U.S. patent number 3,897,935 [Application Number 05/501,564] was granted by the patent office on 1975-08-05 for apparatus for the preparation of a photographic emulsion.
This patent grant is currently assigned to Eastman Kodak Company. Invention is credited to Gerald J. Culhane, Donald M. Forster.
United States Patent |
3,897,935 |
Forster , et al. |
August 5, 1975 |
Apparatus for the preparation of a photographic emulsion
Abstract
Apparatus is disclosed in which each of a silver salt and halide
salt or other salt solution is separately diluted with a part of a
peptizer solution but remote from the bulk of the latter. These
separate mixtures are then comixed and returned to the bulk
peptizer solution. By the diluting and comixing of the reactants
with a part of the bulk peptizer solution outside of the bulk
vessel, greater control can be exercised with respect to a variety
of parameters, irrespective of the bulk size of the peptizer
solution.
Inventors: |
Forster; Donald M. (Rochester,
NY), Culhane; Gerald J. (Rochester, NY) |
Assignee: |
Eastman Kodak Company
(Rochester, NY)
|
Family
ID: |
26974769 |
Appl.
No.: |
05/501,564 |
Filed: |
August 29, 1974 |
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
305764 |
Nov 13, 1972 |
|
|
|
|
Current U.S.
Class: |
366/339 |
Current CPC
Class: |
G03C
1/015 (20130101); B01F 5/0405 (20130101); B01F
5/106 (20130101); G03C 2200/09 (20130101) |
Current International
Class: |
B01F
5/04 (20060101); B01F 5/10 (20060101); B01F
5/00 (20060101); G03C 1/015 (20060101); B01F
005/04 () |
Field of
Search: |
;259/4,18,36,60,150,180 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Hornsby; Harvey C.
Assistant Examiner: Cantor; Alan
Attorney, Agent or Firm: Seebach; L. F.
Parent Case Text
This is a division of application Ser. No. 305,764, filed Nov. 13,
1972.
Claims
We claim:
1. Apparatus for preparing a photographic emulsion, the combination
comprising:
first means for containing a bulk quantity of a peptizer
solution;
second means for containing a bulk quantity of a salt solution;
third means for containing a bulk quantity of a silver salt
solution;
means operatively connected to the first means for moving the
peptizer solution in a prescribed flow path;
means arranged in the flow path and interconnected between the
first means and the moving means for dividing the flow of peptizer
solution between each of two separate and discrete chambers for a
predetermined length of the flow path after which the divided flows
combine;
means interconnecting the second means to one of the chambers for
introducing a flow of the salt solution into the one chamber for
mixing with the flow of peptizer solution being moved therethrough;
and
means interconnecting the third means to the other of the chambers
for introducing a flow of the silver salt solution into the other
chamber for mixing with the flow of peptizer solution being moved
therethrough;
the combined divided flows mixing and precipitating the
emulsion.
2. Apparatus in accordance with claim 1 wherein the moving means
comprises a pump for moving the peptizer solution through the flow
path defined by a conduit, and the dividing means comprises a plate
of predetermined length arranged within a portion of the conduit
for dividing the flow of peptizer solution being moved therethrough
and for dividing the portion of the conduit into two separate and
distinct chambers.
3. Apparatus in accordance with claim 2 wherein the introducing
means are interconnected to their respective chamber at
substantially the same position axially of the conduit and relative
to the length of the plate.
4. Apparatus in accordance with claim 2 wherein the introducing
means are interconnected to their respective chamber at different
positions axially of the conduit and relative to the length of the
plate.
5. Apparatus in accordance with claim 2 wherein the plate is
arranged in the portion of the conduit connecting the first means
to the pump.
6. Apparatus in accordance with claim 1 wherein the introducing
means for the flow of salt solution and for the flow of silver salt
solution are interconnected to their respective chamber so as to
introduce the solutions at an angle to the direction of flow of the
peptizer solution being moved through the chambers.
7. Apparatus in accordance with claim 6 wherein the angle is
generally normal to the direction of flow of the peptizer solution.
Description
FIELD OF THE INVENTION
The invention relates to an improved apparatus for combining and
mixing a number of liquid reactants; and, more particularly, to for
preparing a photographic emulsion.
DESCRIPTION OF THE PRIOR ART
In the preparation of photographic emulsions, it is often desirable
that the silver halide crystals or grains be precipitated in a
finely divided form. The making of such an emulsion with finely
divided silver halide grains has normally been accomplished by the
precipitation of the silver halide grains by means of a so-called
double decomposition reaction in which the reactants are introduced
into an aqueous solution, such as an aqueous solution of gelatin.
Such a solution is normally referred to as a peptizer solution,
although this latter term can be used generically to define
nonaqueous solutions as well as aqueous solutions.
The method by which the decomposition reaction is obtained is
characterized by the manner in which the reactants are introduced
into the peptizer solution. In THE THEORY OF THE PHOTOGRAPHIC
PROCESS, Third Edition, C. E. K. Mees and T. H. James, MacMillan,
1966, Chapter 2, page 34, there is a disclosure of emulsions that
are made by methods which are usually referred to as a "single-jet"
or a "double-jet" method.
In the preparation of an emulsion made by the double-jet method, an
aqueous solution of a water soluble, silver salt and an aqueous
solution of water soluble, halide or other salt are added
simultaneously to an aqueous peptizer (gelatin) solution. As the
silver halide grains are precipitated, the discrete grain sizes
tend to vary considerably, which is not a desired property,
particularly in the preparation of an emulsion wherein narrow grain
size distribution is a requisite. With nonuniformity in the size of
the precipitated silver halide grains, adverse photographic
characteristics will be imparted to the material coated with such
an emulsion; for example, reduced contrast or an undesired
phenomenon known as a "pepper fog" caused by clumped or aggregate
crystals tending to develop spontaneously. These same adverse
characteristics are experienced by photographic emulsions that are
prepared by the single-jet method.
There have been several attempts to produce an emulsion in which
the silver halide grains have a narrow grain size distribution;
that is, an emulsion having grains of substantially uniform size
throughout. Specifically, photographic emulsions have been prepared
which contain substantially fewer nonuniform large grains than were
possible with the prior and well-known precipitation
techniques.
U.S. Pat. Nos. 2,996,287 and 3,415,650 are examples of improved
silver halide precipitation techniques. These patents disclose,
respectively, an apparatus and method for improving the dispersion
of a salt solution into a peptizer solution, and a method of
removing the reaction product from a reaction zone so as to
diminish the possibilities of crystal aggregate formation. While
some of the disadvantages related to single- and double-jet
precipitations have been overcome, the limitations imposed by such
improved methods have also posed problems. For example, the
presently existing methods and apparatus do not permit achievement
of an increase in emulsion production by increasing the
concentration of the liquid reactants, because the resultant grain
size distribution also increases, thereby producing pepper fog as
referred to hereinabove.
In an attempt to increase photographic emulsion bulk or production,
U.S. Pat. No. 3,785,777 discloses a method by which one of the
silver and salt solutions is mixed with a portion of a peptizer
solution while remote from the bulk and prior to ejection into and
contact with the bulk peptizer solution. This is accomplished by a
mixing device enclosed in a housing that is submerged in the bulk
peptizer solution. In such a system, the mixing device is provided
with two mixing chambers in each of which the reactants are mixed
with peptizer solution and then brought into contact with one
another upon being expelled from the mixing device and into the
bulk peptizer solution.
In U.S. Pat No. 3,342,605, a method is disclosed by which addenda
that is prone to cause the formation of coagulated particles in a
gelatin solution is added to the gelatin solution only after being
diluted with the gelatin solution outside of the bulk vessel in
which the gelatin solution is contained. Following this teaching,
the disclosure in Porter et al could be moved outside of the vessel
to obtain somewhat greater control as in U.S. Pat. No.
3,342,605.
However, the amount of emulsion that can be mixed is limited
because of the type of apparatus. In view of the improvements made
in coating an emulsion on a support and, particularly, as related
to the rate at which such coating is effected, preparation of an
emulsion must proceed at a much greater rate than is presently
possible with the processes disclosed by the prior art. In other
words, the prior art processes do not permit greater concentration
and quantities of peptizer solutions and reactant compositions to
be handled in preparation of the emulsion, while at the same time
producing an emulsion in which there is a substantial increase in
the precipitation of silver halide grains with an accompanying
production of silver halide grains that are generally uniform in
size.
The preparation of a photographic emulsion, whether a monodispersed
or a polydispersed emulsion, requires a carefully controlled
environment; that is control of all variables, such as temperature,
pAg, pH, rate of addition, time and uniformity in mixing of two or
more reactants that can be added jointly or severally. These
variables are difficult to control independently as the size of the
emulsion preparation, bulk, or batch becomes larger. For example,
the addition of reactant compositions from at least two separate
sources tends to cause localized, high concentration of the
reactants because it is difficult to disperse small amounts of
reactants uniformly and rapidly into a large volume of emulsion, or
any other fluid or liquid. If these reactant compositions are not
dispersed uniformly, some silver halide crystals will grow more
rapidly than others, thereby resulting in a nonuniform size
distribution of the crystals.
SUMMARY OF THE INVENTION
It is an object of the invention to provide an improved apparatus
by which each of a number of liquid reactants is individually and
separately diluted by the same one reactant and then intermixed to
form a single continuous flow of the reactants.
It is another object of the invention to provide apparatus by which
a large batch of a photographic emulsion can be prepared which will
have uniform size distribution of the silver halide crystals.
It is still another object of the invention to provide apparatus by
which a photographic emulsion can be prepared and in which each of
the silver and halide salts is first diluted with a part of the
peptizer solution but separate from the bulk thereof and which
dilutions are then combined so as to precipitate silver halide
crystals of generally uniform size.
It is yet a further object of the invention to provide apparatus
for the preparation of a photographic emulsion having silver halide
grains of generally uniform size and comparable sensitometric
properties and characteristics.
Further objects and advantages of the invention will be apparent to
those skilled in the art by the description which follows.
The objects of the invention are attained by apparatus in which
each of a silver and salt solution is separately diluted with a
part of a peptizer solution but remote from the bulk thereof. These
separate mixtures are then comixed and returned to the bulk
peptizer solution. The circulatory path through which the bulk
peptizer moves outside of the bulk vessel includes a tube reactor,
having two chambers formed by an axial divider that also splits the
flow of peptizer solution, and a pump. The reactor is arranged
between the bulk vessel and the suction side of the pump. Each of
the silver and salt solutions is metered through a feed line
connected to a respective chamber at a predetermined flow rate by a
pump arranged in each respective feed line. The silver and salt
solutions can be introduced into their respective chamber at
diametrically opposite points or at different points with respect
to each other longitudinally along the divided tube for dilution
with the flow of peptizer solution. The points at which the
solutions are introduced will be determined by the required mixing
time for the solution with that of the peptizer solution.
Preferably, the end of the divided tube is arranged adjacent to the
pump in the circulatory path so that the separate flows of silver
salt and peptizer solution and halide salt and peptizer solution
are combined and mixed immediately within the pump. With such
intermixing of the peptizer, diluted silver and salt solutions, the
silver halide grains are precipitated and the solution is then
returned by the pump to the bulk vessel.
By diluting and comixing the reactants with a part of the bulk
peptizer solution outside of the bulk vessel, greater control can
be exercised with respect to the flow rates, dilution and mixing of
each reactant with respect to the peptizer solution, irrespective
of the bulk size of the peptizer solution. Such control was not
heretofore possible in processes in which the reactants were
combined either directly within the bulk peptizer solution or first
diluted within the peptizer solution. It has been found that the
aforementioned process and apparatus provides more uniform fine
grain growth and such growth is not affected by the size of the
batch of emulsion because of the controls that can now be
exercised. Likewise, the sensitometric characteristics of the
emulsion remain constant irrespective of the emulsion batch size.
Another advantage is that the silver halide grains are not
subjected to a high concentrated silver ion or halide ion
environment when individually diluted and mixed, thereby
eliminating a possible source of nonuniformity in grain morphology,
grain size and photographic sensitivity.
DESCRIPTION OF THE DRAWINGS
Reference is now made to the accompanying drawings wherein like
reference numerals designate like parts and wherein:
FIG. 1 is a schematic view of one embodiment of the invention
showing the manner in which at least two liquid reactants are
combined with a liquid composition on the discharge side of a
pump;
FIG. 2 is a vertical sectional view through the junction at which
each of the two liquid reactants is introduced into a separate flow
of the liquid composition;
FIG. 3 is a schematic view of another embodiment of the invention
in which the introduction of the two liquid reactants into the
liquid composition takes place on the suction side of the pump;
FIG. 4 is a partial, sectional view through one end of a divided
conduit or tube in the circulatory path shown in FIGS. 1 and 3 in
which each liquid reactant is introduced into a respective chamber
for dilution by the liquid composition;
FIG. 5 is a sectional view taken substantially along the lines 5--5
in FIG. 4; and
FIG. 6 is a partial, sectional view through the divided tube shown
in FIG. 4 and showing alternate ways in which the reactant
compositions can be introduced relative to the flow of the other
composition.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Before describing the invention in detail, it is thought that a
better understanding of the invention might be had if a
photographic emulsion making process were first described.
A colloidal system is a multiphase system in which there is one
finely divided discharge phase more or less uniformly distributed
or discharged through a continuous phase usually referred to as the
discharge medium. A quantity obtained in investigating the behavior
of the colloidal particles under the action or forces, chiefly
centrifugal forces, is defined as the sedimentation constant. As a
result, a monodispersed system is one of colloidal particles in
which the value of the sedimentation constant is constant for
successive time intervals, thereby indicating that the system
comprises particles of generally uniform size. On the other hand, a
polydispersed emulsion is one in which the sedimentation constant
is not of uniform value, thereby indicating particles of nonuniform
size.
The process to be described hereinafter is one which can be used
for either aqueous or nonaqueous silver halide emulsions. Such
emulsions can be used in photosensitive and photothermographic
materials and can be applied or coated on transparent or opaque
supports. Hence, the peptizer solution as well as the salts that
are used in an aqueous or nonaqueous emulsion are set forth in more
detail in U.S. Pat. No. 3,672,904, the emulsion per se forming no
part of the present invention.
In general, the term "peptizer solution," as used throughout the
following description and the claims is, therefore, meant to
include either an aqueous or a nonaqueous solution. Also, the terms
"silver" and "halide" salts can be construed to include any of such
salts used in the making of photosensitive emulsions. Even more
generally, in a process in which the reactants must be thoroughly
mixed, first in a dilution stage and then combined, the process and
apparatus about to be described will be found to be applicable and
to provide satisfactory results.
With particular reference to FIG. 1 of the drawings, a gelatin
solution and any required addenda are dissolved in a kettle or tank
10 to form a peptizer solution. A suitable stirring or mixing
device 11 is provided for continously agitating and mixing the
gelatin solution in tank 10 as the process is carried out. A halide
salt is dissolved in a suitable liquid and contained in a tank 12
and a silver salt is dissolved in a suitable liquid and combined in
tank 13. The solvent media will be dependent upon whether the
process is one involving the preparation of an aqueous or
nonaqueous emulsion and related reactants. A circulatory path
comprises a conduit designated by the numeral 15 and a pump 16' for
withdrawing the peptizer solution and moving it through the conduit
15 which returns it to the tank 10, as shown in FIG. 1. The conduit
or path 15 also includes a junction connector 16, as shown in
detail in FIG. 2. The portion of the conduit which passes through
connector 16 includes a plate 23 which divides the conduit at that
point into two chambers designated 25 and 26 which can be of equal
or unequal cross section. It will be noted from FIG. 2 that the
plate 23 extends beyond the point at which the silver and halide
salts are introduced via lines 27 and 28 into the conduit and into
their respective chambers 25 and 26. The plate 23 divides the flow
of the peptizer solution and with the introduction of the silver
and halide salts, mixing and dilution of the salts with the
peptizer solution in their respective chamber takes place before
the mixtures are combined at the downstream end of plate 23. At the
downstream end of plate 23, a plurality of twisted elements 29 are
arranged in serial relation to provide an in-line mixing device for
insuring complete mixing of the silver salt-peptizer and halide
salt-peptizer solutions prior to return and entry into the tank 10.
The flow rate of the peptizer solution from tank 15 to connector 16
is determined by pump 16' . In a similar manner, the pumps 18 and
20 can be controlled by a device 30 to vary the flow rate of the
silver and halide salts into connector 16. It is with such control
rates that the particle size, as well as uniformity of size, can be
closely controlled irrespective of the peptizer batch size within
tank 10. The control device 30 can, by means of a sensor 31 in the
peptizer solution, be responsive to the silver concentration (pAg)
in the peptizer solution and/or the pH of the peptizer solution,
thereby insuring complete control of the emulsion parameters.
With reference to FIG. 3, the peptizer solution is contained within
a tank 40 and is continuously agitated and mixed by the mixer 41.
In this embodiment, the circulatory path comprises a conduit 42 and
a pump 43 interconnected in the conduit or path. The diluted halide
salt is contained in a tank 44 and the diluted silver salt is
contained in a tank 45. Pump 46 moves the halide salt from the tank
44 via line 47 to an inlet in a portion 48 of the conduit or path
42. Likewise, the silver salt solution is moved by a pump 49 via
line 50 into the portion 48 of the conduit 42.
As shown more clearly in FIGS. 3-5, the portion 48 is of a length L
and arranged in the path and relative to pump 43 by a distance
designated as D. The tubular portion 48 is provided throughout its
length L with a plate 51 that divides the portion 48 into two
chambers designated by the numerals 52 and 53, as shown in FIG. 5.
Depending on the requirements of the process, the plate 51 can be
arranged centrally within portion 48 to provide chambers of
generally equal cross section or displaced to provide chambers of
unequal cross section. The lines 47 and 50 introduce the salt
solutions into one of the respective chambers 52, 53 in which the
solutions are diluted by and mixed with the peptizer solution. The
plate 51 divides the flow of peptizer solution for movement through
each of chambers 52, 53. The lines 47 and 50 can be connected by
any one of several junctions or inlets in the portion 48, as
designated by the numeral 54. The location at which the lines 47
and 50 are connected to the portion 48 will determine the time
allotted for mixing of that particular salt with the peptizer
solution. As in the previously described embodiment, the flow rate
of the halide and silver salts can be varied through the media of
pumps 46 and 49 to control the pAg and/or pH of the peptizer
solution. Also, as in the previous embodiment, a sensor 60 can be
positioned in the peptizer solution and utilized to generate a
signal corresponding to the existing pAg and/or pH of the solution
which is then used by device 61 to adjust the flow rates of the
pumps 46 and/or 49. The flow rate of one or both of the halide and
silver salts is thereby adjusted until the desired pAg and/or pH
level is reached.
As shown in FIG. 3, the distance D can be varied and may or may not
include an in-line mixer 29, as shown in FIG. 2. In some instances,
it may be desirable to connect the end of portion 48 directly to
the pump 43 without any intermediate mixing action. When the silver
and halide salts are introduced into the respective chambers 52 and
53, as shown in FIGS. 4 and 5, the solutions are usually introduced
at an angle that is generally perpendicular to the flow of the
peptizer solution. However, as shown in FIG. 6, the desired mixing
action that is required can be varied by arranging the discharge
angle relative to the flow of the peptizer solution. As shown by
the position of the conduit 65, this can be at an angle in
opposition to or as shown by the conduit 66 at an angle with the
flow of peptizer solution. In both cases, the actual angle can be
varied in accordance with the result desired. Also, the direction
of flow of the peptizer solution can be in a vertical direction as
in FIGS. 1 and 6 or in a horizontal direction as in FIG. 3. The
flow of peptizer solution can also be divided so as to form two
flows, each of which is directed into a separate conduit. In this
case, each salt solution will be introduced into a respective
conduit and the separate flows then recombined. As shown in FIGS. 1
and 3, the chambers 25, 26 and 52, 53 can be located on either side
of the pump, that is, on the discharge side (25, 26) or on the
suction size (52, 53).
The type and degree of agitation desired through precipitation can
also be controlled by varying the rate or speed of pump 16' or pump
43. The actual precipitation of the silver halide grains takes
place in the mixing action provided by either pump 43 or the
in-line mixer 29. In addition to the silver and halide salts,
chemical sensitizers, spectral sensitizers and coating aids can
also be introduced through the media of portion 48. Each of such
addenda can be mixed with the proper salt and diluted with the
peptizer solution prior to full mixture in pump 43. The length L as
well as the diameter of the portion 48 can be varied to provide an
optimum velocity and mixing time in accordance with the reactants,
concentrations, temperatures, etc., or any combination of these and
other parameters that might be used.
Although the invention has been described primarily as apparatus
for the preparation of monodispersed emulsions, it will be obvious
to those skilled in the art that the invention can be used for
combining and mixing other reactant compositions wherein dilution
prior to complete mixing will produce a more reliable and
homogeneous mixture. The apparatus is also capable of considerable
flexibility and of vernier adjustment so that the degree and time
of mixing can be controlled within very narrow limits.
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.
* * * * *