U.S. patent number 3,779,518 [Application Number 05/225,194] was granted by the patent office on 1973-12-18 for continuous photographic emulsion processing.
This patent grant is currently assigned to AGFA-Gevaert Aktiengesellschaft. Invention is credited to Kurt Browatzki, Hans Frenken, Josef Friedsan, Hans Gref, Peter Herzhoff, Gunther Koepke, Wolfgang Muller-Bardorff, Wolfgang Schweicher, Karl Voss, Willi Wasser.
United States Patent |
3,779,518 |
Koepke , et al. |
December 18, 1973 |
CONTINUOUS PHOTOGRAPHIC EMULSION PROCESSING
Abstract
A continuous preparation of photographic emulsions by adding a
plurality of individual components, the individual components being
introduced continuously and successively by metering pumps. Each
individual component is completely mixed with the main stream of
emulsion before the next component is introduced. Mixing is carried
out in a static mixing zone or alternatively by producing a
secondary turbulent flow in a particularly designed mixing
zone.
Inventors: |
Koepke; Gunther (Leverkusen,
DT), Muller-Bardorff; Wolfgang (Cologne,
DT), Herzhoff; Peter (Leverkusen, DT),
Gref; Hans (Cologne, DT), Schweicher; Wolfgang
(Leverkusen, DT), Frenken; Hans (Leverkusen,
DT), Voss; Karl (Leverkusen, DT), Wasser;
Willi (Leverkusen, DT), Browatzki; Kurt (Opladen,
DT), Friedsan; Josef (Langenfeld, DT) |
Assignee: |
AGFA-Gevaert Aktiengesellschaft
(Leverkusen, DT)
|
Family
ID: |
5798488 |
Appl.
No.: |
05/225,194 |
Filed: |
February 10, 1972 |
Foreign Application Priority Data
|
|
|
|
|
Feb 11, 1971 [DT] |
|
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P 21 06 526.9 |
|
Current U.S.
Class: |
366/152.3;
366/174.1; 137/93; 366/339; 137/565.33; 137/92; 137/571 |
Current CPC
Class: |
B01F
13/1013 (20130101); G03C 1/015 (20130101); B01F
5/0646 (20130101); B01F 5/0656 (20130101); Y10T
137/86163 (20150401); Y10T 137/2506 (20150401); Y10T
137/2509 (20150401); Y10T 137/86187 (20150401); G03C
2200/09 (20130101) |
Current International
Class: |
B01F
13/10 (20060101); B01F 13/00 (20060101); B01F
5/06 (20060101); G03C 1/015 (20060101); B01f
005/00 (); B01f 015/02 () |
Field of
Search: |
;259/4,7,8,18,36,60
;137/92,93,567,571 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Jenkins; Robert W.
Assistant Examiner: Coe; Philip R.
Claims
What we claim is:
1. A process for the continuous preparation of photographic
emulsions which are ready for casting, wherein individual emulsion
components are introduced into a stream of staring emulsion at
different locations in a series of closed tubular bodies and
dispersed in the stream, the individual components being introduced
continuously and in succession to one another by means of metering
pumps, and a succession of changes in the direction of flow of the
stream are caused by channeling it through a nonlinear static flow
channeling element in a mixing zone in the closed tubular body
downstream from where each individual component is introduced
whereby each individual component is completely admixed with the
stream before the next component is introduced.
2. A process according to claim 1, wherein the admixture takes
place in a static mixing zone.
3. A process according to claim 1, wherein a secondary turbulent
flow is generated in the mixing zone.
4. A process according to claim 1, wherein the average residence
time in the mixing zone of an introduced component is at most 50
seconds.
5. An apparatus for the continuous preparation of photographic
emulsions which are ready for casting, comprising a series of
tubular bodies having inlets arranged at different locations
between them, each of the inlets communicating through metering
pumps with one or more individual emulsion component storage
vessels, a mixing zone which as no parts adapted to be mechanically
moved being arranged between each adjacent pair of inlets, and a
spiral flow channeling element in each of the mixing zones for
causing a succession of changes in the direction of flow in the
mixing zones whereby each component is completely admixed before
the next is introduced.
6. An apparatus according to claim 5, wherein the inlets are in the
form of sprinklers.
7. An apparatus according to claim 5, wherein each metering pump
has a common drive shaft which also drives a main stream pump.
8. An apparatus according to claim 5, comprising sensors adapted to
sense the pH value and viscosity of the substantially completed
emulsion and regulating system adapted to maintain these values
constant.
9. An apparatus according to claim 5 comprising a measuring control
vessel located before the first tubular body in the series.
10. A mixing zone for introducing a liquid additive into a flow
stream comprising at least one tubular conduit, removable heads
connected to each end of the tubular conduit for connecting it as
part of a tubular body, an additive inlet connected to each of the
heads, a spiral lead screw having helical flutes disposed about a
longitudinal core rod being removably inserted within each of the
tubes for generating a secondary turbulent flow within each of the
tubes, and the removable heads being constructed and arranged to
permit removal of the spiral lead screws for cleaning.
11. A mixing zone according to claim 10, wherein the outer
dimension of the flutes is slightly less than the inside dimension
of the tube to form a spiral flow channel within the tube between
the core and the inner wall of the tube.
12. An apparatus for the continuous preparation of photographic
emulsions which are ready for casting, comprising a series of
tubular bodies having inlets arranged at different locations
between them, each of the inlets communicating through metering
pumps with one or more individual emulsion component storage
vessels, a mixing zone which has no parts adapted to be
mechanically moved being arranged between each adjacent pair of
inlets, and each mixing zone comprises two adjacent tubes arranged
in hairpin-fashion in each of which is arranged a spiral flow
channel having a diameter substantially identical in the internal
diameter of the respective tube.
13. An apparatus for the continuous prepartion of photographic
emulsions which are ready for casting, comprising a series of
tubular bodies having inlets arranged at different location between
them, each of the inlets communicating through metering pumps with
one or more individual emulsion component storage vessels, a mixing
zone which has no parts adapted to be mechanically moved being
arranged between each adjacent pair of inlets, each of the mixing
zones includes at least one tubular conduit, removable heads
connected to each end of the conduit for connecting it as part of
the tubular body, one of the inlets being connected to each of the
heads, a spiral lead screw having helical flutes disposed about a
longitudinal core rod being removably inserted within each of the
tubes for generating a secondary turbulent flow within each of the
tubes, and the removable heads being constructed and arranged to
permit removal of the spiral lead screws for cleaning.
14. An apparatus according to claim 12, wherein the spiral flow
channel has a core and a lead along the core, and the ratio of the
lead of the spiral to the distance between the core of the spiral
and the inside of the tube is about 2 : 1 .
15. An apparatus according to claim 13, wherein each of the heads
includes a pair of openings for connection to a pair of the tubes,
one of the heads connecting one end of each of the tubes to each
other, and the other of the heads including an inflow connection to
one of the tubes and an outflow connection to the other of the
tubes.
16. An apparatus according to claim 13, wherein the outer dimension
of the flutes is slightly less than the inside dimension of the
tube to form a spiral flow channel within the tube between the core
and the inner wall of the tube.
17. A mixing zone for introducing a liquid additive into a flow
stream comprising at least one tubular conduit, removable heads
connected to each end of the tubular conduit for connecting it as
part of a tubular body, an additive inlet connected to each of the
heads, spiral lead screw having helical flutes disposed about a
longitudinal core rod being removably inserted within each of the
tubes for generating a secondary turbulent flow within each of the
tubes, and the removable heads being constructed and arranged to
permit removal of the spiral lead screws for cleaning, each of the
heads includes a pair of openings for connection to a pair of the
tubes, one of the heads connecting one end of each of the tubes to
each other, and the other of the heads including an inflow
connection to one of the tubes and the outflow connection to the
other of the tubes.
18. An apparatus for the continuous preparation of photographic
emulsions which are ready for casting, comprising a series of
tubular bodies having inlets arranged at different locations
between them communicating through metering pumps with one or more
individual emulsion component storage vessels, a mixing zone which
has no parts adapted to be mechanically moved being arranged
between each adjacent pair of inlets, and the inlets comprising
tubes arranged tangential to the series of tubular bodies.
Description
The present invention relates to a process for the continuous
preparation of photographic emulsions which are ready for casting
in which the individual components are introduced together into a
closed, tubular body with the starting emulsion and dispersed in
one another, and to an apparatus for carrying out this process.
It is known that metering pumps can be used to carry out reactions
in which reactants cannot all be immediately combined. By means of
such metering pumps, the different reactants can be delivered in
graduated quantities to a reaction vessel. It is possible in this
way for the reaction to be controlled quantitatively and for its
duration to be controlled also.
Various processes for the continuous preparation of emulsions are
already known. Unfortunately, particular problems arise where even
small quantities of certain additives have an appreciable effect
upon the photographic properties of the emulsion. For this reason,
any process in which two or more reactants are continuously
delivered to a reaction vessel and a quantity equal to the sum
total of all the reactants is continuously run off from the
reaction vessel, cannot be considered for use in this case. Through
calculations well known in process technology based upon the
residence time in finite reaction vessels, it is possible to show
that the parts by volume removed from the vessel contain parts by
volume which have a non-uniform residence time in the vessel.
Processes in which the usual sequences of events takes place
successively in different apparatus, are equally unsuitable.
Even in cases where these ideas are further developed, it is of
course not possible with simple formulations to mix the liquids,
for example, to satisfy the stringent requirements made of the
process as to accuracy which are determined by the characteristics
of the photographic emulsion
The particular recipe for preparing photographic emulsions makes it
necessary for the additives to be individually introduced because
otherwise certain properties cannot be achieved. Accordingly, it is
extremely important to only introduce one additive at a time into
the mixture, rather than to combine several additives, because of
the mixing effect at high speeds.
Two liquids can be effectively admixed with one another. However,
suitable apparatus for such admixture has the disadvantage that it
includes mechanically moving components and, if several additives
are to be introduced, it becomes unweildy and unsuitable for the
purpose envisaged.
In another known process, the basic component is carried along in
an ascending stream, whilst the additional components are
superimposed in continuous succession upon the basic component
rotationally symmetrically in a cross-stream. One disadvantage of
this process is that admixture is always incomplete and that it is
impossible to establish consistent mixing times for different parts
of the emulsion.
The object of the invention is to react the smallest possible
proportions by volume of the emulsion and additives as directly and
as quickly as possible. An apparatus which provides the reactants
with temporary protection from the mixture, is thus unsuitable in
principle.
The problem which the invention seeks to solve is discussed in more
detail in the following:
Hitherto, photographic emulsions have been provided in accordance
with certain recipes with a number of additives which impart to
these emulsions advantages such as for example sensitivity in
certain spectral regions, stability during casting, stability
during storage, and favourable fogging characteristics. These
substances have to be added in a certain order and in a certain
chronological sequence in order to achieve the required objective.
This is associated with the fact that, in order to become active,
these substances have to be adsorbed onto the silver halide grain.
A place on the grain surface which is occupied by substance A
either cannot be taken up by substance B at all, or can only be
taken up after a desorption process. These processes are subject to
known physical laws. In general, attempts were made to allow a
small quantity of an active substance to act upon a large
proportion of emulsion for a certain period of time and, in this
way, to ensure that equilibrium is adjusted in the mixture. One
disadvantage of this procedure is that the active substance is
introduced in concentrated form in a relatively small quantity by
volume into a large quantity of emulsion and subsequently has to be
dispersed therein by stirring. The fact that the substances are
insoluble in water is often particularly unfavourable so far as
effective distribution over the grain surfaces of the silver halide
grains is concerned. Accordingly, the idea behind the process was
to rapidly bring one unit by volume of the emulsion into direct
contact with one unit by volume of the active solution so that not
only does rapid admixture in the accepted sense occur, but also the
rate at which adsorption takes place is comparable with the rate at
which precipitation takes place.
Accordingly to the present invention, there is provided a process
for the continuous preparation of photographic emulsions which are
ready for casting, wherein individual emulsion components are
introduced into a stream of starting emulsion in a closed tubular
body and dispersed in the stream, the individual components being
introduced continuously and in succession to one another by means
of metering pumps, each individual component being completely
admixed with the stream in a mixing zone downstream from where it
is introduced before the next component is introduced.
Admixture advantageously takes place in a static mixing zone. In a
mixing zone of this kind, a particularly intense mixing effect can
be achieved by generating a secondary turbulent flow in the mixing
zone.
In a further development of the process according to the invention,
the rate of flow of the main stream is selected in such a way that
the average residence time of a particular component in its
respective mixing zone is at most 50 seconds.
Accordingly to the present invention, there is also provided an
apparatus for the continuous preparation of photographic emulsion
which are ready for casting, comprising a tubular body having
inlets arranged along its length which each communicate through
metering pumps with one or more individual emulsion component
storage vessels, a mixing zone which has no parts adapted to be
mechanically moved being arranged between each adjacent pair of
inlets.
In one advantageous embodiment of the apparatus, the mixing zone
consists of two tubes arranged one behind the other in
hairpin-fashion in each of which tubes a spiral is arranged whose
diameter is substantially identical to the internal diameter of the
tube. The spiral is best dimensioned in such a way that the ratio
of its lead to the distance between its core and the inner surface
of the respective tube is 2:1.
The inlets for the individual components are simply formed by
tangential tubes or, in preferred embodiment, are in the form of
sprinkler heads.
To make cleaning easy, the hairpin-like mixing zones are provided
with quick closures, the spirals being locked in position by
holders when the mixing zones are closed.
Preferably, the metering pumps are not driven through separate
motors, but instead have a common drive.
In order to keep both the pH-value and the viscosity of the
completed mixture constant, suitable measuring sensors and
regulating devices are preferably provided at the end of the mixing
zone. In addition, measuring control vessels are incorporated both
in the upstream end of the tubular pipe and between the inlets for
the additives and their supply vessels for monitoring the mixing
ratio.
By virtue of the process according to the invention, and additives
are quickly and completely admixed with the main stream.
By comparison with the conventional process for the continuous
preparation of emulsions, the time required to complete the
adsorption of photographically active substances from a partly
precipitated heavily diluted solution is greatly reduced. The
effect of guiding flow in the manner described is that the solution
of the photographically active substances of the emulsion is
delivered in small proportions by volume and, through the intensive
admixing effect, passes directly to the silver halide grain before
precipitation can take place. The effect of this is that there is
no need for the hitherto necessary digestion times during
preparation of the emulsion. In the past, it has for the same
reason not been possible to use a large number of very promising
photographically active substances because they change their
physical and chemical qualities during the digestion period.
Accordingly, the process according to the invention also opens up
the use of a new group of photographically active additives.
Another advantage of the process according to the invention is that
it is possible to quickly change from production of one emulsion of
one composition to an emulsion of a different composition. In this
respect the low overall volume achieved through the special
hairpin-like configuration of the mixing zones has a favourable
effect.
It is also readily possible to provide regulating means for
continuously regulating the additives at the individual inlets. In
this case, the installation can be centrally controlled from a
process computer to which all regulating systems are linked.
The installation according to the invention is extremely easy to
maintain and clean. In addition, its reliability in operation is
extremely high because there are no mechanically moved parts in the
emulsion feed zone as a whole.
Referring to the accompanying drawings;
FIG. 1 diagrammatically illustrates the installation as a
whole;
FIG. 2 is a partial cross-actional view which shows the
hairpin-like mixing zone in detail;
FIG. 2A is a cross-sectional view taken through FIG. 2 along the
line 2A--2A;
FIG. 3 is an enlarged fragmental cross-section which shows how the
secondary eddy current is generated;
FIGS. 4 and 5 are cross-sectional views which show special
embodiment of the inlets.
FIG. 1 shows how the stream of emulsion is guided. A starting
emulsion is continuously introduced into the installation at an
inlet 1, flows through a measuring control vessel 2 and is then
pumped by a mainstream metering pump 3 into the hairpin-like mixing
zones 4 which are arranged one behind the other. Additives A.sub.1
to A.sub.7 are successively introduced into the main stream 1 by
reciprocating metering pumps 5 through inlets 6. The main stream
pump 3 and all the metering pumps 5 have a common drive. All the
pumps are best adjusted in phase in such a way that they deliver
the additives in synchronism with one another. The throughput in
the mixing zone can be adjusted substantially as required by a
rotational speed adjustment (not shown), or alternatively can be
automatically regulated in dependence upon their levels and thus
adapted to consumption. The mixing ratio, and hence the composition
of the emulsion, remains constant irrespective of the througput.
The mixing ratio is additionally monitored at fixed time intervals
by the measuring control vessel 2 and by further measuring control
vessels (not shown) which are installed in the feed pipes for
additives A.sub.1 to A.sub.7. Incorrect metering, if any, can be
immediately detected in this way.
The average residence time of any one unit of volume of the
components added in the mixing zone 4 is governed by the
throughput. In the practical operation of the installation,
residence time of b 50 seconds are generally not exceeded because
otherwise the emulsions can change their properties.
Additives A.sub.1 to A.sub.7 can include dyes for optical
sensitisation, organochemical substances for stabilisation, wetting
agents, hardeners, dye components, optical brighteners,
pH-regulators, etc. The mixing effect in the zone 4 is so intense
that complete admixture of a given component with a volume of the
main stream always takes place before a new additive is introduced
into that volume. Spirals 7, which generate a secondary turbulent
flow, are shown in the mixing zones 4.
The last two mixing zones are provided with detectors 8, 9 and
control systems 8', 9' which are adapted to keep the pH-value and
the viscosity, respectively, constant. These values can be
influenced by the additives A.sub.6 and A.sub.7. For this purpose,
the last two metering pumps 5' are provided with an adjustable
piston stroke which is controlled by the regulating systems 8' and
9'. In certain cases, it can be of advantage to distribute an
additive through several metering pumps and mixing zones 4 rather
than introducing it through a single metering pump 5. The emulsion,
ready for casting, is removed from an outlet 10 of the installation
and can be directly delivered to a coating machine.
FIG. 2 and FIG. 2A show hairpin-like mixing zone 4 in detail. It
consists of two tubes 11 which are arranged one behind the other
and in which the spirals 7 are fixed by means of holders 12. The
ends of the tubes 11 are provided with quick closures 13. When the
mixing zones 4 are closed, the spirals 7 are locked in position by
the holders 12. When the quick closure 13 is released, the spirals
7 can be readily removed so that the tubes can be cleaned. The
mixing zones are surrounded by a jacket 14 and can be
thermostatically maintained at a temperature of from 30.degree. to
60.degree.C by means of a tempering liquid which is introduced
through the jacket opening 15. The inlet 6 through which additives
are introduced is situated at the lower end of a tube 11 of the
mixing zone.
FIG. 3 shows a detail of the mixing zone on a larger scale. The
tempering vessel 14, which is filled with a heating medium,
concentrically surrounds the tube 11 of the mixing zone. A
particularly intense mixing effect is achieved if the spiral 7 is
dimensioned in such a way that the ratio of lead a to internal
space b is about 2:1. With these dimensions, secondary turbulent
flow 16 is developed in the spiral 11, as shown in the drawing.
FIGS. 4 and 5 show embodiments of the inlet 6. FIG. 4 shows an
inlet in the form of a simple tangentially arranged tube. The
component to be added flows through an inlet tube 17 substantially
perpendicularly of the direction of the main stream at the lower
end of the mixing tube 11.
An improved mixing effect is obtained where the inlet 6 is in the
form of a sprinkler as shown in FIG. 5. In this case, the component
to be added flows through the inlet tube 17 into an annular duct 18
and through openings 19, perpendicularly of the direction of the
main stream, into the mixing tube 11.
The static form of mixing zone is provided by omitting spirals 7
from mixing zones 4, and a complete static mixing zone apparatus is
as shown in FIGS. 1, 2 and 2A without any spirals 7.
* * * * *