This is a continuation-in-part of U.S. Serial No. 763,382, filed September 20, 1991.

ziέid. o the Invention

The invention relates to the precipitation of radiation sensitive silver halide emulsions useful in photography.

Bac Q Qmid o_£ t e Invention Radiation sensitive silver halide emulsions containing one or a combination of chloride, bromide and iodide ions have been long recognized to be useful in photography. Each halide ion selection is known to impart particular photographic advantages. Although known and used for many years for selected photographic applications, the more rapid develop- ability and the ecological advantages of high chloride emulsions have provided an impetus for employing these emulsions over a broader range of photographic applications. As employed herein the term "high chloride emulsion" refers to a silver halide emulsion containing at least 50 mole percent chloride and less than 5 mole percent iodide, based on total silver. During the 1980's a marked advance took place in silver halide photography based on the discovery that a wide range of photographic advan¬ tages, such as improved speed-granularity relation¬ ships, increased covering power both on an absolute basis and as a function of binder hardening, more rapid developability, increased thermal stability, increased separation of native and spectral sensiti-

zation imparted imaging speeds, and improved image sharpness in both mono- and multi-emulsion layer formats, can be realized by increasing the propor¬ tions of selected tabular grain populations in photo- graphic emulsions.

The various photographic advantages were associated with achieving high aspect ratio tabular grain emulsions. As herein employed and as normally employed in the art, the term "high aspect ratio tabular grain emulsion' has been defined as a photo¬ graphic emulsion in which tabular grains having a thickness of less than 0.3 μm and an average aspect ratio of greater than 8:1 account for at least 50 percent of the total grain projected area of emul- sion. Aspect ratio is the ratio of tabular grain effective circular diameter (ECD) , divided by tabular grain thickness (t) .

Although the art has succeeded in preparing high chloride tabular grain emulsions, the inclusion of high levels of chloride as opposed to bromide, alone or in combination with iodide, has been diffi¬ cult. The basic reason is that tabular grains are produced by incorporating parallel twin planes in grains grown under conditions favoring {111} crystal faces. The most prominent feature of tabular grains are their parallel {111} major crystal faces.

To produce successfully a high chloride tabular grain emulsion two obstacles must be overcome. First, conditions must be found that incorporate parallel twin planes into the grains.

Second, the strong propensity of silver chloride to produce {100} crystal faces must be overcome by finding conditions that favor the formation of {111} crystal faces.

Wey U.S. Patent 4,399,215 produced the first silver chloride high aspect ratio (ECD/t > 8) tabular grain emulsion. An aiπmoniacal double-jet precipitation technique was employed. The tabularity of the emulsions was not high compared to contempo¬ raneous silver bromide and bromoiodide tabular grain emulsions because the ammonia thickened the tabular grains. A further disadvantage was that significant reductions in tabularity occurred when bromide and/or iodide ions were included in the tabular grains. ey et al U.S. Patent 4,414,306 developed a. process for preparing silver chlorobromide emulsions containing up to 40 mole percent chloride based on total silver. This process of preparation has not been successfully extended to high chloride emulsions.

Maskasky U.S. Patent 4,400,463 (hereinafter designated Maskasky I) developed a strategy for preparing a high chloride, high aspect ratio tabular grain emulsion capable of tolerating significant inclusions of the other halides. The strategy was to use a particularly selected synthetic polymeric peptizer in combination with a grain growth modifier having as its function to promote the formation of {111} crystal faces. Adsorbed aminoazaindenes, preferably adenine, and iodide ions were disclosed to be useful grain growth modifiers. The principal disadvantage of this approach has been the necessity of employing a synthetic peptizer as opposed to the gelatino-peptizers almost universally employed in photographic emulsions.

This work has stimulated further investiga¬ tions of grain growth modifiers for preparing tabular grain high chloride emulsions, as illustrated by Takada et al U.S. Patent 4,783,398, which employs

heterocycles containing a divalent sulfur ring atom; Nishikawa et al U.S. Patent 4,952,491, which employs spectral sensitizing dyes and divalent sulfur atom containing heterocycles and acyclic compounds; and Ishiguro et al U.S. Patent 4,983,508, which employs organic bis-quaternary amine salts.

Maskasky U.S. Patent 4,713,323 (hereinafter designated Maskasky II) , continuing to use aminoazaindene growth modifiers, particularly adenine, discovered that tabular grain high chloride emulsions could be prepared by running silver salt into a dispersing medium containing at least a 0.5 molar concentration of chloride ion and an oxidized gelatino-peptizer. An oxidized gelatino-peptizer is a gelatino-peptizer treated with a strong oxidizing agent to modify by oxidation (and eliminate or reduce as such) the methionine content of the peptizer. Maskasky II taught to reduce the methionine content of the peptizer to a level of less than 30 micromoles per gram. King et al U.S. Patent 4,942,120 is essen¬ tially cumulative, differing only in that methionine was modified by alkylation.

While Maskasky II overcame the synthetic peptizer disadvantage of Maskasky I, the requirement of a chloride ion concentration of at least 0.5 molar in the dispersing medium during precipitation presents disadvantages. At the elevated temperatures typically employed for emulsion precipitations using gelatino-peptizers, the high chloride ion concentra- tions corrode the stainless steel vessels used for the preparation of photographic emulsions. Addition¬ ally, the high chloride ion concentrations increase the amount of emulsion washing required after precip¬ itation, and disposal of the increased levels of

chloride ion represents increased consumption of materials and an increased ecological burden.

Tufano et al U.S. Patent 4,804,621 disclosed a process for preparing high aspect ratio tabular grain high chloride emulsions in a gelatino-peptizer. Tufano et al observed that over a wide range of chloride ion concentrations ranging from pCl 0 to 3 (1 to 1 X 10-3 M) and a wide range of pH levels, ranging from 2.5 to 9, selected 4,6-diaminopyrimidines were capable of promoting the formation of tabular grains. Tufano et al specifically investigated the use of a 4,6- di(hydroamino)-5-aminopyrimidine (specifically, adenine), but failed to obtain tabular grains using these compounds and explicitly excluded the possibility of having an amino substituent present in the 5-posi- tion on the pyrimidine ring.

Japanese patent application 03/116,133, published May 17, 1991, discloses a method of manufacturing photographic silver halide emulsions comprising silver chloride grains or silver chlorobromide grains containing at least 80 mole percent chloride. At least 50 percent of the total projected area of the silver chloride or chlorobromide grains is accounted for by tabular grains with a thickness of less than 0.5 μm, a diameter of not less than 0.5 μm, and an aspect ratio of not less than 2:1. The method of manufacturing the emulsion is characterized in that the silver chloride or chlorobromide grains are prepared by the reaction of silver and halide salts in an aqueous solution in the pH range of from 4.5 to 8.5 and in the presence of adenine.

Related Patent Applications

Maskasky U.S. Serial No. 762,971, filed September 20, 1991, and commonly assigned, titled IMPROVED PROCESS FOR THE PREPARATION OF HIGH CHLORIDE TABULAR GRAIN EMULSIONS (II) , (hereinafter designated Maskasky III) discloses a process for preparing a high chloride tabular grain emulsion in which silver ion is introduced into a gelatino-peptizer dispersing medium containing a stoichiometric excess of chloride ions of less than 0.5 molar and a grain growth modifier of the formular

where

Z ² is -C(R ² )= or -N=; Z ³ is -C(R ³ )= or -N=;

Z ⁴ is -C(R ⁴ )= or -N=ι

Z ⁵ is -C(R ⁵ )= or -N=;

Z ⁶ is -C(R ⁶ )= or -N=; with the proviso that no more than one of Z ⁴ , Z--- and Z ⁶ is -N=;

R ² is H, NH or CH ₃ .

R ³ , R ⁴ and R-5 are independently selected, R ³ and R*-* ¹ being hydrogen, hydroxy, halogen, amino or hydrocar¬ bon and R ⁴ being hydrogen, halogen or hydrocarbon, each hydrocarbon moiety containing from 1 to 7 carbon atoms; and

R ⁶ is H or NH2-

Maskasky and Chang U.S. Serial No. 763,013, filed September 20, 1991, and commonly assigned, titled IMPROVED PROCESS FOR THE PREPARATION OF HIGH CHLORIDE TABULAR GRAIN EMULSIONS (III) , (hereinafter designated

Maskasky et al) discloses a process for preparing a high chloride tabular grain emulsion in which silver ion is introduced into a gelatino-peptizer dispersing medium containing a stoichiometric excess of chloride ions of less than 0.5 molar and a grain growth modifier of the formula:

where

Z ⁸ is -C(R ⁸ )= or -N=; R ⁸ is H, NH ₂ or CH ₃ . _and

R--- is hydrogen or a hydrocarbon containing from 1 to 7 carbon atoms.

Maskasky U.S. Serial No. 763,030, filed September 20, 1991, and commonly assigned, titled ULTRATHIN HIGH CHLORIDE TABULAR GRAIN EMULSIONS,

(hereinafter designated Maskasky IV) discloses a high chloride tabular grain emulsion in which greater than 50 percent of the total grain projected area is accounted for by ultrathin tabular grains having a thickness of less than 360 {111} crystal lattice planes. A {111} crystal face stabilizer is adsorbed to the major faces of the ultrathin tabular grains.

Summary ΩL the invention

In one aspect, this invention is directed to a process of preparing a radiation sensitive high aspect ratio tabular grain emulsion, wherein tabular grains of less than 0.3 μm in thickness and an average aspect ratio of greater than 8:1 account for greater

than 50 percent of the total grain projected area, the tabular grains containing at least 50 mole percent chloride, based on silver, comprising introducing silver ion into a gelatino-peptizer dispersing medium containing a stoichiometric excess of chloride ions of less than 0.5 molar, a pH of at least 4.6, and a triaminopyrimidine grain growth modifier containing mutually independent 4, 5 and 6 ring position amino substituents, the 4 and 6 ring position substituents being hydroamino substituents.

It has been discovered quite unexpectedly that by properly selecting the stoichiometric excess of chloride ion and the pH present in a gelatino-peptizer dispersing medium during precipitation of a high chloride silver halide emulsion a high aspect ratio tabular grain emulsion can be produced by including in the dispersing medium a 4,6-di(hydroamino)pyrimidine grain growth modifier that additionally contains an independent 5 ring position amino substituent. The discovered utility of this class of pyrimidines as useful grain modifiers runs exactly contrary- to the teachings of the art. The lowered stoichiometric excess of chloride ion avoids the corrosion, increased washing, materials consumption and ecological burden concerns inherent in the Maskasky II process. The disadvantage of Maskasky I of requiring a synthetic peptizer is also avoided. Thus, a novel process is provided by this invention which offers a more attrac¬ tive route to providing a high chloride high aspect ratio tabular grain emulsion.

Brief DRsπription o_£ he Drawings

Figures 1 to 3 inclusive are carbon replica electron photomicrographs showing emulsions prepared according to the invention.

Figure 4 is a scanning electron photomicro¬ graph of an emulsion prepared according to the inven¬ tion.

Description ΩL Preferred Embodiments The present invention is directed to an improved process of preparing a high chloride high aspect ratio tabular grain emulsion.

An aqueous gelatino-peptizer dispersing medium is present during precipitation. Gelatino- peptizers include gelatin—e.g., alkali-treated gelatin (cattle bone and hide gelatin) or acid-treated gelatin (pigskin gelatin) and gelatin derivatives—e.g., acetylated gelatin, phthalated gelatin, and the like. The process of the invention is not restricted to use with gelatino-peptizers of any particular methionine content. That is, gelatino- peptizers with all naturally occurring methionine levels are useful. It is, of course, possible, though not required, to reduce or eliminate methionine, as taught by Maskasky II or King et al, both cited above and here incorporated by reference.

During the precipitation of photographic silver halide emulsions there is always a slight stoichiometric excess of halide ion present. This avoids the possibility of excess silver ion being reduced to metallic silver and resulting in photo¬ graphic fog. It is a significant advantage of this invention that the stoichiometric excess of chloride ion in the dispersing medium can be maintained at a level of less than 0.5 M while still obtaining a high aspect ratio tabular grain emulsion. It is generally preferred that the chloride ion concentration in the dispersing medium be less than 0.2 M and, optimally, equal to or less than 0.1 M.

The advantages of limiting the stoichiometric excess of chloride ion present in the reaction vessel during precipitation include (a) reduction of corrosion of the equipment (the reaction vessel, the stirring mechanism, the feed jets, etc.), (b) reduced consump¬ tion of chloride ion, (c) reduced washing of the emulsion after preparation, and (d) reduced chloride ion in effluent. It has also been observed that reduction in the chloride ion excess contributes to obtaining thinner tabular grains.

The pH of the dispersing medium is maintained at a level of at least 4.6. Whereas the Examples of Maskasky I report relevant halide compositions having a pH of 2.6 and 3.0, the Examples of Maskasky II report a pH of 4.0 and Tufano et al report a pH of 4.0 for the adenine control, it has been discovered that, for the pyrimidines employed in the practice of this invention to be effective growth modifiers in gelatino-peptizers with a limited stoichiometric excess of chloride ion present, the pH must have a value of at least 4.6. The maximum pH contemplated during precipitation can range up to 9. It is generally preferred to conduct precipitation in the pH range of from 5.0 to 8.0. A strong mineral acid, such as nitric acid or sulfuric acid, or a strong mineral base, such as an alkali hydroxide, can be employed to adjust the pH within a selected range. When a basic pH is to be maintained, it is preferred not to employ ammonium hydroxide, since it has the unwanted effect of acting as a ripening agent and is known to thicken tabular grains. However, to the extent that thickening of the tabular grains does not exceed the 0.3 μm thickness limit, ammonium hydroxide or other conventional ripening agents (e.g., thioether or thiocyanate ripening agents) can be present within the dispersing medium,.

Any convenient conventional approach of monitoring and maintaining replicable pH profiles during repeated precipitations can be employed (e.g., refer to Research Disclosure Item 308,119, cited below) . Maintaining a pH buffer in the dispersing medium during precipitation arrests pH fluctuations and facilitates maintenance of pH within selected limited ranges. Exemplary useful buffers for maintaining relatively narrow pH limits within the ranges noted above include sodium or potassium acetate, phosphate, oxalate and phthalate as well as tris(hydroxymethyl)- aminomethane.

In addition to the precipitation criteria noted above, it is contemplated to have present a triaminopyrimidine grain growth modifier containing mutually independent 4, 5 and 6 ring position amino substituents with the 4 and 6 ring position substituents being hydroamino substituents. As employed herein the term "hydroamino" designates an amino group containing at least one hydrogen substituent--i.e. , a primary or secondary amino group. The 5 position amino ring substituent can be a primary, secondary or tertiary amino group. In referring to the amino groups as "independent" it is meant that each amino group can be selected independently of the others and that no substituent of one amino group is shared with another amino group. In other words, substituents that bridge amino groups are excluded. Pyrimidine grain growth modifiers satisfying the above general description are herein referred to as "invention" grain growth modifiers.

In a specifically preferred form the grain growth modifier can satisfy the following formula:

(I)

H

where

N ⁴ , N-^ and N-* are independent amino moieties. In the simplest contemplated form each of N ⁴ ,

N--- and N^ can be a primary amino group (-NH2) • Any one or combination of N ⁴ , N--- and N-*- can be a primary amino group. Any one or combination of N ⁴ , N--* and N*^ can alternatively take the form of a secondary amino group (-NHR) , where the substituent R is in each instance an independently chosen hydrocarbon containing from 1 to 7 carbon atoms. R is preferably an alkyl group—e.g., methyl, ethyl, π-propyl, i-propyl, n-butyl, i-butyl, t-butyl, etc., although other hydrocarbons, such as cyclohexyl or benzyl, are contemplated. To increase growth modifier solubility the hydrocarbon groups can, in turn, be substituted with polar groups, such as hydroxy, sulfonyl or amino groups, if desired, or the hydrocarbon can be substituted with other groups that do not materially affect their properties (e.g., a halo substituent. In another alternative form N*-* can, independently of N ⁴ and N>, take the form of a tertiary amino group (-NR2), where R is as previously defined.

In one specific form the grain growth modifiers of this invention satisfy the formula:

(II)

where R ¹ is independently in each occurrence hydrogen or alkyl of from 1 to 6 carbon atoms.

The following are illustrations of varied pyri idine compounds within the purview of the invention:

PY-1 4 , 5 , 6-Triaminopyrimidine

PY-2 5 , 6-Diamino-4- (N-methylamino) pyrimidine

PY-3 4, 5, 6-Tri (N-meth lamirno ) pyrimidine

PY-4 4,6-Diamino-5-(N,N-dimethylamino)pyrimi¬ dine

PY-5 4,6-Diamino-5-(N-hexylamino)pyrimidine

In forming high chloride high aspect ratio tabular grain emulsions, tabular grains containing at least 50 mole percent chloride, based on silver, and having a thickness of less than 0.3 μ must account for greater than 50 percent of the total grain projected area. In preferred emulsions the tabular grains having a thickness of less than 0.2 μ account for at least 70 percent of the total grain projected area and, optimally, at least 90 percent of the total grain projected area.

For tabular grains to satisfy the projected area requirement it is necessary first to induce

twinning in the grains as they are being formed, since only grains having two or more parallel twin planes will assume a tabular form. Second, after twinning has occurred, it is necessary to restrain precipitation onto the major {111} crystal faces of the tabular grains, since this has the effect of thickening the grains. The pyrimidine grain growth modifiers employed in the practice of this invention are effective during precipitation to produce an emulsion satisfying both the tabular grain thickness and projected area parameters noted above.

It is generally recognized that introducing twin planes in the grains at a very early stage in their formation offers the capability of producing thinner tabular grains than can be achieved when twinning is delayed. For this reason it is usually preferred that the conditions within the dispersing medium prior to silver ion introduction at the outset of precipitation be chosen to favor twin plane forma- tion. To facilitate twin plane formation it is contem¬ plated to incorporate the pyrimidine grain growth modifier of the invention in the dispersing medium prior to silver ion addition in a concentration of at least 2 X 10 ^"4 M, preferably at least 5 X 10 ^-4 M, and optimally at least 7 X 10 ^"4 M. Generally little increase in twinning can be attributed to increasing the initial grain growth modifier concentration in the dispersing medium above 0.01 M. Higher initial grain growth modifier concentrations up to 0.05 M, 0.1 M or higher are not incompatible with the twinning function. The maximum growth modifier concentration in the dispersing medium is often limited by its solubility. It is contemplated to introduce into the dispersing medium growth modifier in excess of that which can be initially dissolved. Any undissolved growth modifier

can provide a source of additional growth modifier solute during precipitation, thereby stabilizing growth modifier concentrations within the ranges noted above. It is preferred to avoid quantities of grain growth modifier in excess of those observed to control favor¬ ably tabular grain parameters.

Once a stable multiply twinned grain popula¬ tion has been formed within the dispersing medium, the primary, if not exclusive, function the grain growth modifier is called upon to perform is to restrain precipitation onto the major {111} crystal faces of the tabular grains, thereby retarding thickness growth of the tabular grains. In a well controlled tabular grain emulsion precipitation, once a stable population of multiply twinned grains has been produced, tabular grain thicknesses can be held essentially constant.

The amount of grain growth modifier required to control thickness growth of the tabular grain population is a function of the total grain surface area. By adsorption onto the {111} surfaces of the tabular grains the pyrimidines of the invention restrain precipitation onto the grain faces and shift further growth of the tabular grains to their edges. The benefits of this invention can be realized using any amount of grain growth modifier that is effective to retard thickness growth of the tabular grains. It is generally contemplated to have present in the emulsion during tabular grain growth sufficient grain growth modifier to provide a monomolecular adsorbed layer over at least 25 percent, preferably at least 50 percent, of the total {111} grain surface area of the emulsion grains. Higher amounts of adsorbed grain growth modifier are, of course, feasible. Adsorbed grain growth modifier coverages of 80 percent of monomolecular layer coverage or even 100 percent are

contemplated. In terms of tabular grain thickness control there is no significant advantage to be gained by increasing grain growth modifier coverages above these levels. Any excess grain growth modifier that remains unadsorbed is normally depleted in post-precip¬ itation emulsion washing.

Prior to introducing silver salt into the dispersing medium at the outset of the precipitation process, no grains are present in the dispersing medium and the initial grain growth modifier concentrations in the dispersing medium are therefore more than adequate to provide the monomolecular coverage levels noted above as grains are initially formed. As tabular grain growth progresses it is a simple matter to add grain growth modifier, as needed, to maintain monomolecular coverages at desired levels, based on knowledge of amount of silver ion added and the geometrical forms of the grains being grown.

The pyrimidine grain growth modifiers of the invention described above are capable of use during precipitation as the sole grain growth modifier. That is, these grain growth modifiers are capable of influencing both twinning and tabular grain growth to provide high chloride high aspect ratio tabular grain emulsions.

It has been discovered that improvements in precipitation can be realized by employing a combina¬ tion of a pyrimidine grain growth modifier of the invention described above and at least one other grain growth modifier. For example, it is contemplated to employ a more tightly adsorbed grain growth modifier for tabular grain thickness growth reduction and to employ a less tightly adsorbed of grain growth modifier for twinning. Specifically, it has been observed that 6-hydroaminopurines satisfying the following formula:

(III)

where N ⁴ is as previously defined, produce improved emulsions when added to the reaction vessel after twinning in the presence of a less tightly absorbed pyrimidine satisfying formula (II) above .

Other grain growth modifiers can be employed in combination with a pyrimidine of the invention to perform one of the twinning and tabular grain thickness control functions.

It is specifically contemplated to employ during twinning or grain growth a grain growth modifier of the following structure:

(IV)

wherein Z is C or N; R]_, R ₂ and R3, which may be the same or different, are H or alkyl of 1 to 5 carbon atoms; when Z is C, R ₂ and R3 when taken together can be -CR4=CR5~ or -CR4=N-, wherein R4 and R5, which may be the same or different are H or alkyl of 1 to 5 carbon atoms, with the proviso that when R ₂ and R3 taken together form the -CR4=N- linkage, -CR4= must be

joined to Z. Grain growth modifiers of this type and conditions for their use are disclosed by Tufano et al, cited above, the disclosure of which is here incorpo¬ rated by reference. It is also contemplated to employ during grain twinning or growth a grain growth modifier of the type disclosed by Maskasky III, cited above. These grain growth modifiers are effective when the dispers¬ ing medium is maintained at a pH in the range of from 3 to 9 (preferably 4.5 to 8) and contains a stoichio¬ metric excess of chloride ions of less than 0.5 molar. These grain growth modifier satisfy the formula:

(V)

I * 7 ³

H

where

Z ² is -C(R ² )= or -N=;

Z ³ is -C(R ³ )= or -N=;

Z ⁴ is -C(R ⁴ )= or -N=;

Z ⁵ is -C(R ⁵ )= or -N= Z ⁶ is -C(R ⁶ )= or -N=; with the proviso that no more than one of Z ⁴ , Z--* and Z*-> is -N=;

R ² is H, NH ₂ or CH ₃ .

R ³ , R ⁴ and R*-* are independently selected, R ³ and R5 being hydrogen, hydroxy, halogen, amino or hydrocar¬ bon and R ⁴ being hydrogen, halogen or hydrocarbon, each hydrocarbon moiety containing from 1 to 7 carbon atoms; and

R ⁶ is H or NH ₂ .

Another class of grain growth modifier useful during grain twinning or growth under similar condi¬ tions as the grain growth modifiers of formula V are the xanthine type grain growth modifiers of Maskasky et al, cited above. These grain growth modifiers are represented by the formula:

(VT)

where Z ⁸ is -C(R ⁸ )= or -N=;

R ⁸ is H, NH ₂ or CH ₃ . _and

R ^x is hydrogen or a hydrocarbon containing from 1 to 7 carbon atoms.

Still another type of grain growth modifier contemplated for use during grain growth is iodide ion. The use of iodide ion as a grain growth modifier is taught by Maskasky I, the disclosure of which is here incorporated by reference.

In Maskasky U.S. Patent 5,061,617 (hereinafter referred to as Maskasky VT) it is taught to maintain a concentration of thiocyanate ions in the dispersing medium of from 0.2 to 10 mole percent, based on total silver introduced, to produce a high chloride tabular grain emulsion. It is here contemplated to utilize thiocyanate ion in a similar manner to control tabular grain growth.. However, whereas Maskasky VT employs a 0.5 M concentration of chloride ion in the dispersing medium, the presence of the pyrimidine grain

growth modifier of the invention in the dispersing medium at the outset of precipitation allows lower chloride ion levels to be present in the dispersing medium, as described above. The thiocyanate ion can be introduced into the dispersing medium as any convenient soluble salt, typically an alkali or alkaline earth thiocyanate salt. When the dispersing medium is acidic (i.e., the pH is less than 7.0) the counter ion of the thiocyanate salt can be ammonium ion, since ammonium ion releases an ammonia ripening agent only under alkaline conditions. Although not preferred, an ammonium counter ion is not precluded under alkaline conditions, since, as noted above, ripening can be tolerated to the extent that the 0.3 μm thickness limit of the tabular grains is not exceeded.

In addition to or in place of the preferred growth modifiers for use in combination with the pyrimidine growth modifiers of this invention it is contemplated to employ other conventional growth modifiers, such as any of those disclosed by Takada et al, Nishikawa et al, Ishiguro et al and Tufano et al, cited above and here incorporated by reference. In general thinner tabular grain populations can be realized when the pyrimidine grain growth modifier of the invention is present during grain twinning with other grain growth modifiers, when employed, being introduced during tabular grain growth following twinning.

Since silver bromide and silver iodide are markedly less soluble than silver chloride, it is appreciated that bromide and/or iodide ions, if introduced into the dispersing medium, are incorpo¬ rated into the grains in the presence of the chloride ions. The inclusion of bromide ions in even small amounts has been observed to improve ^ he tabularities

of the emulsions. Bromide ion concentrations of up to 50 mole percent, based on total silver are contem¬ plated, but to increase the advantages of high chloride concentrations it is preferred to limit the presence of other halides so that chloride accounts for at least 80 mole percent, based on silver, of the completed emulsion. Iodide can be also incorporated into the grains as they are being formed. It is preferred to limit iodide concentrations to 2 mole percent or less based on total silver. Thus, the process of the invention is capable of producing high chloride tabular grain emulsions in which the tabular grains consist essentially of silver chloride, silver bromochloride, silver iodochloride or silver iodobro- mochloride, where the halides are designated in order of ascending concentrations.

Either single-jet or double-jet precipita¬ tion techniques can be employed in the practice of the invention, although the latter is preferred. Grain nucleation can occur before or instantaneously following the addition of silver ion to the dispers¬ ing medium. While sustained or periodic subsequent nucleation is possible, to avoid polydisper≤ity and reduction of tabularity, once a stable grain popula- tion has been produced in the reaction vessel, it is preferred to precipitate additional silver halide onto the existing grain population.

In one approach silver ion is first intro¬ duced into the dispersing medium as an aqueous solu- tion, such as a silver nitrate solution, resulting in instantaneous grain nuclei formation followed immediately by addition of the growth modifier to induce twinning and tabular grain growth. Another approach is to introduce silver ion into the dispers- ing medium as preformed seed grains, typically as a

Lippmann emulsion having an ECD of less than 0.05 μm. A small fraction of the Lippmann grains serve as deposition sites while the remaining Lippmann grains dissociate into silver and halide ions that precipi- tate onto grain nuclei surfaces. Techniques for using small, preformed silver halide grains as a feedstock for emulsion precipitation are illustrated by Mignot U.S. Patent 4,334,012; Saito U.S. Patent 4,301,241; and Solberg et al U.S. Patent 4,433,048, the disclosures of which are here incorporated by reference. In still another approach, immediately following silver halide seed grain formation within or introduction into a reaction vessel, a separate step is provided to allow the initially formed grain nuclei to ripen. During the ripening step the proportion of untwinned grains can be reduced, thereby increasing the tabular grain content of the final emulsion. Also, the thickness and diameter dispersities of the final tabular grain population can be reduced by the ripening step. Ripening can be performed by stopping the flow of reactants while maintaining initial conditions within the reaction vessel or increasing the ripening rate by adjusting pH, the chloride ion concentration, and/or increasing the temperature of the dispersing medium. The pH, chloride ion concentration and grain growth modifier selections described above for precipitation can be first satisfied from the outset of silver ion precip¬ itation or during the ripening step. Except for the distinguishing features discussed above, precipitation according to the invention can take any convenient conventional form, such as disclosed in Research Disclosure Vol. 225, January 1983, Item 22534; Research Disclosure Vol. 308, December 1989, Item 308,119 (particularly

Section I); Maskasky I, cited above; Wey et al, cited above; and Maskasky II, cited above; the disclosures of which are here incorporated by reference. It is typical practice to incorporate from about 20 to 80 percent of the total dispersing medium into the reac¬ tion vessel prior to nucleation. At the very outset of nucleation a peptizer is not essential, but it is usually most convenient and practical to place peptizer in the reaction vessel prior to nucleation. Peptizer concentrations of from about 0.2 to 10 (preferably 0.2 to 6) percent; based on the total weight of the contents of the reaction vessel are typical, with additional peptizer and other vehicles typically be added to emulsions after they are prepared to facilitate coating.

Once the nucleation and growth steps have been performed the emulsions can be applied to photo¬ graphic applications following conventional prac¬ tices. The emulsions can be used as formed or further modified or blended to satisfy particular photographic aims. It is possible, for example, to practice the process of this invention and then to continue grain growth under conditions that degrade the tabularity of the grains and/or alter their halide content. It is also common practice to blend emulsions once formed with emulsions having differing grain compositions, grain shapes and/or tabular grain thicknesses and/or aspect ratios.

Exaπroles The invention can be better appreciated by reference to the following examples.

The mean thickness of tabular grain popula¬ tions was measured by optical interference for mean thicknesses >0.06 μ (measuring more than 1000 tabular

grains) , and using edge-on views observed by scanning electron microscopy for samples too thin to measure by the optical interference technique (<0.06 μm) (measuring from 50 to 100 tabular grains) . The terms ECP and t are employed as noted above; r.v. represents reaction vessel; TGPA indicates the percentage of the total grain projected area accounted by tabular grain of less than 0.3 μ thick¬ ness.

Examples 1-14

All of the following emulsions of the examples contained tabular grains of which more than 80% were regularly-shaped tabular grains, i.e., trian¬ gles and hexagons with 3-fold symmetry.

Example 1. Ultrathin AgCl High Aspect Ratio Tabular

Grain Emulsions Made at 40°C with a pH Shift After Nucleation Example 1A

A stirred reaction vessel containing 400 mL of a solution which was 2% in bone gelatin, 1.8 mM in 4,5,6-triaminopyrimidine, 0.040 M in NaCl, and 0.20 M in sodium acetate was adjusted to pH 6.0 with HNO3 a 0°C. To this solution at 40°C were added a 4 M AgN0 ₃ solution at 0.25 mL/min and a salt solution at a rate needed to maintain a constant pAg of 7.67 (0.04 M in chloride) . The salt solution was 4 M in NaCl and 15.9 mM in 4,5, 6-triaminopyrimidine and was adjusted to a pH of 6.33 at 25°C. After 4 min of addition, the additions were stopped and the pH of the reaction vessel was adjusted to 5.1 with HNO3 requiring 45 sec. The flow of the AgN03 solution was resumed at 5 mL/min until 0.13 mole of Ag had been added. The flow of the salt solution was also resumed at a rate needed to

maintain a constant pAg of 7.67. When the pH dropped below 5.0, the flow of solutions was temporarily stopped and the pH was adjusted back to 5.1. The results are given in Table I. A carbon replica of the grains is shown in the photomicrograph of Figure 2.

Example IB

This emulsion was prepared similar to that of Example 1A, except that the 5 mL/min flow of the AgN0 ₃ solution was extended until a total of 0.27 mole of AgN0 ₃ had been added. The results are presented in

Table I.

Example 2. AgCl High Aspect Ratio Tabular Grain

Emulsion Made with No Growth Modifier in Salt Solution To a stirred reaction vessel containing 400 mL of a solution at pH 6.0 and at 40°C that was 2% in bone gelatin, 1.5 mM in 4,5,6-triaminopyrimidine, 0.040 M in NaCl, and 0.20 M in sodium acetate were added a 4 M AgNθ ₃ solution and a 4 M NaCl solution. The AgN0 ₃ solution was added at 0.25 mL/min for 1 min then its flow rate was accelerated to 3.0 mL/min during period of 18 min. A total of 0.13 mole of AgN0 ₃ was added.

The 4 M NaCl solution was added at a rate needed to maintain a constant pAg of 7.67. The results are _^ presented in Table I.

Example 3. Low Methionine Gelatin

This emulsion was prepared similar to that of Example 1A, except that the bone gelatin had been pretreated with H ₂ O ₂ so that its methionine content was reduced from -55 μmole methionine per gram gelatin to less than 4 μmole methionine per gram gelatin. The results are shown in Table I.

TABLE I

Ultrathin (<360 Lattice Planes) Tabular Grain Emulsions

Tabular Grain Population Pro- Final jected PY-I per area as

I to

* c = constant flow rate after nucleation, a = accelerated flow rate ** ECD < 0.2 μm

Example 4. AgCl High Aspect Ratio Tabular Grain Emulsion Made at 40°C with a pH Shift After Nucleation This emulsion was prepared similar to that of Example 1A, except that the 5 mL/min flow of the AgNθ3 solution was extended until a total of 0.40 mole of AgN0 ₃ had been added. The results are given in

Table II.

Example 5. AgCl High Aspect Ratio Tabular Grain Emulsion Made at 40°C with a pH shift to

4.6 after Nucleation -

Example 5A

To a stirred reaction vessel containing 400 ml of a solution at pH 6.0 and at 40°C that was 2% in bone gelatin, 1.8 mM in 4,5,6-triaminopyrimidine

(PY-I), 0.040M in NaCl, and 0.20M in sodium acetate were added a 4M AgN0 ₃ solution at 0.25 mL/min and a salt solution at a rate needed to maintain a constant pAg of 7.67. The salt solution was 4M NaCl and 15.9 mM in ,5,6-triaminopyrimidine and was adjusted to a pH of

6.33 at 25°C. After 4 min of addition, the flow of solutions was stopped, and the pH of the reaction vessel was adjusted to 4.6 with HN0 ₃ . After 1 min. the flow of the AgN0 ₃ solution was resumed at 0.25 mL/min for 1 min then its flow rate was accelerated to 5 mL/min during a period of 30 min and finally held constant at 5 mL/min until 0.40 mole of AgNθ3 was added. The salt solution was added at a rate needed to maintain a constant pAg of 7.67. The results are given in Table II.

Example 5B

This emulsion was prepared similar to that of Example 5A, except that the precipitation was stopped

after 0.27 mole of AgNθ3 had been added. The results are shown in Table II.

Example 6. AgCl Tabular Grain Emulsions Made at

40°C and at pH 7.0 Example 6A

To a stirred reaction vessel containing 400 mL of a solution at pH 7.0 and at 40°C that was 2% in bone gelatin, 1.8 mM in 4,5,6-triaminopyrimidine, 0.040 M in NaCl, and 0.20 M in sodium acetate were added a 4 M AgNθ ₃ solution and a salt solution. The AgNθ ₃ solution was added at 0.25 mL/min for 1 min then its flow rate was accelerated over an additional period of 30 min (20X from start to finish) and finally held constant at 5 mL/min until 0.4 mole of AgNθ ₃ was _. added. The salt solution was 4 M in NaCl and 15.9 mM in 4,5,6- triaminopyrimidine and was adjusted to a pH of 6.33 at 25°C. it was added at a rate needed to maintain a constant pAg of 7.67, which was a rate nearly equal to that of the AgN0 ₃ solution. When the pH dropped 0.05 below the starting value of 7.0, the flow of solutions was momentarily stopped and the pH was adjusted back to the starting value. The results are _. summarized in Table II.

Example 6B This emulsion was prepared similar to that of

Example 17A, except that the precipitation was stopped after 0.27 mole of AgNθ ₃ had been added. The results are shown in Table II.

Example 6C This emulsion was prepared similar to that of

Example 6A, except that the precipitation was stopped after 0.13 mole of AgNθ ₃ had been added. The results are shown in Table II.

Example 7. AgCl High Aspect Ratio Tabular Grain

Emulsions Made at 40°C and at pH 6.0 Example 7A

This emulsion was prepared similar to that of Example 6A, except that it was precipitated at a pH of 6.0. The results are given in Table II.

Example 7B

This emulsion was prepared similar to that of Example 6B, except that it was precipitated at a pH of 6.0. The results are summarized in Table II.

Example 7C

This emulsion was prepared similar to that of Example 6C, except that it was precipitated at a pH of

6.0. The results are given in Table II.

Example 8. AgCl High Aspect Ratio Tabular Grain

Emulsions Made at 40°C and at pH 5.1 Example 8A

This emulsion was prepared similar to that of Example 6A, except that it was precipitated at a pH of 5.1. The results are given in Table II.

Example 8B

This emulsion was prepared similar to that of Example 6B, except that it was precipitated at a pH of

5.1. The results are summarized in Table II.

Example 8C

This emulsion was prepared similar to that of Example 6C, except that it was precipitated at a pH of 5.1. The results are presented in Table II.

Control 9 Control Emulsion Made at 40°C and at pH

4.2 This emulsion was prepared similar to that of Example 6A, except that it was precipitated at a pH of 4.2. The resulting emulsion consisted of nontabular grains. This was not a tabular grain emulsion.

Example 10. AgCl High Aspect Ratio Tabular Grain

Emulsion Made with No Growth Modifier in Salt Solution. Emulsion Made at 40°C Using Accelerated Flow Rate Addition

Example 10A

To a stirred reaction vessel containing 400 itiL of a solution at pH 6.0 and at 40°C that was 2% in bone gelatin, 1.5 mM in 4,5,6-triaminopyrimidine, 0.040 M in NaCl, and 0.20 M in sodium acetate were added a 4 M AgNθ ₃ solution and a 4 M NaCl solution. The AgN0 ₃ solution was added at 0.25 mL/min for 1 min then its flow rate was accelerated to 5.0 mL/min during a period of 30 min and finally held constant at 5 mL/min until 0.40 mole of AgN0 ₃ was added. The 4 M NaCl solution was added at a rate needed to maintain a constant pAg of 7.67. The results are given in Table II. A carbon replica of the grains is shown in the photomicrograph of Figure 3.

Example 10B

This emulsion was prepared similar to that of Example 10A, except that the precipitation was stopped after a total of 0.27 mole of AgNθ ₃ had been added.

The results are summarized in Table II.

Example 11. AgCl High Aspect Ratio Tabular Grain

Emulsion Made with Lower Concentration of Growth Modifier and the Precipitation Divided into Nucleation, Ripening, and Growth Steps

Example 11A

To a stirred reaction vessel containing 400 mL of a solution at pH 6.0 and at 40°C that was 2% in bone gelatin, 0.75 mM in 4,5,6-triaminopyrimidine, 0.040 M in NaCl and 0.20 M in sodium acetate were added a 4 M AgNθ ₃ solution and a 4 M NaCl solution to main¬ tain a constant pAg of 7.67. The AgN0 ₃ solution addition rate was 0.25 mL/min for 2 min then stopped for 15 in ^* then 0.25 mL/min for 1 min, accelerated to 5 mL/min in 30 min and finally held at 5 mL/min until 100 mL had been added. The results are given in Table II.

Example 11B

This emulsion was prepared similar to that of Example 11A, except that the precipitation was stopped after a total of 0.27 mole of AgN0 ₃ had been added.

The results are given in Table II.

Example 11C

This emulsion was prepared similar to that of Example 11A, except that the precipitation was stopped after a total of 0.13 mole of AgN0 ₃ had been added.

The results are presented in Table II.

Example 12. AgCl Tabular Grain Emulsion Made Similar to Example 10 But at 60°C Example 12A This emulsion was prepared similar in that of

Example 10A, but it was precipitated at 60°C and pAg of 7.05. The results are given in Table II.

Example 12B

This emulsion was prepared similar to that of Example 10A, but it was precipitated at 60°C, pAg of 7.05 and 0.27 mole of AgNθ ₃ had been added. The results are given in Table II.

Example 12C

This emulsion was prepared similar to that of Example 10A, except that it was precipitated at 60°C, pAg of 7.05 and 0.13 mole of AgNθ ₃ had been added. The results are given in Table II.

Example 13. AgCl High Aspect Ratio Tabular Grain

Emulsions Made at 60°C Example 13A

To a stirred reaction vessel containing 400 mL of a solution at pH 6.1 and at 60°C that was 2% in bone gelatin, 1.8 mM in 4,5,6-triaminopyrimidine, 0.030 M in NaCl, and 0.20 M in sodium acetate were added a 4 M AgNθ ₃ solution and a salt solution. The AgNθ ₃ solution was added at 0.25 mL/min for 1 min, then its flow rate was accelerated to 5 mL/min during a period of 30 min and finally held constant at 5 mL/min until 0.40 mole of AgN0 ₃ was added. The salt solution was 4

M in NaCl and 15.9 mM in 4,5,6-triaminopyrimidine and was adjusted to a pH of 6.33 at 25°C. It was added at a rate needed to maintain a constant pAg of 7.05. The results are presented in Table II.

Example 13B

This emulsion was prepared similar to that of Example 13A, except that the precipitation was stopped after a total of 0.27 mole of AgN0 ₃ had been added.

The results are given in Table II.

Exa ple 13C

This emulsion was prepared similar to that of Example 13A, except that the precipitation was stopped after a total of 0.13 mole of AgN0 ₃ had been added. The results are summarized in Table II. A carbon replica of the grains is shown in the photomicrograph of Figure 1.

Example 14. AgBrCl (-10 Mole % Br) High Aspect Ratio Tabular Grain Emulsions Example 14A. 10.6 Mole % Br

To a stirred reaction vessel containing 400 mL of a solution at pH 6.1 and at 60°C that was 2% in bone gelatin, 1.8 mM in 4,5,6-triaminopyrimidine, 0.030 M in NaCl, 0.002 M in NaBr, and 0.20 M in sodium acetate were added a 4 M AgNθ ₃ solution and a salt solution. The AgNθ ₃ solution was added at 0.25 mL/min for 1 min, then its flow rate was accelerated to 3.0 mL/min during a period of 18 min. A total of 0.13 mole of AgNθ ₃ was added. The salt solution was 3.6 M in NaCl, 0.4 M in NaBr, and 15.9 M in

4,5,6-triaminopyrimidine. It was adjusted to pH 6.3 at 25°C. The salt solution was added at a rate needed to maintain a constant pAg of 7.05. The results are given in Table II. A scanning electron photomicrograph of the grains is shown in Figure 4.

Example 14B. 10.0 Mole % Br

This emulsion was made similar to that of Example 14A, except that NaBr was not initially present in the reaction vessel. The results are given in Table II.

TABLE II

I ω

TABLE II (Continued)

I w σ.

* 10.6 mole % Br ** 10.0 mole % Br

Examples 15-17:

This general procedure was used to prepare all of the examples.

A stirred reaction vessel containing 400 mL of a solution which was 2% in bone gelatin, 0.04M in NaCl, 0.20M in sodium acetate and a concentration of growth modifier as given in Table III was adjusted to pH 6.0 with HNO3 at 40°C. To this solution at 40°C was added 4.0M AgN03 solution at 0.25 mL/min. Also, added as needed to maintain a constant pAg of 7.67, was a solution 4.0M in NaCl and growth modifier as indicated in Table III. The resulting NaCl-growth modifier solu¬ tion was adjusted to a pH of 6.3. After 2 min, the additions were stopped for 15 min to ripen the emulsion grains, then resumed by adding the AgN0 ₃ solution at

0.25 mL/min for 1 min and then the flows were accelerated at a rate of 0.10 mL/min/min until the amount of AgN0 ₃ indicated in Table III was added. The pAg was maintained at 7.67 by the. double- et addition of the NaCl-growth modifier solution. When the pH dropped to 5.8, the additions were momentarily stopped and the reaction vessel mixture was adjusted back to 6.0 with NaOH. The results are summarized in Table III.

Example 18 High AgCl High Aspect Ratio Tabular

Grain Emulsions Made Using 7-Azaindole and 4,5,6-Triaminopyrimidine

Example 18A

To a stirred reaction vessel containing 400 mL of a solution at pH 6.0 and at 40°C that was 2% in bone gelatin, 0.040 M in NaCl and 0.20 M in sodium acetate was added 0.60 mmole of 7-azaindole dissolve in 2 mL of methanol. Then a 4M AgN0 ₃ solution and a 4 M

NaCl solution were added. The AgN0 ₃ solution was added

at 0.25 mL/min for 4 minutes, then its flow was stopped for 10 minutes, after which 0.06mmole of the second grain growth modifier, 4,5,6-triaminopyrimidine sulfate dissolved in 25 mL of distilled water was added. The AgN0 ₃ solution flow was resumed at 0.25 mL/min for 1 minute, then the flow rate was accelerated over an additional period of 30 minutes (30X from start to finish) and finally held constant for 5 mL/min until 0.4 mole of AgN0 ₃ was added. The NaCl solution was added at a similar rate as needed to maintain a constant pAg of 7.67. When the pH dropped 0.2 units below the starting value of 7.0, the flow of solutions were momentarily stopped, and the pH was adjusted back to the starting value. The results are given in Table III.

Example 18B

This emulsion was prepared similar to that of

Example 18A, except that the precipitation was stopped after 0.27 mole of AgN0 ₃ had been added. The results are presented in Table III.

Example 18C

This emulsion was prepared similar to that of

Example 18C, except that the precipitation was stopped after 0.13 mole of AgN0 ₃ had been added. The results are presented in Table III.

TABLE III'

I

OJ

I

* a = adenine; b = 7-azaindole; 4,5, 6-triaminopyridine

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