abrasion, manufacturing and use pressure events experienced during production, e.g. during manufacturing and for transporting the film within the camera. Indicates a film composition that is less sensitive to the pressure exerted by rollers used for vinegar. The resulting pressure marks cause unsightly defects in the final image.

Table 22 = Photoabrasion status in the red, green and blue sensitized layers of the element M at Dmin change ML-401+0.06+0.06+0.04ML-402+0.06+ 0.07 +0.03ML-403+0.06 +0.05 +〇,02ML- 404 + 0104 + 0.04 + 0.06 Emulsification - 405 + 0.04 + 0.04 + 0.05 As can be easily seen, all of these samples or showed very low sensitivity to photoabrasion.

Apply the following layers to the cellulose triacetate transparent support in the order listed. A color photographic element, sample ML-501, was prepared by. Amount of silver halide is expressed in g/m1 of silver. The amounts of other substances are given in g/rn2.

The batter compound is a coupler solvent, both as commonly used in the art. , used as an emulsion containing surfactants and stabilizers or as a solution. This photo test Coupler solvents used in the sample include tricresyl phosphate, di-n-butyl Phthalate, N, N-di-n-ethyllaurinamide, N, N-di-n-buty Lulaurinamide, 2,4-di-t-amylphenol, N-butyl-N-phene Nyl acetamide and 1,4-cyclohexylene dimethylene bis-(2-ethoxy cyhexanoate). Mixtures of compounds are commonly practiced in the art. They were used as individual dispersions or as co-dispersions as described above. This sample is further , sodium hexametaphosphate, 3,5-disulfonic acidol disodium, sulfur It consisted of gold oxide, propargyl-aminobenzoxazole, etc. Halogen The silver emulsion contained 2 g of 4-hydroxy-6-methyl-1,3,3a per mole of silver. , stabilized with 7-tetraazaindene.

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

Layer 2 (lowest sensitivity red sensitized layer): Red sensitized silver chloride (100) side at 0.807g Platy emulsion, average equivalent circular diameter 1.2 μm, average grain thickness 0.12 μm20,70 cyan dye-forming image coupler C-1 at g, D-3 at 0,075 g; 2.04 Gelatin in g.

Layer 3 (highest sensitivity red sensitized layer 1: red sensitized silver chloride (100) side at 0.538g Platylet emulsion, average equivalent circular diameter 1.4 μm, average grain thickness 0.14 μm; 0.12 Cyan dye-forming image coupler C-1 at 9g; D-15 at 0.048g: 2. 15g of gelatin.

Layer 4 (middle layer): 1.29 g of gelatin.

Layer 5 (highest sensitivity blue sensitized layer 1: green sensitized silver chloride (100) side at 0.807 g Platylet emulsion, average equivalent circular diameter 1.2 μm, average grain thickness 0.12 μm: 0, 32 Magenta dye-forming image coupler C-2 at 3 g; D-17 at 0.065 g; 2.15g of gelatin.

Layer 6 (highest sensitivity blue sensitized layer 1: green sensitized silver chloride (100) side at 0.538 g Plate-like emulsion, average equivalent circular diameter 1.4 μm, average grain thickness 0.14 μm20,08 Magenta dye-forming image coupler C-2 at 6 g; D-+6 at 0.032 g ; 1.72g of gelatin.

Layer 7 (middle layer): 1.29 g of gelatin.

Layer 8 (lowest sensitivity blue sensitized layer 1: 0.43g blue sensitized silver chloride (100) faceplate emulsion, average equivalent circular diameter 1.2 μm, average grain thickness 0.12 μm; 1.08 g Yellow dye-forming image coupler C-3 at 0.108 g D-18: 1 ．． 72g of gelatin.

Layer 9 (highest sensitivity blue sensitized layer): 0.646g blue sensitized silver chloride (100) surface Platylet emulsion, average equivalent circular diameter 1.4 μm, average grain thickness 0.14 μm; 0.12 Yellow dye-forming image coupler C-3 at 9g: D-+8 at 0.086g; 1.72g of gelatin.

Layer 10 (protective layer): 0. DYE-8 at 108g; unsensitized at 0.108g Silver bromide Lippmann emulsion; 0.026g silicone lubricant; tetraethyl ammonium perfluorooctane sulfonate: -octylphenoxoethoxye Tylsulfonic acid sodium salt, 0.0538g anti-matting polymethyl methacrylate Rate beads, 1.61g gelatin.

This film was treated with 2% by weight of bis-vinylsulfonylmethane based on the total gelatin. It was hardened at the time of application. surfactants, as commonly practiced in the art; Coating aids, scavengers, soluble absorber dyes and stabilizers were added to the various layers of this sample. added to. The total dry thickness of the photosensitized film was about 14.4 μm, and the applied karakin The total dry thickness was approximately 20.2 μm.

Sample LIL-502 except that compound B-1 was added to layer 2 at 0.043 g. It was the same as sample ^IL-501.

Sample 9 IL-503 contained 0.065 g of compound C-42 in layer 2 and 0.043 g of compound C-42 in layer 2. Added 0.065 g of Compound C-40 to layer 3 and added 0.065 g of compound C-40 to layer 5. Sample LIL-502 was similar except that 43 g was added to layer 6.

Sample & IL-504 except for compounds D-3, D-15 and D-18, Then the following compounds were added. That is, 0.075 g of D-4 was added to layer 2, and the layer Add 0.048 g of D-1 to layer 3, add 0.108 g of layer 8 HD-7, and Same as sample klL-501 except that 0.086 g of D-7 was added to layer 9. there were.

IL-505 was added to the sample except that compound B-1 was added to layer 2 at 0.043 g. It was the same as sample ML-504.

Sample ML-506 contains 0.065 g of compound C-42 in layer 2 and 0.043 g of compound C-42 in layer 2. Added 0.065 g of Compound C-40 to layer 5, 0.04 g of Compound C-40 to layer 5, Similar to sample ML-505 except that 3 g was added to layer 6.

Sample ML-507 had layer 2. 3. Double the amount of silver chloride emulsion in 5 and 6, The amounts of compounds D-1, D-4, D-16 and D-17 in these layers were also doubled. The rest was the same as sample ML-504. These changes will increase the film thickness by approx. 1.1 μm was added.

Sample N-508 was layer 2. 3. Double the amount of silver chloride emulsion in 5 and 6, The amounts of compounds D-3, D-15, D-16 and D-17 in these layers were also doubled. Other than that, it was the same as Sample Sanka-501.

B. Pass the density measurement sample of the exposed and developed element through a graduated density test object. The film was exposed to white light and then processed using the Kogutsu C-41 process. process The bleaching solution used was changed to consist of 1,3-propylenediaminetetraacetic acid.

The Status M concentration generated in the Dmin region of each sample was measured after treatment. [S.O. Speed - Exposure level 10 stops higher than point (i.e. 3.01ogE) The status Ma degree generated after processing was measured.

ISO speed-point creates status Ml1 degree 0.15 higher than Dmin This is the exposure necessary to Difference between Dmin and Dmax in concentration production was calculated by subtraction. This difference represents the useful image density range for each sample. D mi n or photographic fog density and useful image forming density are shown in Table 23.

Table 23 = Status M Capri density and useful image forming density ML-5010,031 ,660,1! 2.18 0.14 2.82ML-5020,042,25 0,1+ 2.33 0.14 2.87ML-5030,062,370,1 42,330,142,58ML-5040,022,010,102,300 ,0? 2.96λ-5050,042,060,122,320,092, 91ML-5060,052,200,142,46o,08 2.73Ail -5070,042,350,152,470,073,01AIL-5080 , 062, 900, 151, 960, 112, 91 As readily recognized, the book The useful imaging densities of multilayer, multicolor elements made in accordance with the invention are as follows: is equal to or exceeds that of a comparative commercial 100 speed film sample. , the fog value is smaller, resulting in improved image-capri discrimination. Furthermore, the present invention The manufactured elements are more uniform in three color records than commercially available film samples. I created a concentration generation.

Measuring the effectiveness of C masking couplers 1. Use of cyan dye-forming, preformed magenta dye-releasing couplers Photo samples &1L-502, ML-503, &1L-505 and H&1L-5061 Exposure to light through a density test object and a Kodak Wratten 29 filter did. This arrangement allows red light separation exposure. Next, this sample was transferred to Kogutsuku C-4. 1 processing was used for development processing. The bleaching solution used in the treatment was diluted with 1,3-propylene. It was changed to consist of aminetetraacetic acid.

As a function of red light exposure, the difference between DIIlin and Dmax at green status M density Changes between the two were measured. This change in green density is shown in Table 24.

Table 24: Change in green density as a function of red light exposure Sample masking coupler No change in green density -502 +0.42 ML-503C-42+0.18 Without ML-505 +0.38 ML-506C-42+0.15 Samples ML-503 and ML-506 containing masking couplers have improved color separation. The undesirable green density accompanying exposure and development of the red light sensitized layer was The presence of masking coupler C-42 in L-503 and ML-506 Therefore, it decreased.

2. Use of magenta dye-forming, preformed yellow dye-releasing couplers Photographic samples are scaled with KA-502, ML-503, ML-505 and ML-506. The test object was exposed to light through a Kodak Wratten 74 filter. . This arrangement allows green light separation exposure. This sample was then transferred to Kogutsuk C-41. It was developed using a process. The bleaching solution used in the treatment was mixed with 1,3-propylenediamine The mixture was changed to consist of tetraacetic acid.

As a result of green light exposure, the difference between Dmin and Dmax at blue status Ma is Changes were measured. This change in blue density is shown in Table 25.

Table 25: Change in blue density as a function of green light exposure Sample masking coupler Change in blue density without IL-502 +0.47 NIL-503C-40+0.22 &1L-505less +0.49 8IL-506C-4o +0.25 Samples ML-503 and IL-506 containing masking couplers had improved color exhibits separation properties and reduces undesirable blue densities associated with exposure and development of the green light sensitized layer. Ta.

D. Multilayer effect sample ML-501 induced by solubilized thiol-releasing couplers. , to IL-502. IL-504 and ML-505 are tested for concentration with a scale. Expose to white light through the object or red light using a Kodak Wratten 29 filter. Ta. This sample was then developed using Kogutsu C-41 processing. used for processing The bleach solution used in 1. It was changed to consist of 3-propylenediaminetetraacetic acid.

The cyan image then formed in the red light sensitizing element of this sample under both exposure conditions. The gamma was measured. The light density gamma formed after red light exposure is converted to the shape after white light exposure. The ratio divided by the light density gamma made is the green light sensitizing element and interlayer effect on red caused by development-inhibiting products released into the blue-light sensitizing element. (onto redinterimage effect). this The product from the green and blue light sensitized layers in case of red light exposure and development processing. It is not released, but is released during white light exposure and development processing. These fi In the sample, the development-inhibiting products released are present in the green and blue light sensitized layers. It is a development inhibitor released from intentionally added DIR compounds. in this way The higher the value of the gamma ratio measured with is an indicator of greater color saturation in contrast. Solubilized aliphatic thiol releasing type The compound (compound B-1 is an example of such a solubilized thiol-releasing compound) is is known to interfere with the inhibitory reaction between the development inhibitor and the silver iodobromide emulsion. child The samples evaluated in this test were tested for the presence or absence of Compound B-1. The only difference is that The results of this evaluation are shown in Table 26.

Table 26: Gamma ratio KN of red light exposure and white light exposure Compound B-1 red gun in layer 2 Without MAHI ML-501 1.30 λIL-502W 1.07 Without ML-504 1.03 ML -505 grow 0.98 As can be seen, solubilized aliphatic thiols can be released in elements of the invention. By adding such compounds, color saturation can be substantially suppressed.

E Multilayer effect sample ML-5 induced by development inhibitor releasing (DIR) compound Containing 01, ML-504, ML-507, ML-508 and silver iodobromide emulsion Pass a commercially available 100-speed color negative film through a graduated density test object. The samples were exposed to white light or red light using a Kodak Wratten 29 filter. next This sample was developed using Kodak processing. 1 bleach solution used for treatment ．． It was changed to consist of 3-propylenediaminetetraacetic acid.

The cyan image then formed in the red light sensitizing element of this sample under both exposure conditions. The gamma was measured. The light density gamma formed after red light exposure is converted to the shape after white light exposure. The ratio divided by the light density gamma made is the green light sensitizing element and interlayer effect on red caused by development-inhibiting products released into the blue-light sensitizing element. It is a measure of These products form a green light sensitizing layer in case of red light exposure and processing. and is not released from the blue light sensitized layer, but is released during white light exposure and processing. It will be done. In these film samples, the released development-inhibiting products were green light sensitized. Development inhibitors released from DIR compounds intentionally added to the layers and blue light sensitized layers. It is. The larger value of gamma ratio measured in this way is is an indicator of greater color saturation in prints made from. This evaluation The results are shown in Table 27.

ML-5011,30 ML-5041,03 ML-5071,10 ML-5081,32 Commercially available 100 speed film 1.30 As can be seen, the elements of the present invention Substantial color saturation can be obtained. Selection of DIR compounds to use and depending on the details of the composition of the element, greater or lesser color saturation is desired. It can be obtained by

Apply the following layers to the cellulose triacetate transparent support in the order listed. A color photographic element, sample ML-601, was prepared by: silver halide The amount is g/m of silver! Indicated by The amounts of other substances are given in g/m'.

Organic compounds can be used in combination with coupler solvents, buffers, etc., as commonly used in the art. It was used as an emulsion containing surfactants and stabilizers or as a solution. In this photo sample Coupler solvents used included tricresyl phosphate, di-n-butyl phthalate, rate, N,N-di-n-ethyllaurinamide, N,N-di-n-butyllaurinamide Phosphoramide, 2,4-di-t-amylphenol, N-butyl-N-phenyla Cetamide and I,4-cyclohexylene dimethylenebis-(2-ethoxyhexyl Sanoate) was included. Mixtures of compounds are common practice in the art. They were used as individual dispersions or as co-dispersions. This sample was further Sodium Sametaphosphate, 3.5-Disulfonic Tecol Disodium, Di-sulfide It consisted of gold, propargyl-aminobenzoxazole, etc. silver halide The emulsion contained 2 g of 4-hydroxy-6-methyl-1,3°3a,7- Stabilized with tetraazaindene.

Layer 1 (antihalation layer 1: DYE-1 at 0.011g; O, 013 DYE-2 in g; C-39 in 0.065g; DYE-6 in 0.108g; DYE-9 at 0.075g; Gray colloidal silver at 0.215g; DYE-9 at 0.005g 5QL-1.

5QL-2 at 0,005 g; gelatin at 2.41 g.

Layer 2 (intermediate layer 1: S-1 at 0.108 g; gelatin 1.08 g.

Layer 3 (lowest sensitivity red sensitized layer), red sensitized silver iodobromide emulsion at 0.538 g, iodine Approximately 4 mol% of compounds, average equidistant diameter 0.5 μm, average particle thickness 0.08 μm; 0 ．． C-1 at 753g; D-15 at 0.022g; C-42 at 0.054g; 0.043g is B-1; 0.005g is S-2; 1.72g is gelatin hmm.

Layer 4 (medium sensitivity red sensitized layer 1: 0.592 g red sensitized silver iodobromide emulsion, iodide about 3.7 mol%, average equivalent circular diameter 1.0 μm, average particle thickness 0.09 μm; C-1 at 0.097g; D-15 at 0.022g; C-4 at 0.032g 2; o, oosg is D-17; o, oosg is S -2; 1.72g is ze Latin.

Layer 5 (highest sensitivity red sensitized layer 1: 0.592g red sensitized silver iodobromide emulsion, iodide about 3.7 mol%, average equivalent circular diameter 1.2 μm, average particle thickness 0.13 μm; 0.538g; C-1 at 0.086g; D-15 at 0.022g; 0. C-42 at 022g; D-17 at 0.016g; S-22 at 0.005g 1.72g of gelatin.

Layer 6 (middle layer): S-1 at 0.054 g; gelatin 1.29 g.

Layer 7 (Highest sensitivity blue sensitized layer 1: 0.603g green sensitized silver iodobromide emulsion, iodide about 4 mol%, average equivalent circular diameter 0.57 μm, average particle thickness 0.14 am: C-2 at 0.355g; D-17 at 0.011g; C-40 at 0.043g : o, oosg S-2; 1.4g gelatin.

Layer 8 (medium sensitivity red sensitized layer 1: 0.592 g of green sensitized silver iodobromide emulsion, iodide about 3.7 mol%, average equivalent circular diameter 0.85 μm 1 average particle thickness 0.12 μm; C-2 at 0.086g: D-17 at 0.016g; C-4 at 0.038g 0: S-2 at 0.005g; Gelatin at 1.4g.

Layer 9 (highest sensitivity blue sensitized layer) 20. 592g green sensitized silver iodobromide emulsion, average equivalent Circular diameter 1.05 μm, average particle thickness 0.12 μm; C-2 at 0.086 g ; D-16 at 0.005g; C-40 at 0.038g; S at o, oosg -2; Gelatin at 1.72g.

Layer 101 intermediate layer): S-1 at 0.054g; DYE-9 at 0.108g; DYE-7 in 0.108g; gelatin 1.29g.

Layer II + highest sensitivity blue sensitized layer 1: 0.172 g of blue sensitized silver iodobromide emulsion, iodine about 4 mol% of compound, average equivalent circular diameter 0.5 μm, average particle thickness 0.08 μm: o, 172g blue sensitized silver iodobromide emulsion, iodide approximately 3.7 mol%, average equivalent circular diameter 0.7 0μm, average particle thickness 0.09μm; C-3 at 1.08g, 0,065g D-18: B-1 at 0.005g, S-2 at 0,011g, Zella at 1,08g Chin.

Layer 12 (highest sensitivity blue sensitized layer): 0.43g blue sensitized silver iodobromide emulsion, iodide approx. 3 mol%, average equivalent circular diameter 0.8 μm, average particle thickness 0.08 am; 0.1 C-3 at 29g; D-18 at 0.043g; B-1 at o, oosg; 0. OIIg and S-2 + 1.13g of gelatin.

N15 (protective layer -+1: DYE-8 at 0.118g; unincreased at 0.108g Silver bromide Lippmann emulsion; N, N, N-)limethyl-N-(2-perfluoro- Cutylsulfonamido-ethyl)ammonium iodite, tri-isopropyl Sodium naphthalene sulfonate: 5QL-Cl at 0.043 g, 0.0 DYE-1 for 06g; gelatin for 1.08g.

Layer 14 (Protective layer-2): 0.026g silicone lubricant; tetraethyla ammonium perfluorooctane sulfonate; t-octylphenoxyethoxyethoxylate Sodium ethyl sulfonate; 0.0538 g for anti-matting polymethyl Methacrylate beads; 0.91 g of gelatin.

This film was treated with 2% by weight of bis-vinylsulfonylmethane based on the total gelatin. It was hardened at the time of application. surfactants, as commonly practiced in the art; Coating aids, scavengers, soluble absorber dyes and stabilizers were added to the various layers of this sample. added to. The total dry thickness of the photosensitized layer was approximately 15.1 μm, and The total dry thickness of the gold plate was approximately 23.1 μm.

Sample ML-602 contains a silver iodobromide emulsion in layer 11 and layer 12 (two blue light sensitized layers). was replaced with an equimolar amount of a cubic blue-sensitized silver chloride emulsion as described below. It was the same as ML-601.

layer! 1, blue sensitized chloride with an average edge length of 0.28 μm at 0.344 g Added silver cubic emulsion, Layer 12 contains blue sensitized silver chloride with an average edge length of 0.6 μm at 0.43 g. Add square emulsion.

Sample ML-603 contains a silver iodobromide emulsion in layer 11 and layer 12 (two blue light sensitized layers). was replaced with an equimolar amount of (100) open tabular blue-sensitized silver chloride emulsion as follows: It was the same as sample ML-601 except for the difference.

Layer 1.1 had an average equivalent circular diameter of 1.2 μm and 0.14 μm at 0.344 g. Addition of blue-sensitized silver chloride (ioo>face plate emulsion with average grain thickness, layer 12) , an average equivalent circular diameter of 1.4 μm and an average particle thickness of 0.14 μm at 0.43 g. Blue sensitized silver chloride (added with 1001-plane tabular emulsion).

B. Measuring the film optics of the lower layer of the treated element as a function of spatial frequency in the film plane. Sample ML-6 to measure the modulation transfer function (MFT) percent response as a number 01, ML-602 and ML-603 were exposed to white light in a sinusoidal pattern. . The samples were then processed using Kogutsu C-41 processing. used for processing The bleach solution was changed to consist of 1°3-propylenediaminetetraacetic acid. exposure and processing Measure the MFT percent response as a function of spatial frequency in the plane of the film Evaluated to do so. The specific details of this exposure-evaluation cycle are described above in R. It is described in a paper by Amberts and F. C. Eisen.

MTF percent response of the green and red light sensitized layers of these multilayer multicolor films. monitor the spatial frequency at which the MT″F percent response drops to 50%. Recorded. Higher spatial frequencies indicate films with superior resolution. this test The results of the experiment are shown in Table 28.

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 Light reflection monitor skis to measure scene illumination as part of the control sea fence. This is important when you intend to use it with an automatic exposure camera that uses a scheme. It is. This value is also listed in Table 28.

Table 28 Resolution and reflected light ML at 600 nm as a function of emulsion type in the second upper layer 601 Flat Ag1Br 70 41 31%ML-602 Cubic AgC16 23826% samples ML-601 to ML-603 are the emulsion contained in the blue light sensitized layer. Identical except for morphology and iodide content. In these samples, the blue light sensitized layer Closer to the exposure source than the green or red light sensitized layer. Cubic silver chloride in the upper blue sensitized layer By comparison with results from control elements containing emulsions or tabular silver iodobromide emulsions. As can be seen, according to the present invention, the blue light sensitized layer is sensitized (1001 plate-like AgC1 By including the emulsion, the resolution of the lower layer is thicker (improved).(100) plane A reduced frontal reflection was also obtained by using the platelet AgCl emulsion.

Apply the following layers to the cellulose triacetate transparent support in the order listed. A color photographic element, sample ML-701, was prepared by. Amount of silver halide is expressed in g/mt of silver. The amounts of other substances are given in g/m2.

The organic compound is a coupler solvent, both as commonly used in the art. , used as an emulsion containing surfactants and stabilizers or as a solution. This photo test Coupler solvents used in the sample include tricresyl phosphate, di-n-butyl Phthalate, N, N-di-n-ethyllaurinamide, N, N-di-n-buty Lulaurinamide, 2,4-di-t-amylphenol, N-butyl-N-phene Nyl acetamide and 1,4-cyclohexylene dimethylene bis-(2-ethoxy cyhexanoate). Mixtures of compounds are commonly practiced in the art. They were used as individual dispersions or as co-dispersions as described above. This sample is further , sodium hexametaphosphate, 3,5-disulfonic acidol disodium, sulfur It consisted of gold oxide, propargyl-aminobenzoxazole, etc. Halogen The silver emulsion contained 2 g of 4-hydroxy-6-methyl-1,3,3a per mole of silver. , stabilized with 7-tetraazaindene.

Layer 1 (antihalation layer): DYE-1 at 0.011g;, 0.01 DYE-3 at 1g; C-39 at 0.065g; DYE-6 at o, toag; 0.075g of DYE-9+ 0.215g of gray colloidal silver; 0.005 5QL-1 in g.

5QL-2 at 0.005 g; gelatin at 2.41 g.

Layer 2 (middle layer): 0. 108g of S-1-0,022g of B-1; Gelatin 1.08g.

Layer 3 (lowest sensitivity red sensitized layer): Red sensitized silver chloride (100) opened at 0.538g Tabular emulsion, average equidistant diameter 1.2 μm, average grain thickness 0.12 μm-〇, 5 C-1 at 38g, D-15 at 0,011g; o, C-42 at osiig; 0 , D-3 at 054 g; C-41 at 01032 g; S-2:1 at 0.005 g ．． 72g of gelatin.

Layer 4 (medium sensitivity red sensitized layer) 2 0.592g red sensitized silver chloride (100) open plate emulsion, average equivalent circular diameter 1.5 μm, average grain thickness 0.14 μm; 0,075 C-1 in g; D-15 in 0.011 g; C-42 in 0.032 g; 0.03 D-17 at 2g; C-41 at 0.022g; S-2: 1.7 at 0.005g 2g of gelatin.

Layer 5 (highest sensitivity red sensitized layer 1, Q, 592g red sensitized silver chloride (100) square root Platy emulsion, average equivalent circular diameter 2.2 μm, average grain thickness 0.12 μm: 0,075 g C-1; 0,011 g D-15; 0.022 g C-42; 0.0 D-17 at 32g; C-41 at 0.011g, S-2 at 0,005g; 1.7 2g of gelatin.

Layer 6 (Middle layer 1: S-1 at 0.054g: D-25 at 0.032g; Gelatin 1.08 g.

Layer 7 (highest sensitivity red sensitized layer 1: 0.484g green sensitized silver chloride (100) square root Tabular emulsion, average equivalent circular diameter 1.2 μm, average grain thickness 0.12 μm.

0.355 g C-2; 0.022 g D-17; 0.043 g C-4 0; D-8 at 0,022 g; S-2 at 0.011 g; Gelatin at 1.13 g .

Layer 8 (medium sensitivity red sensitized layer 1: green sensitized silver chloride (100) opened at 0.592g) Tabular emulsion, average equivalent circular diameter 1.5 μm, average grain thickness 0.14 μm; 0,08 C-2 at 6 g; D-17 at 0.022 g; C-40 at 0.038 g: 0. 011g S-2; 1.4g gelatin.

Layer 9 (Highest sensitivity red sensitized layer 1: Green sensitized silver chloride (100) opened at 0.592g Tabular emulsion, average equivalent circular diameter 2.2 μm, average grain thickness 0.12 μm; 0,07 C-2 at 5 g; D-16 at 0.022 g; C-40 at 0.038 g; 0, 022 g D-7 + 0.011 g S-2; 1.35 g gelatin.

Layer 10 (middle layer 1: S-1 at 0.054g; DYE-7 at 0.108g , gelatin 0.97 go Layer 11 (lowest sensitivity blue sensitized layer 1: 0.344g blue sensitized silver chloride cubic emulsion , average edge length 0.28μm; C-3 at 1.08g; D at 0.065g -18.

D-19 at 0,065 g; B-1 at o, oosg: S-2 at 0.011 g ; 1, 34 g of gelatin.

Layer 12 + highest sensitivity blue sensitized layer); 0.43g blue sensitized silver chloride cubic emulsion, average Edge length 0.6μm; C-3 at 0.108g; D-18 at 0.043g; o, oosg for B-1; 0.011g for S-2, 1, 13g for gelatin.

Layer 13 (Protective layer-11: DYE-8 at 0.054g; DY at 0.108g E-9; 0,054 g DYE-10; O, 108 g unsensitized silver bromide lip Mann emulsion; N, N, N-trimethyl-N-(2-perfluorooctylsulfur) Honamido-ethyl)ammonium iodite; tri-isopropylnaphthalene Sodium sulfonate; 5QL-ct at 0.043g; Zet at 1.08g Latin.

Layer 14 (protective layer-21: silicone lubricant at 0.026 g; tetraethylammo perfluorooctane sulfonate;-octyl lephenoxyethquine Ethyl sulfonic acid sodium salt; 0.0538 g to prevent matting polymethyl Tacrylate beads; 0.91 g of gelatin.

This film was treated with 2% by weight of bis-vinylsulfonylmethane based on the total gelatin. It was hardened at the time of application. surfactants, as commonly practiced in the art; Coating aids, scavengers, soluble absorber dyes and stabilizers were added to the various layers of this sample. added to. The total dry thickness of the photosensitized layer was approximately 12.1 μm, and the applied The total dry thickness was approximately 20.5 μm.

Sample ML-702 contains silver chloride cubic from within layer 11 and layer 12 (two blue light sensitized layers). Excluding the body emulsion, prepare an equimolar amount of (100) plate-like blue sensitized silver chloride milk as follows. It was the same as sample ML-701 except that it was replaced with the agent.

Layer 11 has an average uniform device diameter of 1.2 μm at 0.172 g and an average of 0.12 μm. Blue sensitized silver chloride with grain thickness (1001-sided tabular emulsion and 0.172 g of 1 ．． Blue sensitized chloride to develop an average equivalent circular diameter of 5 μm and an average grain thickness of 0.14 μm Silver (added 1001 planar tabular emulsion, layer 12, average of 2.2 μm at 0.43 g) Blue sensitized silver chloride (100) surface with equivalent circular diameter and average grain thickness of 0.12 μm Add platelet emulsion.

Sample ML-703 was prepared as follows, excluding coupler C-3 from layer 1] and layer 12. Same as sample ML-702 except that the same amount of coupler C-29 was substituted. It was.

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

Sample No.-704 was prepared as follows by removing coupler C-2 from layer 7, l1i8 and layer 9. Same as sample ML-703 except that coupler C-18 was replaced as shown in It was.

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

Sample ML-705 was prepared by removing coupler C-2 from layer 7, layer 8, and layer 9 as follows. Same as sample ML-703, except that couplers C-15 and C-16 were replaced. It was the same.

Layer 7 added 0.16g C-15 and 0.16g C-16; layer 8 added 0.16g C-15 and 0.16g C-16; Added 0.039 g of C-15 and 0.039 g of C-16 and added 0.039 g of C-16 to layer 9. ．． Added 0.033 g of C-15 and 0.033 g of C-16.

Sample ML-706 was prepared by removing coupler C-2 from layer 7, layer 8, and layer 9 as follows. Sample ML-703 was the same as sample ML-703 except that coupler C-15 was used. .

Added 0.32 g of C-15 to layer 7, added 0.077 g of C-15 to layer 8. and layer 9, added 0.068 g of C-15.

Sample ML-707c, 0.006g (7) DYE-2 was added to layer 13, and 0.006g (7) DYE-2 was added to layer 13. Similar to sample ML-706 except that 0.65 g of BA-1 was added to layer 1. .

Sample ML-708c, 0.006g (7) DYE-2 was added to layer 13, and 0.006g (7) DYE-2 was added to layer 13. Similar to sample ML-706 except that 258 g of BA-2 was added to layer I. Ta.

B Measurement of film optics of lower layer of treated element Samples ML-701 to ML-7 08 and a commercially available 100 speed color negative film consisting of a silver iodobromide emulsion in the photosensitized layer. The illum was exposed to white light in a sinusoidal pattern and then treated with Kogutsu C-41. It was developed and processed.

sinusoidal to measure MTF percent response as described in Example 14. Evaluated the pattern.

Monitor the MTF percent response of the red light sensitized layer of these multilayer multicolor films; The spatial frequency at which the MTF percent response dropped to 50% was recorded. higher Higher spatial frequencies indicate a film with better resolution. Table 29 shows the results of this test. Shown below.

ML-701 cubic AgC125 ML-702 (100) Tabular AgCl 33ML-703 (1001 Tabular A gC134ML-704 (1001 flat AgC133ML-705floo 1 Flat AgCl 35ML-706+100) Flat AgC131ML-7 08 (+001 tabular AgC138 (red absorption side dye BA-2 added to layer 1) As is readily apparent, the present invention provides a (100) tabular AgCl emulsion in the upper layer. compared to those obtained using cubic silver chloride emulsions or silver iodobromide emulsions. This gave the lower layer improved resolution. This resolution is due to the anti-halation layer further improved by using red light absorbing dyes.

Measurement of spark sensitivity of C element Samples ML-701-ML-708 and radiation-sensitive layer consisting of silver iodobromide emulsion Commercially available 100 speed color negative film is exposed to ultraviolet and visible light through the base. exposure to a spark discharge that produces a The image was developed using Kogutsuku C-41 processing containing a synthetic bleaching solution. Then, according to the present invention, silver chloride Interfacial white color between elements using tabular emulsions and control samples using silver iodobromide emulsions The relative sensitivities to light and ultraviolet light were compared. Elements of the invention have comparable visible light When adjusted to sensitivity, it has spark and electrostatic discharge properties that are superior to those of the control sample. exhibits a sensitivity to ultraviolet light that is approximately 100 times (i.e., 1-01ogE) Ta.

Although the invention has been described in detail with particular reference to preferred embodiments thereof, variations and modifications thereof It goes without saying that this may be done without departing from the spirit and scope of the present invention.

Continuation of front page (72) Inventor: Brust, Thomas Prownell, New York, USA 14559° Rochester, Cottage Street 13 (72) Inventor Ma Skasky, Joe Nidward New York, USA 14625° Rochester, Sherwood Drive (72) Inventor Hartsell, Debra Lyn United States, New York 14612゜Rochester, Snughar Barcoat (72) Inventor Black, Donald Lee United States, New York 14580° Webster, Hightower Way 803 (72) Invention Maril, James Parker United States, New York 1462 6゜Rochester, Club Apple Lane (72) Inventor Pohan, Anne Elizabeth United States, New York 14610° Rochester, Han Berg Avenue 71

Claims (21)

[Claims] 1. consisting of a dispersing medium and silver halide grains, and in reactive association with an image dye a support having at least one radiation-sensitive emulsion layer having a forming compound; a color photographic element comprising: (A) at least 50% of the total grain projected area; , connected by {100} principal surfaces with adjacent edge ratios smaller than 10, each with a small dominated by tabular grains having an aspect ratio of at least 2, and ( B) The emulsion layer also contains photographically useful groups in reactive association and is oxidized. Contains a compound capable of reacting with the base drug thereby releasing a photographically useful group. , color photographic elements. 2. Color photograph according to claim 1, having an average aspect ratio of at least 5. element. 3. A color photographic element according to claim 1, having an average aspect ratio greater than 8. 4. 2. A color photographic element according to claim 1, wherein the edge ratio is less than 5. 5. 2. A color photographic element according to claim 1, wherein the edge ratio is less than 2. 6. The method according to claim 1, wherein the tabular grains have a thickness of less than 0.3 μm. ra photo elements. 7. The method according to claim 1, wherein the tabular grains have a thickness of less than 0.2 μm. ra photo elements. 8. Claim 1, wherein the tabular grains have a thickness of less than 0.06 μm. Color photo elements. 9. Claim 1, wherein the tabular grains contain at least 70 mol% chloride. Color photographic elements included. 10. Claim 1, wherein the tabular grains contain at least 90 mole percent chloride. Color photographic elements described. 11. A color photographic element according to claim 10, wherein the tabular grains are silver iodochloride grains. Basic. 12. A color photograph according to claim 1, wherein the photographically useful group is a development inhibitor. element. 13. The color according to claim 12, wherein the compound containing a development inhibitor is a coupler. -Photo elements. 14. The development inhibitor may be mercaptotetrazole, mercaptooxadiazole or 13. A color photographic element according to claim 12, wherein is mercaptothiadiazole. 15. Claim 1, wherein the development inhibitor is benzotriazole or tetrazole Color photographic element according to item 2. 16. Photographically useful groups include bleach accelerators, development accelerators, competitive pullers, and electron transfer agents. 2. A color photographic element according to claim 1, which is a bleach inhibitor or a dye. 17. Claim 1, wherein the developing agent is a p-phenylenediamine developing agent. color photo elements. 18. A color photograph according to claim 1, wherein the radiation-sensitive emulsion layer is blue-sensitized. True element. 19. at least one red-sensitized silver halide emulsion layer; at least one green-sensitized silver halide emulsion layer; It consists of a silver halide emulsion layer and at least one blue-sensitized silver halide emulsion layer. Tabular grains bonded by {100} major faces are present in at least one of these emulsion layers. A color photographic element according to claim 1. 20. At least one tabular silver chloride grain bonded by {100} major surfaces A color photograph according to claim 19, wherein the silver halide emulsion layer of is blue-sensitized. element. 21. At least one tabular silver chloride grain bonded by {100} major surfaces A color photograph according to claim 19, wherein the silver halide emulsion layer of is red sensitized. element.