U.S. patent number 3,733,994 [Application Number 05/072,739] was granted by the patent office on 1973-05-22 for apparatus for washing of photographic material.
This patent grant is currently assigned to Stek Corporation. Invention is credited to Clarence J. Armstrong, Alvin Cronig.
United States Patent |
3,733,994 |
Armstrong , et al. |
May 22, 1973 |
APPARATUS FOR WASHING OF PHOTOGRAPHIC MATERIAL
Abstract
An apparatus for controlling the contamination level of photo
wash water supporting an environment for ionic substitution of
simple thiosulfate salts in the water with complex argento
thiosulfates on the photographic emulsion surface. A water purifier
is placed in closed loop with the wash tank to control the level of
contamination.
Inventors: |
Armstrong; Clarence J. (Lowell,
MA), Cronig; Alvin (Lexington, MA) |
Assignee: |
Stek Corporation (Lexington,
MA)
|
Family
ID: |
26753687 |
Appl.
No.: |
05/072,739 |
Filed: |
September 16, 1970 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
610127 |
Jan 18, 1967 |
3531284 |
|
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Current U.S.
Class: |
202/152; 159/2.1;
396/626; 202/236 |
Current CPC
Class: |
G03C
5/31 (20130101); G03D 3/065 (20130101) |
Current International
Class: |
G03C
5/31 (20060101); G03D 3/06 (20060101); G03d
003/02 () |
Field of
Search: |
;95/89R,96,97 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Matthews; Samuel S.
Assistant Examiner: Braun; Fred L.
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATIONS
This a division of U.S. application Ser. No. 610,127, filed Jan.
18, 1967, now U.S. Pat. No. 3,531,284.
Claims
What is claimed and desired to be secured by Letters Patent of the
United States is:
1. Apparatus for washing photographic material comprising:
a bath for containing wash water through which the material
passes;
means for removing the wash water which is contaminated by the
material from the bath;
means for lowering the contamination level of the removed
water;
means for introducing partially decontaminated water into the wash
bath; and,
means for maintaining the level of contamination in the wash water
within a range of from about 80 to about 10,000 parts per
million.
2. An apparatus of claim 1 further including
means for shunting a quantity of the contaminated water around the
contamination lowering means; and,
means for mixing quantities of the decontaminated water with the
shunted water prior to introduction into the bath.
3. An apparatus of claim 2 wherein said mixing means includes a
contamination sensor and a contamination control operatively
connected to said sensor whereby the level of contamination of the
wash water in the bath is kept at a constant level.
4. An apparatus of claim 3 wherein the means for lowering the
contamination level comprises a flash evaporator.
5. An apparatus of claim 1 wherein the pH of the wash water is
within the range from about 4.7 to about 4.9.
Description
BACKGROUND
1. Field of the Invention
The present invention relates to a method and an apparatus for
washing of developed photographic material and more particularly to
such method and apparatus wherein the contamination content of the
water is maintained within predetermined levels.
2. Description of the Prior Art
In silver halide photographic processing systems, the surface of
the photographic material as it leaves the developer bath and
enters the fixing bath, includes metallic silver in the developed
areas of the image, and silver halide in the undeveloped areas. A
chemical reaction takes place in the fix bath in which the silver
halide forms complex salts such as the argento complexes. Also,
free silver liberated from the emulsion of the photosensitive
surface is introduced into the fixing solution. The amount of free
silver in the photographic fixing solution is directly related to
the amount of film that is passed through the solution. Hence, as
the film footage increases, the amount of metallic silver in the
solution increases and more silver is available to react with the
emulsion on the surface of the photographic material, resulting in
heavier or more complex argento compounds. These compounds and the
simple salts on the surface of the film must be removed to
eliminate staining, spotting and fading of the finished photograph.
The heavier or more complex the salt with the emulsion, the more
difficult it is to remove the compound from the material
surface.
In the prior art, it has been common practice to wash the film with
large quantities of water for extended periods of time to remove
these salts. The obvious disadvantages of protracted washing is
that the emulsion tends to swell and distort as it is subjected to
more and more water, thus distorting the photographic image. In
many uses of the image for precise measurement and maximum
information retrieval, such as photogrammetry and reconnaisance,
the distortion due to prolonged or uncontrolled washing reduces or
eliminates the precision and retrieval capability. Further as the
emulsion becomes softer, it absorbs a good deal of water,
increasing drying time of the material. Prolonged drying or drying
at elevated temperatures necessitated by over-washing further
compounds the image distortion problems.
Most commercial photographic processing plants are located in areas
of high population concentration. For example, the motion picture
and television industries in the United States are located in Los
Angeles, Chicago, and New York City. As years go on, more concern
is shown for water conservation and purification. Indicative of the
purification problem is concern over the disposal of contaminated
solutions into sewerage systems. Also, in many tactical military
situations film processors are placed in locations where water
supplies are rather limited. Often the water is unfit for any use,
particularly photographic washing. Therefore, much effort has been
directed toward photographic processing systems incorporating
closed loop water reclamation systems in attempts to minimize clean
water requirements. In such systems water from the wash bath is
cycled through water purification apparatus and returned to the
wash bath in a purified state. As has been disclosed above, prior
art systems have used considerable quantities of water. Therefore,
such reclamation systems necessitate large storage tanks and
reclamation or purification systems, capable of processing great
quantities of water. Such purification systems are
characteristically cumbersome and overly expensive, generally unfit
for tactical and commercial applications.
SUMMARY OF THE INVENTION
The present invention provides a method and an apparatus for
drastically reducing the amount of wash water to which it is
necessary to subject photographic material. By carefully
controlling the contamination level of the wash water, it is found
that an ionic exchange occurs between complex salts and in the
photographic material and simple salts in the wash water. Since it
is much easier to remove the simple salts than the heavy ones,
providing an environment for ionic exchange effects a substantial
economy of water and drastically reduces washing time. The surface
of the emulsion is not subjected to the distortion mentioned
hereinabove. Also drying time is greatly decreased. This is due not
only to the fact that the amount of water to which the material is
subjected to decreases, but is also due to the fact that the
hardness of the emulsion can be kept in its natural hard gel state.
This is effected because of the ease with which the simple salts
are removed from the emulsion and because the pH of the water is
kept within closely controlled limits at the iso-electric point of
the gelatin. The simple salt in the water counteracts the acetic
acid carried into the wash tank from the fixing bath.
To further reduce the quantities of water used, a closed loop water
reclamation system may be utilized. Since the levels of
contamination of the water are controlled as described above and
either only a portion of the water need be purified in the cycling
operation, or only partial purification of the water takes place,
an unobvious and unexpected advantage occurs by utilizing the ionic
exchange concept described above in a closed loop system. An
advantage of ionic exchange is that the amount of water used is
drastically reduced, because the water does not have to be pure. In
fact, it is undesirable to completely purify the water. Thus only a
partial purification of the water is necessary, or alternatively,
the purification process does not have to be complete or extremely
efficient. The storage facilities, reservoirs and purifiers are
reduced in size. The total volume of water necessary to operate
such a system is greatly reduced over the closed loop reclamation
systems of the prior art.
An object of the present invention is the provision of a method and
apparatus for achieving high quality photographic images.
Another object of the present invention is the provision of a
method and apparatus for rapid photographic processing.
Yet another object of the invention is the provision of apparatus
and a system for photographic processing wherein the quantities of
water utilized are significantly reduced.
Still another object if the provision of a closed cycle
photographic washing system enabling disposal of wash water in an
uncontaminated state.
Other objects and provisions of the invention will become more
fully understood in light of the following specification taken in
conjunction with the sole FIGURE of drawing which illustrates in
schematic form, a closed loop photographic water reclamation
system.
DESCRIPTION OF THE EMBODIMENTS
Throughout the following specification, we will allude to the
processing of photographic film. It should be carefully understood
that this is merely illustrative and any photographic materials may
be processed by the practice of the method and use of the apparatus
of this invention. It is intended that this invention be limited
only by the scope of the appended claims.
In the processing of silver halide photographic film, it is very
common to use sodium potassium and ammonium salts throughout the
various baths of the developing process. Sodium sulfite (Na.sub.2
SO.sub.3) or potassium metabisulfite (K.sub.2 S.sub.2 O.sub.5) are
commonly used as a preservative to prevent aerial oxidation. In the
fixing bath sodium or ammonium thiosulfate, Na.sub.2 S.sub.2
O.sub.3 or (NH.sub.4).sub.2 S.sub.2 O.sub.3, is used to dissolve
the silver halides in the unexposed portion of the image on the
film. The reaction between the silver halides and the simple
thiosulfate salts yields argento thiosulfate complexes which remain
entrapped in the emulsion. Examples of such thiosulfate complexes
are Na.sub.2 Ag S.sub.2 O.sub.3 and (NH.sub.4).sub.2 Ag S.sub.2
O.sub.3. As the amount of film processed through the fixer bath is
increased, the amount of silver carried on the film from the
developer bath to the fixing bath is increased, thus more free
silver is available to form these argento complexes. As the fixing
solution becomes older, heavier or more complex, argento salts are
formed on the emulsion. Various polythionates such as sodium
tetrathionate Na.sub.2 (Ag)S.sub.4 O.sub.7 may be formed. As
mentioned herein before, the more complex or the heavier the salt
carried by the emulsion into the washing bath, the more difficult
it is to remove these salts. We have found that by carefully
controlling the contamination, that is, the percentage of soluble
contaminants including the simple thiosulfate salt in the wash
water, we may create a favorable atmosphere for ionic exchange.
Water containing very low concentrations of dissolved salts does
not wash as effectively as those containing moderate to high
concentrations of dissolved salts in the water. Also, above a
certain level of contamination, the wash water will not remove
thiosulfates from the emulsion in any measurable degree.
Although the ionic exchange is dependent upon the percentage of
simple thiosulfate salt in the wash water, the contamination levels
mentioned throughout the specification and recited in the claims
refer to the total level of contaminants dissolved or soluble in
the wash water and not to simple thiosulfates alone. It has been
found by empirical methods that the total concentration of soluble
contaminants disclosed contain simple thiosulfates in proportions
which create a favorable atmosphere for ionic substitution. The
ability to measure the total soluble contamination levels, rather
than measuring the level of simple thiosulfate salt greatly
simplifies the sensing equipment.
It is quite obvious that the ratio of simple thiosulfate salt to
the total soluble contaminant will not remain constant over a
protracted period of use of any photoprocessing equipment. However,
we have noted in various test runs and throughout long periods of
actual practice of the invention, examples of which are presented
below, that this factor is of no concern and may be neglected for
all practical applications within our experience. Nevertheless, if
the complex salts become a problem, a very simple expedient for the
removal of gross thiosulfate complexes from the water is available.
The chemical addition of suitable reagents to precipitate the
sulphur from the thiosulfate complex and filtration of the sulphur
from the water will remove the contaminating substances.
To explain the ion exchange theory advanced herein, it is found
that if an emulsion containing the thiosulfate ion is considered to
be an anion exchange resin, and is made basic by the addition of
suitable chemicals, an ideal solution for anion exchange exists
where R.sub.2 S.sub.2 O.sub.3 + 20H.sup.- 2ROH + S.sub.2 O.sub.3
.sup.=. However, when relatively pure water is presented to the
thiosulfate bearing emulsion, no ion exchange can be expected
because only a few sulfate ions are present in the wash water. Thus
by leaving a predetermined quantity of contamination in the wash
water, the thiosulfate ions will exchange with the argento
polythiosulfate radicals present in the argento polythiosulfate
complexes on the film, leaving thiosulfate salts which are readily
removed from the surface of the film. Obviously, if the
contamination level of the water is above a particular limit which
depends upon the efficiency of the washer, the ionic exchange
reaction ceases and the argento thiosulfates will remain in the
emulsion.
The prior art references wash conditioning or hypo eliminating
baths using thiosulfites, such as ammonium and sodium thiosulfite.
This invention eliminates the need for any prewash conditioning.
There are two obvious advantages to the elimination of a wash
conditioner or hypo eliminator bath. Firstly, the film processing
time is decreased by the elimination of one step in the wash cycle
and the size, weight and efficiency of the equipment is also
decreased. Additionally, since the sulfite salts are neutralized,
acetic acid in the hypo will increase the pH of the wash bath. In
the present system, the acidity of the fixer is counterbalanced by
the basic pH of the thiosulfates; thus we are able to keep the pH
of the film emulsion at a level between 4.7 and 4.9. This has been
found to be the "natural" gel point or isoelectric point of the
film. Less water, therefore, is absorbed by the gel. Hence the
quality of the photograph is enhanced by decreasing the amount of
water to which the film is subjected, by decreasing the wash time,
by decreasing the drying time and by lowering the pH of the wash
bath. The combination of these factors enables us to achieve
archival quality of films; that is, the films processed utilizing
the method and apparatus of the invention, are of as high quality
as the photographic properties of the film allow. No distortion
occurs due to gelatin swelling, displacement or scratching of the
surface of the emulsion.
Since the water is never completely purified, the lower limit of
contaminant being approximately 80 parts per million and the upper
limit being of the order of 10,000 parts per million, this
invention particularly adapts itself to utilization in a closed
loop system of water reclamation. In one apparatus used we have
found that only one part of clean water is necessary in the
recycling operation for every seven parts of contaminated
water.
Turning now to the sole FIGURE of drawing, a photo processor
washing apparatus 31 is connected in closed loop to a water
decontaminating or purification apparatus 21 through a wash water
support unit 11.
Water from an indiginous source (not shown) passes through the
support unit 11 via input line 12 and line 22 to a water processor
or purifier such as heat pump evaporator 21 where the water is
purified. The purified water exists from the processor 21 via
output line 23 and solenoid mixing valve 13 to line 14. Input line
12 also supplies indiginous water to line 14 via solenoid operated
mixing valve 15.
Line 14 is connected to the washing unit 31 of a photo processor
(not shown) having a contamination sensor 32 mounted therein. The
sensor 32 is connected to a contamination control instrument 16 in
support unit 11 which controls the mixing valves 13 and 15.
Processor wash tank 31 has an output or overflow pipe 33 which is
connected to a storage tank 17 in the support unit 11. Line 18,
leads from the storage tank 17 to the mixing valve 15 via a pump
37. Water from wash tank 31 is fed into storage tank 17, a portion
of the water from tank 17 is passed to purifier 21 via line 22 and
a portion to line 14 via mixing valve 15. Mixing valves 13 and 15
control the ratio of pure to contaminated water.
Once the system is filled, a valve 19 is closed and the system
operates in closed loop. The ratio of pure to contaminated water is
sensed by sensor 32, which transmits a signal to control 16 which
in turn operates the valves 13 and 15 to control the level of
contamination of the water. The control 16 is shown as a variable
control and may be set to any desired contamination level.
If it is desirable to flush or drain the system, valves 34 and 15
are closed, and valves 35 and 13 are opened. Thus, the system may
be drained with all of the water passing through purifier 21. With
this arrangement, all of the water flushed from the system will be
pure and the possibility of contaminating an indiginous supply is
eliminated.
In a particular embodiment it was found desirable to use a flash
evaporator or heat pump as the purification unit 21. The major
advantage of such a system are that the unit is relatively small
and compact. As is well known, a flash evaporator lowers the
pressure inside the unit below the ambient level of pressure and
thus the temperature of the solution to be purified does not have
to attain atmospheric boiling temperature. Thus associated
refrigeration apparatus necessary is extremely small. Additionally,
the use of a flash evaporator facilitates complete purification of
the water upon disposal. Further, the flash evaporator is extremely
stable and requires no regeneration as in ion exchange resin
systems.
It should be obvious, however, because of the quantity of water
utilized in this system due to the level of contamination of water
which is found to be desirable, that any purification apparatus
will work and the system as a whole will operate in a manner far
superior to that of prior art systems. For example, if a reverse
osmosis technique is used, wherein water enters a chamber under
high pressure and is then forced through a semipermeable membrane
effecting cleanup of the water, no holding reservoirs would be
necessary. The effectiveness of the membrane could be designed such
that a desired level of contamination would be maintained. The
advantage of such a unit is balanced by the disadvantage of
disposal of the water upon completion. It is further noticed that
with a flash evaporator utilized as the water processor,
maintenance is slight. It was found that the water could be used
for an indefinite period of time. Additionally, maintenance or
cleaning of the scaling on the evaporator may occur only once every
6 months.
The following examples are indicative of results obtainable by
utilizing the method and apparatus of the instant invention.
EXAMPLE I
A heat pump AMF RP-720 manufactured by American Machine and Foundry
Corporation of Waterford, Conn. was placed in closed loop as shown
in the sole FIGURE of drawing with a Versamat II CM photographic
processor manufactured by Eastman Kodak Company of Rochester N.Y.
The developing solution used consisted of:
water 500 ml monomethyl paramido - phenol sulphate 2.2g sodium
sulfite 96 g hydroquinone 8.8g sodium carbonate monohydrated 56g
potassium bromide 5g and add water to make 1 liter
This developer is commercially available from Eastman Kodak Company
and generally known as Kodak Developer D-19.
The fixer or hypo used consists essentially of
sodium thiosulphate hydrated 250g sodium sulphite 10g glacial
acetic acid 1.35 specific gravity 50cc
and add water to make one liter. This is commercially available
from Eastman Kodak Company and is sold under the tradename of Kodak
Rapid Fix (without hardener).
The film is processed was Eastman Kodak plus X Aerecon of 5 inches
in width. The properties of this film are shown in Eastman Kodak
Manual of Physical Properties published by Eastman Kodak Company,
Rochester New York, in section 19, type number 8401 March 1963.
The processor was completely flushed, filled with tap water, and
allowed to run without film being processed for 35 minutes before
processing started.
Contamination in PPM Soluble Contaminents
Time Proc. Proc. Dist. Proc. Dist. Resid. Output Input Input Hypo
mg/in..sup.2 Start 0 1100 105 60 8.05 10.1 1/2 hr 1100 330 50 4 hrs
5500 3650 190 5.5 6 hrs 8000 3900 270 5.1 4.3 .020 10 hrs 9500 3250
210 5.2 4.25 0.030 15 hrs. 11500 2350 330 5.0 3.8 .015 21 hrs 25000
4500 550 5.0 3.7 .040+ 30 hrs 24500 4400 720 5.2 3.9 .040 44 hrs
25000 3400 760 5.5 5.0 0.20 Total footage 31,370 feet Total water
recirculated 9,290 gallons Total water to start--25 gallons Total
water to end--25 gallons
EXAMPLE II
In this example three Versamat processes of the type used in
example 1 were connected in parallel with the heat pump and support
system shown in the cycle. All other systems parameters were the
same as they were used in Example I. ##SPC1##
Total footage processed (cumulative) 8972.5 ft. 9.5" 1450 ft. 5"
Total water recirculated -- 5446 gallons Make up water required --
0 gallons
EXAMPLE III
A single Versamat processor was utilized. Sea water was obtained
from Myrtle Beach, South Carolina with contamination level of 7,500
parts per million and a pH of 5.4. One hour 25 minutes was required
to convert 36 gallons of sea water to 20 gallons distilled water.
However, 5 gallons of distilled water, enough to start to utilize
the water reclamation system, was obtained in 11 minutes.
EXAMPLE IV
Twenty gallons of swamp water was obtained from an indiginous
slough located between Sumter, South Carolina and Columbia, South
Carolina. One hour 5 minutes was required to distill this water.
Five gallons of liquid were available after 12 minutes. Again,
sufficient water to start operation of a single processor. A single
processor as shown in the sole FIGURE of drawing was connected in
parallel utilizing the distilled swamp water. The following table
illustrates the operation of the system utilizing the distilled
swamp water as shown in the table. ##SPC2##
Total footage 8510 feet
While this invention is especially adapted for use with silver
halide photographic processing systems, it will be understood that
this invention is equally as useful in any of those photographic
systems for which fixing and washing can be applied to chemical
development or physical development of latent images where the
developed portions of the print comprise metal images and the
non-exposed portions comprise metal salts. Examples of photographic
systems other than metal halides to which this image can be adapted
are those disclosed in U. S. Pat. No. 3,152,903 and co-pending
application Ser. Nos. 199,211 filed May 14, 1962 now abandoned,
514,200 filed Dec. 16, 1965, now U.S. Pat. No. 3,512,974, and
514,176 filed Dec. 16, 1965, now U.S. Pat. No. 3,512,973. Thus the
photographic system for which this invention is adapted comprises
an oxidizing agent which is usually the image former. The preferred
oxidizing agents comprise the inorganic and organic metal salts
having reducible metal ions having at least the oxidizing power of
the cuperic ion (Cu.sup.+.sup.2). Examples of such salts are the
salts of the reducible metal ions, Ag + , Hg .sup.+.sup.2, Pb
.sup.+.sup.4, Au .sup.+.sup.3, Pt .sup.+.sup.4, Ni .sup.+.sup.2, Sn
.sup.+.sup.2, Pb .sup.+.sup.2, Cu .sup.+.sup.2, and Cu
.sup.+.sup.1.
Thus we find that by practicing the method and using the apparatus
of the present invention, the quality of the photographic film or
other photographic materials washed is limited only by the
characteristics of the photographic material or processes other
than washing. Severe constraints which might be placed on the use
and disposal of water in the future are virtually eliminated by
practice of this invention and additionally, the maintenance
problems of the apparatus are significantly reduced over prior art
systems.
Various modifications are contemplated and may obviously be
resorted to by those skilled in the art without departing from the
spirit and scope of the inventor as hereinafter defined by the
appended claims.
* * * * *