U.S. patent number 3,773,516 [Application Number 05/213,543] was granted by the patent office on 1973-11-20 for process for preparing silver halide emulsions.
This patent grant is currently assigned to Polaroid Corporation. Invention is credited to Edgar B. Gutoff.
United States Patent |
3,773,516 |
Gutoff |
November 20, 1973 |
PROCESS FOR PREPARING SILVER HALIDE EMULSIONS
Abstract
Poly-disperse photographic silver halide emulsions comprising
silver halide grains of uniform habit are produced by utilizing a
continuous precipitation technique.
Inventors: |
Gutoff; Edgar B. (Brookline,
MA) |
Assignee: |
Polaroid Corporation
(Cambridge, MA)
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Family
ID: |
22795506 |
Appl.
No.: |
05/213,543 |
Filed: |
December 29, 1971 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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7817 |
Feb 2, 1970 |
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Current U.S.
Class: |
430/567;
430/569 |
Current CPC
Class: |
G03C
1/015 (20130101); G03C 2001/03564 (20130101); G03C
2001/03588 (20130101) |
Current International
Class: |
G03C
1/015 (20060101); G03c 001/02 () |
Field of
Search: |
;96/94,114.7 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
"Making and Coating Photographic Emulsions," Zelikman and Levi, pp.
228-233 (1964)..
|
Primary Examiner: Torchin; Norman G.
Assistant Examiner: Suro Pico; Alfonso T.
Parent Case Text
The present invention is a continuation-in-part of my copending
U.S. Pat. application Ser. No. 7817, filed Feb. 2, 1970 now
abandoned.
Claims
What is claimed is:
1. A process for preparing a photosensitive poly-disperse silver
halide emulsion comprising octahedric silver halide grains of at
least 80 percent silver bromide constituency which comprises the
continuous precipitation in a reaction vessel of said silver halide
grains in the presence of a protective colloid, with constant
agitation, under ammoniacal conditions which promote formation of
an octahedric grain habit, and at a pBr between 1.0 and 1.4, and
with the continuous removal of the resultant silver halide emulsion
in order to provide a predetermined average grain residence time in
said vessel of less than 8 minutes.
2. The invention of claim 1 wherein said protective colloid is
gelatin.
3. A process for preparing a photosensitive poly-disperse silver
halide emulsion comprising cubic silver halide grains of at least
80 percent silver bromide constituency which comprises the
continuous precipitation in a reaction vessel of said silver halide
grains in the presence of a protective colloid, with constant
agitation, under ammoniacal conditions which promote formation of a
cubic grain habit, at a pBr above 1.6, and with the continuous
removal of the resultant silver halide emulsion in order to provide
a predetermined average grain residence time in said vessel of less
than 8 minutes.
4. The invention of claim 3 wherein said protective colloid is
gelatin.
Description
The present invention is concerned with the preparation of
photographic silver halide emulsions and, more particularly, with
the preparation of emulsions having predictable properties and
comprising grains of uniform crystal habit.
In a common method of preparing photographic silver halide
emulsions, a water-soluble silver salt, such as silver nitrate, is
reacted with at least one water-soluble halide such as potassium or
ammonium bromide, preferably together with potassium or sodium
iodide in an aqueous solution of a colloidal peptizing agent, such
as gelatin. The dispersion of silver halide thus formed contains
water-soluble salts as a by-product of the double decomposition
reaction in addition to an unreacted excess of either of the
initial salts. Such water-soluble salts must be removed from the
emulsion before chemical ripening (afterripening) to enhance the
emulsion's sensitivity to light, which will be discussed more fully
hereinbelow. Such techniques are well known to those skilled in
emulsion-making technology.
There are generally two recognized techniques for controlling the
precipitation of silver halide in a gelatinuous protective colloid
environment. Such techniques comprise, respectively, the single jet
and double jet precipitation systems. In the former system, a
peptizing agent is combined with one of the reactants, normally the
halide, and the other reactant, e.g., silver nitrate, is introduced
therein with agitation. The first portion of silver nitrate reacts
with the halide solution to form silver halide nuclei; the latter
portions form additional nuclei and also add onto other existing
nuclei to form large crystals. The rate of addition thus effects
the crystal size distribution. The crystal size distribution is
also normally adjusted by holding the reaction mixture at elevated
temperatures either after all the silver nitrate has been
introduced or after only a portion has been introduced, or both.
The smaller particles having a higher solubility than the larger
particles dissolve to subsequently recrystallize out on the larger
ones. This process of physical or Ostwald ripening broadens the
particle size distribution and produces a coarse grain. The crystal
habit of photographic emulsions made by a single jet technique
normally consists of highly twinned crystals due to the large
excess of halide ions present during the precipitation and physical
ripening stages. Double jet precipitation, on the other hand,
involves the introduction of a stream of an aqueous solution of a
silver salt, as for example, silver nitrate; and the concomitant
introduction of a stream of an aqueous solution of at least one
alkali metal halide with or without a peptizing agent, into a
reaction vessel generally containing a peptizing agent such as,
preferably, gelatin. As the flow rates of both the silver nitrate
and the halide solutions can be carefully regulated, the excess
halide present in the reaction vessel can be maintained constant
and untwinned crystals may be formed. When the flow rates of the
solutions are low and the solutions are highly concentrated (about
3 N), nucleation takes place rapidly, usually in less than a
minute, and then only growth of the nuclei occurs. Crystals over 1
micron in size can be grown with a very narrow particle size
distribution. With continued additions the distance between
particles increases until the time it takes for new material to
reach the surface of the particles is larger than the nucleation
time, fresh nucleation occurs, and a dimodal distribution
results.
According to the present invention, streams of reactants are
continuously fed at a controlled rate in a reaction vessel equipped
with an efficient agitator, with the reaction product being removed
at a continuous rate. At steady state, nuclei are continuously
being formed and grown. Since the reaction mixture is well mixed
the effluent contains grains of all sizes. In the presence of
ammonia, crystals of cubic or octahedral habit can be rapidly grown
to a micron size in an average residence time of only a few minutes
compared to the many hours required by conventional double jet
precipitation techniques.
The art has taught that silver halide emulsions can be made
continuously. See U.S. Pat. No. 3,519,426 which defines a
continuous technique for producing fine grain emulsions.
Monodisperse emulsions comprising crystals about 1 micron in size
would take about at least 16 minutes since typical growth rates are
up to about 0.06 micron per minute under ammoniacal conditions, 0.2
N NH.sub.4 OH, and less at neutral conditions (Berry &
Skillman, J. Photo. Chem. 68, 1138 [1964]). If growth conditions
are altered to enhance crystal growth, one would expect twinned
crystals to result because of the inability of stacking faults to
diffuse out at such high growth rates, so twin planes form and
continue to grow (Berry & Skillman, J. Photo. Sci. 16, 137
[1968]).
Contrary to what is dictated by the art, the process of the present
invention provides polydisperse emulsions with average grain size
between 0.5 and 1.1 microns, the grains being of uniform octahedral
or cubic habit, in average residual times of less than 8 minutes,
and preferably between 0.8 to 5.0 minutes.
It is, accordingly, a primary object of the present invention to
provide a novel method for the preparation of photographic silver
halide emulsions with highly predictable photographic
characteristics.
It is another object of the present invention to provide
photographic silver halide emulsions comprising silver halide
grains of uniform habit and wide particle size distribution.
It is an additional object of the present invention to provide a
method for the preparation of poly-disperse silver halide
photographic emulsions comprising silver halide grains of uniform
habit which comprises a system for continuously precipitating
silver halide.
Other objects of the present invention will, in part, be obvious
and will, in part, appear hereinafter.
The invention, accordingly, comprises the several steps and the
relation and order of one or more of such steps with respect to
each of the others which are exemplified in the following detailed
disclosure and the scope of the application which will be indicated
in the claims.
For a fuller understanding of the nature and objects of the
invention, reference should be had to the following detailed
description taken in connection with the accompanying drawings
wherein:
FIG. 1 denotes a typical flow diagram definitive of the present
invention;
FIGS. 2 through 5 are graphical representations depicting the
particle size distribution relationship of emulsions of the present
invention.
It will be recognized that numerous advantages may be achieved
within photographic systems if the characteristics of silver halide
emulsions utilized therein can be predicted with reasonable
certainty; characteristics such as speed, sensitivity,
distribution, and so forth, being considered the most desirable
parameters which would hopefully be made subject to accurate
prediction and control according to the present invention.
Although crystals of pure silver halide such as the chloride, or
bromide, may be and have been used in photographic emulsions,
highest sensitivity is generally produced with silver bromide,
which additonally contains a small percentage of iodide ions.
Microcrystals of pure or mixed silver halide of uniform crystal
habit which are suitable for utilization in photographic emulsions
may be precipitated according to the present invention by feeding
into a reaction vessel at a continuous rate streams comprising a
silver salt, such as silver nitrate; halides of at least 80 percent
bromide constituency with up to 20 percent iodide and/or chloride,
such as potassium or ammonium bromide, etc; a protective colloid
such as gelatin; and, preferably, ammonia. Upon mixing in the
reaction vessel, microcrystals of silver halides are formed and
grow to a predetermined particle size distribution and average
particle size. This growth mechanism takes place in the presence of
continuously incoming streams of reactants. Physical ripening, if
desired, can take place in an additional vessel or vessels and
depends upon the assumption that very small crystals are more
soluble than larger ones and so dissolve, thereby forming a
super-saturated solution with reference to the larger crystals.
Thus, larger crystals, by this physical or Ostwald ripening
mechanism, grow at the expense of the smaller ones. In the absence
of ammonia, physical ripening takes place at a very slow rate due
to the low solubility of silver halides with the small excess
bromide ion levels required to produce cubic or octahedral
grains.
The ultimate particle size distribution of crystals emanating from
the precipitation vessel can be accurately regulated by controlling
the average residence time of the crystals within the reaction
vessel, the concentration of reactants, the temperature and the
degree of agitation. It will be appreciated that under these
conditions, certain particles will remain within the reaction
vessel longer than others, thereby attaining larger sizes than the
particles removed from the system prior to the average residence
time. Simple experimentation is all that is required to determine
the necessary conditions (agitation, concentration, temperature,
etc.) to produce a silver halide emulsion with a particle size
distribution in the predetermined desired range. By judiciously
choosing such a range, speed latitude of a photographic product
produced with the emulsion fabricated according to the present
procedure may be accurately predicted. The particle size
distribution may be further regulated by controlling the degree of
physical ripening subsequent to the precipitation stage.
A second parameter for which the instant invention provides
accurate predictability is crystal habit. According to the present
invention, emulsions comprising, substantially, a uniform crystal
habit, either cubic or octahedral, may be prepared; the
predominance of each being a function mainly of the silver ion
concentration (bromide ion concentration) and of the ammonia
concentration in the reaction mixture. It has been found that cubic
crystals are generally produced at low halide ion concentrations
and octahedral crystals are produced at higher concentrations. At
intermediate values of halide ion concentration, as more fully
herein below described, emulsions may be produced which comprise
both octahedral and cubic crystals. If the halide ion concentration
becomes too high, twinned crystals result. By raising the ammonia
concentration, the halide ion concentration at which the
transformation occurs from cubes to octahedra and from octahedra to
twinned crystals is increased and also the crystal growth rates are
increased.
As aforenoted, iodide ion content in the silver halide emulsion
aids in increasing the speed of the emulsion. Iodide also increases
the nucleation rate of silver halide.
It will be recognized that the halide ion concentration and the
silver ion concentration are related by means of the solubility
product, and the silver ion may, in fact, be the primary parameter
for controlling crystal habit. However, since emulsions of at least
80 percent bromide constituency are contemplated by the present
invention, and further since the examples define control parameters
in terms of bromide ion concentration, for convenience sake,
bromide ion concentration is referred to as a primary control
throughout the specification. The negative common logarithm of
bromide ion concentration, or pBr, is commonly used as a measure of
bromide ion concentration. At zero pBr, or one normal bromide, only
twinned crystals, such as flat platelets, truncated pyramides,
etc., are formed in a system utilized according to the present
invention. At a temperature of about 60.degree. C. and an ammonia
concentration of 0.66 N, with a pBr of 1.0 to 1.4, octahedra are
formed; and at pBr values above 1.6, cubic grains are formed. Mixed
grains consisting of grains with cubic and octahedral habits are
generally formed at pBr values of about 1.5. In the absence of
ammonia, uniform crystal habits may be achieved only at higher pBr
values, which are difficult to control.
It is necessary to utilize an ammoniacal precipitation gelatinous
medium in the present invention in order to control the bromide ion
concentration to provide the requisite value in the production of
the habit and particle size distribution desired, and to obtain
high growth rates. It is theorized that the ammoniacal condition,
that is, the presence of ammonium hydroxide in the precipitating
system, allows stacking faults to anneal out rapidly enough to
repress twin grain formation and results in untwinned silver halide
grains at high concentrations of bromide ion.
The precipitating system is generally operated at normal emulsion
making temperatures, e.g., 60.degree. C. with ultimate flocculation
and washing being generally accomplished below the gelation
temperature of the emulsion being formed. Such temperatures,
washing means, etc., are within the expertise of one of ordinary
skill in the art to determine and are well known to such artisans.
Further in the context of the present invention, it has been
recognized that the precipitation vessel should preferably be
maintained in a constant temperature environment, e.g., water
jacket, etc. The same holds true, for example, for any ripening
system which is utilized in conjunction with the precipitation
mechanism in a continuous emulsion-making procedure. Agitation of
the precipitating medium and/or agitation of the medium in the
physical ripening environment (that is, ripening) under conditions
where no additional reactants are being added to the system) is
also suitably determined by the operator and is in the range of
good engineering practice. Adequate mixing is needed in the
precipitation stage to prevent agglomeration, etc.
The instant invention may be more fully appreciated with reference
to FIG. 1 of the drawings which is a flow diagram of the preferred
embodiment of the present invention. In that figure, a stream of
silver nitrate solution and a stream of a solution comprising
ammonium bromide, potassium iodide, gelatin, and ammonium hydroxide
are continuously fed into a jacketed, baffled reaction vessel which
is kept at a predetermined constant temperature. The volume of the
vessel, and the respective concentrations and flows of the incoming
streams are adjusted to provide predetermined residence time and
reactant concentrations under constant agitation. The resultant
emulsion is then continuously withdrawn from the precipitation
vessel and, if desired, fed into a second jacketed, agitated vessel
where physical ripening takes place during a second predetermined
average residence time after which the material is fed to
flocculating, washing, afterripening, and storage stages, in that
order, such flocculation, washing, etc. being accomplished either
continuously or according to conventional batch procedures. It will
be appreciated that the essence of the present invention is the
continuous precipitation and withdrawal of silver halide emulsion
while maintaining the bromide ion concentration in the system at a
predetermined constant level. Sensors to measure the bromide ion
concentration may be placed, for example, in the precipitation
vessel, in the physical ripening stage, in the flocculation stage,
or in the lines from one stage to another. They are preferably
placed just after the precipitating stage. Likewise suitable
temperature sensors may be placed strategically throughout the
system to accurately measure temperature. These sensors may be
mated with control devices to provide automatic variable
control.
The present invention will be more clearly understood with
reference to the following examples:
EXAMPLE I
Into a 144 ml. reaction vessel containing four vertical baffles and
a four-bladed turbine rotating at 1725 rpm is fed a stream
comprising 1.0 N silver nitrate, at a metered rate of 24.8 mls. per
minute, and a second stream comprising a mixture of 16.6 mls, per
minute of 3.30 N ammonium hydroxide, and 41.4 mls. per minute of
0.589 N ammonium bromide, 0.03 N potassium iodide, and 1.293
percent trimellitic anhydride derivatized gelatin for a total flow
of 82.8 mls. per minute into the vessel. The reaction vessel is
maintained at 60.degree. C. by means of a water jacket and by
heating the reactant streams. It will be appreciated that the
average residence time of the silver halide in the vessel is 144
mls./82.4 mils./min. or 1.74 minutes. The gelatin is, in
particular, acid pigskin gelatin derivatized with 5.5 percent
trimellitic anhydride. In one case, the silver halide emulsion is
continuously removed from the vessel and fed into a 144 ml.
physical ripening vessel for an average residence time of 1.74
minutes. In another case, the ripening vessel is bypassed. In both
cases, the emulsions are continuously fed into a flocculating stage
maintained at 20.degree. C. and 2 N sulfuric acid is continuously
added to maintain a pH of 2 to 3. From the flocculation stage, the
flocculated emulsion is collected, washed, afterripened, sensitized
with gold and sulfur, and stored. During this experiment bromide
ion concentration was measured by a silver bromide coated silver
electrode and a standard reference electrode using a standard pH
meter and the pH was measured by a glass electrode and the same
reference electrode, all electrodes being in the flocculation
stage. The pBr measured in this experiment was 1.8 to 1.9. The
uniform cubic structure and poly-disperse condition of the finished
emulsion are immediately evident. FIG. 2 graphically depicts the
particle size distribution in the finished emulsion. Likewise, FIG.
3 shows a graphical depiction of the particle size distribution of
the emulsion which has been through the physical ripening stage.
Both emulsions were found suitable for use in photographic
negatives.
EXAMPLE II
The procedure of Example I was repeated, all parameters being the
same except that the ammonium bromide concentration was 0.697 N
resulting in a measured pBr of 1.2 to 1.26. The particle size
distribution of the finished emulsion with no physical ripening is
graphically depicted in FIG. 4. FIG. 5 is a graphical depiction of
the particle size distribution of the same emulsion which has been
physically ripened.
It will be appreciated that by the present invention, photographic
silver halide emulsions may be produced with a high degree of
predictability particularly as to speed and sensitiivity
distribution, which, it is recognized, is responsible for the gray
scale in a photographic silver halide environment.
Heretofore, if one desired to produce emulsions with silver halide
grains of cubic or octahedral habit comprising the wide particle
size distributions evident in the instant invention, it was
necessary to provide separate monodisperse emulsions of uniform
habit and blend such emulsions. It will be evident that such has
been obviated by the instant invention.
The emulsions of the present invention may be chemically sensitized
by any of the accepted procedures. For example, the emulsion may be
digested with naturally active gelatin, or sulfur compounds can be
added such as those described in U. S. Pat. Nos. 1,574,944;
1,623,499; and 2,410,689.
The emulsions may also be treated with salts of the noble metals
such as ruthenium rhodium, palladium, iridium, and platinum, all of
which belong to Group VIII of the Periodic Table of Elements and
have an atomic weight greater than 100. The salts may be used for
sensitizing in amounts below that which produce any substantial fog
inhibition, as described in U. S. Pat. No. 2,448,060 and as
antifoggants in higher amounts, as described in U. S. Pat. Nos.
2,566,245 and 2,566,263.
The emulsions may also be chemically sensitized with gold salts as
described in U. S. Pat. No. 2,399,083 or stabilized with gold salts
as described in U. S. Pat. Nos. 2,597,856 and 2,597,915.
The emulsions may also be chemically sensitized with reducing
agents such as stannous chloride as described in U. S. Pat. No.
2,487,850; amines such as diethylenetriamine as described in U. S.
Pat. No. 2,518,698; polyamides such as spermine as described in U.
S. Pat. No. 2,521,925; or bis-(.beta. -aminoethyl)-sulfide and its
water-soluble salts as described in U. S. Pat. No. 2,521,926.
The emulsions may also be stabilized with the mercury compounds of
U. S. Pat. Nos. 2,728,663; 2,728,664; and 2,728,665.
The emulsions may also be optically sensitized with cyanine and
merocyanine dyes as described in U. S. Pat. Nos. 1,846,301;
1,846,302; 1,942,854; 1,990,507; 2,112,140; 2,165,338; 2,493,747;
2,493,748; 2,503,776; 2,519,001; 2,666,761; 2,734,900; 2,739,149;
and 2,739,964.
The emulsions may also contain speed-increasing compounds of the
quaternary ammonium type as described in U. S. Pat. Nos. 2,271,623;
2,288,226; and 2,334,864; and of the polyethylene glycol type as
described in U. S. Pat. No. 2,708,162.
Where desired, suitable antifoggants, restrainers, accelerators,
preservatives, coating aids, and/or stabilizers may be included in
the composition of the emulsions.
Hardening agents such as inorganic agents providing polyvalent
metallic atoms, especially polyvalent aluminum or chromium ions,
for example, potash alum [K.sub.2 Al.sub.2 (SO.sub.4).sub. 4.sup. .
24H.sub.2 O] and chrome alum [K.sub.2 Cr.sub.2 (SO.sub.4).sub.
4.sup. . 24H.sub.2 0] and organic agents of the aldehyde type such
as formaldehyde, glyoxal, mucochloric acid, etc.; the ketone type
such as diacetal; and the quinone type may be incorporated in the
emulsions according to procedures well known in the art.
The term "photosensitive" and other terms of similar import are
herein employed in the generic sense to describe materials
possessing physical and chemical properties which enable them to
form usable images when exposed to actinic radiation.
Throughout the specification, the term "poly-disperse" has been
utilized. Such term is intended to define emulsions possessing wide
particle size distributions.
Since certain changes may be made in the above process and product
without departing from the scope of the invention herein involved,
it is intended that all matter contained in the above description
shall be interpreted as illustrative and not in a limiting
sense.
* * * * *