,
Patented Nov. 8, 1949
‘2,487,569
UNITED vSTAT ES. PATENT or FlCE
‘2,487,563
,ANTISTAIN BATHS Eon copoa
.PHQIOGBABHIO MATERIALS
assignor
ScudderMeekey, Binghamicn, N. Y.,New‘York,
'& Film Corporation,
to General Aniline
‘N. "Y., :a -eorporation of Delaware
No Drawing. Applicationluly 21, 1948,
ZSeriaLNO- 4.0;010
4 Claims.
. (Cl. 95-1-88)
:1
This invention relates'to photographic enti
2
triazines contemplated for reaction with the
formaldehyde have'the following formulae:
stain baths, to .antiestain 'ba’ihsiemployed in -
multielayer color photography, and especially '150
(,1)
final rinse ‘baths for the washing of multi-layer
color photographic material -.foll.owing ‘the ‘?xing
treatment-s0 as to prevent the iormation ‘0i stain
,It is vknown thatin the processing of multie
color reversible
and mum-color reversible
White opaque the exposed mm .or exnosedrwhite
opaque, is ?rst developed with a normal black 10
and white developer to produce a negative image.
After development, the vblack and white negative
material, without being ?xed, is exposed to gen
eral ‘illumination, followed by a second develop
ment with a coloreforming developer. During‘the .15
?rst and second development,_the silver-‘halides
and
in all the layers are reduced to metallic silver.
After the second development, the material is
cleared in running'water, hardened in an aqueous
solution consisting of either alum or potassium go
chrome alum, andthen washed in running water
Aiter the latter treatment, vthe silver present
N
all the layers formed during the ?rst and second
development is ‘converted into a salt by and 19f
the, known silver-salt formers, commonly llsnown
as bleaching baths, and the silver-salt $113115
iormedis then removed by dissolvingitin a silver-.
In'Formula l at least one Y is an amino group
having at least one reactive hydrogen atom, the
remaining 'Y’s being a radical such as hydrogen,
,
' amino, hydroxy, halogen, i. e., chlorine, bromine,
etc., alkyl, i. e., methyl, ethyl, propyl, isopropyl,
salt solvent such as, for example, hypo. The ma
butyl, etc., alkylene, i. e., l-butenyl, etcqaryl, ‘i. ‘e.,
phenyl, naphthyl, etc., and aralkyl, ~i. e., benzyl,
methylbenzyl, ethylbenzyl, etc. 'In‘Formula :2 ‘Z
represents hydrogen, amino, alkyl, 1. e., methyl,
terial is then washed for .a long period of timeand
thenrdried.
During the ?nal washing operation 'it‘is essen- '
tial that the residual second or :oolor developer
and bleach solutions be removed, otherwise stains
will be formed during the drying operation, which
ethyl,'~butyl, etc., p'henyl, phenylenahydroxy, alk
ox-y, vii. e., methoxy, ethoxy, propoxy, etc., ‘mer
- are particularly noticeable in the ‘white area. ‘In ,. _;
order to prevent this staining, an extended ?nal
washing time in running water of irom ?fteen
minutes to two vhours ‘has ‘been ‘proposed. ‘Even if
this proposal be adopted, stains arenevertheless.
formed during and after ‘the drying ‘operation.
It is ‘believed that the ‘staining results from the
oxidation of'traces ofthe color developer retained
eapto, alkylthio (alkyl-S-), ‘i. e., methylthio,
ethylthio, propylthio, etc., and hydrazino, at least
two Z’s being primary amino or hydrazino. In
Formula 3 X is hydrogen or a primary amino and
I
T1‘. represents
halogen, hydrazino, "phenyl, hy
methoxy, ethoxy, propoxy, I
40 droxy, alkoxy, i. e., _‘
in the layers of the material following color-form
ing development, which then. react with the am
used color immer
An object of the present invention is teeiiinir
nate excessive washing time of color developed
inultieeetlorphotographic ma rial while prevent
butoxy, etc,, or an alkylthio (alkyl-S-i group, i. e.,
methylthio, ethylthio, propylthio, etc.
The water-soluble addition products of form
aldehyde and an azine characterized by Formula
v1 are prepared according to the methods de
scribed ‘in United States Patent 2,197,357. The
water-soluble products while utilizing the azines
of Formulae 2 and 3 are prepared according to
the methods described in United States Patents,
ingthe intimation .ei Stain.
"
50 ‘2,211,? {10 and 2,211,709, respectively.
. A iii-147K153?‘ object at theinvention isa?nalrinee
'By utilizing this ?nal rinse bath, in lieu of ex
bath which clears undesirable matter from a‘ .
multi-color photographic material in a short time
while avoiding staining.
Other objects and ‘features of the invention “,Will
become apparent as the. description proceeds.
I
I have discovered that the above .pb'iects are
accomplished lay-employing as a ?nal rinse‘bat-h
i-an aqueous solution containing a small quantity
of a water-soluble addition product :of formalde'e
hyde
a diazine
triazine. The
tended washing in water. the washing time after
"?xing is considerably reduced, and stain ‘forma
tion prevented, The exact operation of the wa
ter-soluble addition products of ‘formaldehyde
and an azine in the ?nal rinse ‘bath is unknown
and to date has been unascertainable. it is
known that the tendency to stain formation en
countered lin the processing of color film by the
v"coilggprforming development method is attributable
60
and.
3
2,487,569
4
in the main to the retention in the layers of the
.
three printing primaries will produce all of the
multi-layer material of small amount of the
color developer. This becomes progressively ox
other colors in the ?nished ?lm or print.
The color negative ?lm is made up in the same:
manner as the color reversible ?lm with the exception that it may contain a layer of clear"
idized by atmospheric conditions, the oxidized
products reacting with unused and unremoved
color former.
gelatin between the red sensitive layer and the‘
It is likewise known that this tendency to
green sensitive layer. The color reversible white
stain formation can be obviated by the utiliza
opaque material is prepared in the same manner
tion of reducing agents such as alkali sul?te,
as color reversible ?lm and the color negative
hydrazines, hydroxylamines and the like which
?lm with the exception that the base consists of
operate to destroy the retained color developer.
an opaque white ?lm. The color paper is also
Rather peculiarly, it has been found that the
constructed in the same manner as the color re
addition products referred to hereinabove are
versible ?lm and the color negative ?lm, with the
analogous to the reducing agents to the extent
exception that the emulsion is coated on a baryta
that both overcome the tendency to stain‘ forma 15 coated paper base. Suitable methods for the
tion. Despite the factv that the addition products
preparation of photographic multi--layer ma
would not appear to be constituted in a fashion
terials have been described in the literature re
to permit them to act as reducing agents, it
lating to color photography and are, therefore,
would, nevertheless, appear that they may have
not described here.
this property because of the results they achieve. 20
The following examples describe in detail.
In any case, the conclusion is inescapable that
methods for accomplishing the above objects, but
the addition products either function as reducing
it is to be understood that. they are inserted
agents to destroy the color developer, or react
merely for purposes of illustration and are not
With the color developer or the oxidation prod
to be construed as limiting the scope of the in
ucts thereof in a manner to prevent subsequent 25 vention.
reaction of the color developer with retained
Example I
color former.
The concentration of the addition products re
A 4" x 5" full color transparency sheet of color."
quired may vary from as little as 0.5%, an amount
?lm was printed by contact on two 4" x 5" sheets‘
which in general has been found to eliminate 30 of color reversible white opaque ?lm.
stain for the most part, to as much as 5%, an
The two sheets of 4" x 5" color reversible white
amount which is an assurance that stain forma
opaque ?lm were ?rst developed for twelve
tion will not ensue. Amounts higher than 5%
minutes at 68° F. in a developer of the follow
give little improvement. Concentrations ranging .
ing composition:
from between 2 and 4% are most desirable from 35
a commercial standpoint.
p-Monomethylaminephenol sulfate__grams__
The photographic multi-layer materials, which
may be processed with the anti-stain bath of the
present invention, are color reversible ?lm, color
Sodium carbonate (monohydrate)____do____ 40
negative ?lm, color reversible white printing ma
Sodium thiocyanate ________________ __do____
Potassium bromide ________________ __do____
Water to make ____________________ __liter__
terial coated on an opaque base, and color posi
tive printing material coated on paper, irre
spective of whether the dyestuff images are pro
duced with color formers present in the emulsion,
or by a selective second exposure followed by de
velopment with developing solutions containing
color formers and color developing agents.
3
Sodium sul?te ____________________ __do____ 50
Hydroquinone ____________________ __do____ 6
2
2
1
The developed ?lm was short stopped for three
45 minutes at 68° F. in a 5% aqueous solution of
sodium bisul?te.
The ?lm was washed for two minutes in run
ning water 68° F. and re-exposed to white light.
The color reversible ?lm consists of an in
The re-exposed ?lm was color developed for
tegral tripack emulsion coated on the usual clear
cellulose acetate or nitrate ?lm base. Each of 50 ?fteen minutes at 68° F. in a developer of the
following composition:
the emulsion are sensitized to one of the primary
colors of light, namely, blue, green, and red.
p-Aminodiethylaniline HCl ________ __grams__ 4
The top layer is blue sensitive. A filter layer,
Sodium sul?te ____________________ __do____ 20
yellow in color and blue absorbing, lies under
Hydroxylamine HCl ________________ __do____ 2,
the top layer. Below this ?lter layer, lies a green 55
Sodium carbonate ________________ __do____ 80
sensitive emulsion layer, and below this is a red
Potassium bromiden ______________ __do____ 1
sensitive emulsion layer. Each of the three sil
Water to make ____________________ __liter__ 1
ver-halide emulsion layers contain dye-forming
compounds which unite during the development
of a silver image in an aromatic amine develop
The color developed ?lm was rinsed for four
60 minutes in running water at 68° F., and hardened
ing agent to form a dye with the oxidation prod
uct of the developing agent, or may be free from
color formers in which case the ?lm is processed
with the color formers in the color developers by
the selective second exposure and color develop
ment method as described in United States Pat
ents 1,897,866, 1,900,870, 1,928,709 and 1,980,941.
As silver is formed during development, it must
be removed after color development by treatment
in a bleach, followed by treatment in a bath of
sodium thiosulfate, according to usual practice.
A yellow dye is formed in the blue sensitive emul
sion; a magenta dye is formed in the green sensi
tive emulsion; and a cyan dye is formed in the
red sensitive emulsion.
Combinations of these 75
for ?ve minutes in a 3% aqueous solution of po
tassium chrome alum.
The hardened ?lm‘ was washed for ?ve min
utes in running water at 68° F. The washed ma
terial was then treated with a bleach bath of
the following composition:
Di-potassium mono-sodium ferri
cyanide ______________________ __grams__ 100
Potassium bromide _______________ __do____ 15
Disodium phosphate ______________ __do____
40
Sodium bisulfate _________________ .._do__.._
Formalin (40%)s _____ __cubic centimeters"
25
20
Water to make ___________ -‘. _______ __liter__
1
'The bleached ?lm‘ was washed for ?ve min‘
aromas
the brand name of "Ila-rial: MR1! and having the
‘utes at 68° F., and then ?xed for- five minutes in
‘fol-lowing formula:
a solution of the following composition:
’
Water to maker _____________ _;_‘__.._ll-i‘ter__
omen
n
Hypo __________________________ _'_grams__ 200
Borax ___________________________ __do____ 10
1
After ?xing, the material waswashed forten
minutes in running water at 68° F.
'
After the ?nal washing, one pr'nt was allowed
to dry while the other was rinsed for ?ve min
utes in an aqueous solution consisting of 98 ‘parts
The ‘color print washed inwater showed objec
tionable stains after drying, while ‘the print
treated with the solution containing the-trimeth
by weight of water and’ 2 parts by weight of a
ylolmelamine was clear and unstained.
Similar ‘results were obtained as in the pre
' water-soluble addition product of "formaldehyde
and cyanurtrihydrazide,
methylol-cyanurtrihy- '
drazide, prepared according to Example I of
United States Patent 2,211,709, and then allowed
to dry. At this point, the prints appeared iden
tical. After normal drying, the print'rinsed in
the solution containing the addition product of
ceding examples when the addition products of
‘Examples .2,- 4, “and "5 of United States Patent
2,211,709, Examples 3, 4, and 16 of United States
Patent 2,211,710, and Examples 4, 7, and 15 of
United ‘States Patent 2,197,357 were employed.
formaldehyde and cyanurtrihydrazide showed
brighter colors and more brilliant highlights.
11 to IV inclusive were stored for several months.
The treated and untreated prints of Examples
The untreated prints showed marked staining
The print given only a water washing for ?ve
during storage and the color balance after stor
age was completely ruined by yellow stains,
to twenty minutes showed a slight highlight
stain.
.
whereas no stains were evident on the treated
When the drying was carried out under con
prints and the color balance was una?ected.
ditions of high humidity so that the drying time
was extended for several hours, the water-rinsed
Instead of employing the water-soluble addi
tion products of formaldehyde and an azine in
print showed even greater highlight stains While
aqueous solutions as a ?nal rinse bath, they may
the print rinsed in the aqueous solution contain 30 be
incorporated into gelatin solutions in a con
ing the addition product did not change.
centration ranging from 2—5% and such gelatin
After storing both prints, 1. e., treated and un
solutions utilized as a surface coating for the
treated for several months, it was observed that
processed
multi-layer photographic material.
the color balance of the treated print was un
The above speci?c examples are to be regarded
affected, whereas the color balance of the un 35 as being merely illustrative of the invention and
treated print was completely ruined by yellow
not in any sense restrictive. It will be obvious to
stain appearing overall, while at the same time
those skilled in the art that many modi?cations,
the densities of the original yellow image were
such as substituting equivalent materials and
lowered.
40
Example II
Example I was repeated with the exception
that the colored material employed was a color
paper and the ?nal rinse bath consisted of 98
parts by weight of water and 2 parts by weight of
a water-soluble addition product of formalde~
hyde and 2,4,6 - triaminopyrimidine, 2,4,6 - tri
methylolaminopyrimidine, prepared according to
Example I of United States Patent 2,211,710. The
color print washed in water showed objectionable
strains on slow drying, while the print washed
with the aqueous solution containing the addition
product was clear and unstained.
varying the proportions of the materials used,
may be made. The scope of the invention is to
be limited solely by the appended claims.
I claim:
1. In a process of producing color photographic
images in a silver-halide emulsion by exposing
the emulsion, color-forming developing the same,
bleaching, ?xing, and washing, the improvement
which comprises'avoiding the formation of stain,
after the bleaching and washing operation, by
rinsing the said silver-halide emulsion with an
aqueous solution containing a water-soluble addi
tion product of formaldehyde and an azine
selected from the class consisting of those having
the following formulae:
Example III
Example I was repeated with the exception
that the colored material employed was a color
transparency sheet and the ?nal rinse bath con
sisted of 97 parts by weight of water and 3 parts 60
by weight of a water-soluble addition product of
formaldehyde and melamine, trimethylolmel
amine, prepared according to Example VI of
United States Patent 2,197,357. After ?xing and
washing, the color print washed in water showed
objectionable stains, while the color print treated with the aqueous solution containing the addi
tion product was clear and unstained.
(3)
Example IV
Example I was repeated with the exception
that the ?nal rinse consisted of 98 parts by
weight of water and 2 parts by weight of tri
methylolmelamine available commercially under 75 wherein at least one Y is an amino group having
r 2,487,569
at least one reactive hydrogen atom, the remain
ing Y’s being a radical selected from the group
consisting of hydrogen, hydroxyl, halogen, alkyl,
alkylene, aryl and aralkyl, Z represents a mem
ber selected from the group consisting of hydro
gen amino, hydroxy, alkyl, alkoxy, phenyl,
phenylene, mercapto, alkylthio and hydrazino, at
8
bleaching, ?xing, and washing, the improvement
which comprises avoiding the formation of stain,
after the bleaching and washing operation, by
rinsing the said silver-halide emulsion with an
aqueous solution containing 2,4,6-trimethylo1
aminopyrimidine.
_
4. In a process of producing color photographic
images in a silver-halide emulsion by exposing
least two Z’s being a member selected from the
class consisting of amino and hydrazino group,
the emulsion, color-forming developing the same,
X represents a member selected from the group 10 bleaching, ?xing, and washing, the improvement
consisting of hydrogen and a primary amino
which comprises avoiding the formation of stain,
group, R represents a member of the group con
after the bleaching and washing operation, by
rinsing
the said silver-halide emulsion with an
phenyl, and alkylthio groups.
aqueous solution containing trimethylolmel
2. In a process of producing color photographic 15 amine.
images in a silver-halide emulsion by exposing
E. SCUDDER MACKEY.
the emulsion, color-forming developing the same,
bleaching, ?xing, and washing, the improvement
REFERENCES CITED
which comprises avoiding the formation of stain,
The
following
references are of record in the
after the bleaching and washing operation, by 20
?le of this patent:
rinsing the said silver-halide emulsion with an
aqueous solution containing methylolcyanurtri
UNITED STATES PATENTS
sisting of halogen, hydroxy, hydrazino, alkoxy,
hydrazide.
Number
3. In a process of producing color photographic
images in a silver-halide emulsion by exposing 25 2,384,658
2.440.954
the emulsion, color-forming developing the same,
Name‘
Date
Vittum __________ __ Sept. 11, 1945
Jennings _________ __ May 4, 1948