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Патент USA US2137336

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‘Nov. 22,1938.
"
g GASPAR
'
'
2,137,336
METHOD OF PRODUCING COLOREO COLLOID LAYERS FOR PHOTOGRAPHI‘C
‘
PURPOSES AND MATERIAL THEREFOR
Filed June 20, 1936
L1 ht‘
Lightsehsifaye
' gaggla?fjdh?r '
'
LagerContammg,
’
ILXXxX/XXXXXX
Preclpltatmg Agent
xx >53;
_S upporfi)
I
Fastl? Dyed Llghf
sens Ltl Ve Lager
Light Sensitive
Lager Containing,
Preclpita?ng Agent
.IN\'IENTOR
“
ATTORNEY
Patented vNov. 22,1938 I .
1 UNITED’ STATES PATsNroF-rlcr:
'
2,131,330,
METHOD or raonucmo ooLonEn col.- Y
Loin Lamas ron rno'roensrmo run.
' rosns AND MATERIAL 'rnsanroa
Bela. Gaspar, Brussels, Belgium
Application June 20, 1936, .Serial No. 88,427
In Germany Junev 21, 1935
‘
J
l
13 Claims. >
> hi. 955-2)
For many purposes in connection with photo4 to be colored by a water-insolubie'precipitate of
graphic and color photographic processes it is water-soluble dyestuffs are produced by adding
necessary to produce colored gelatine layers, the the precipitating agent to the gelatine either be
color of which does not bleed or, in the case oi’ fore pouring the same ‘or to the layer coated on a
l a plurality of layers, diffuse from one colored support, and'applying thereafter an aqueous solu- 5
layer into an adjacent layerrwhich may beeither tion of the dyestu?' to the coating. The addition
‘ colorless'or-may be difi'erentlycolored.
It has
been proposed to mordant the dyestu?s used for
dyeing the, gelatine by treating the layer after
10' dyeing with metal salts. It has also been pro
posed to precipitate the dyestuil.’ within the emul
sion prior, to pouring. Furthermore for the same
purpose it is known to cause mutualprecipitation
of dyestuifs of contrary reaction or to eifect double
l5 decomposition of dyestuffs . and precipitating
‘agents, a di?icultly soluble salt of the dyestuif be
ing formed by this double decomposition. ‘Diffu
sion of the dyestu?s present in adjacent layers of a
multilayer material has been prevented by the
20 formation in the boundary zone of such layers of
an extremely dispersed dyestu?? precipitate pro
duced by mutual precipitation of ‘the dyestu?s
contained in each of the layers or of one dyestuil'
contained in one of the layers and a colorless'pre
25 cipitating agent present within the other layer.
Applicant has discovered, contrary to what
might be expected, that such dyestu? precipitates
'in the boundary zone are no'obstacle to'di?usion
of dyestuffs from aqueous solution through the
30 boundary zone into the deeper strata of the gela
tine. Even with thick layers of gelatine, contain
ing a precipitating agent- and in which a very
?nely dispersed dyestufi‘ precipitate is formed by
treating with aqueous dyestuii' solution, there is
35 no di?lculty for complete dyeing of the gelatine.
For example, it has been found, that a gelatine
of the precipitating agent-to the‘ gelatine or emul- ‘
sion prior to coating is preferable if it is desired
to have a distinct amount 01’ dyestui’l precipitated‘
within the layer, as the quantity of precipitating ‘1o
agent determines to a great extent the quantity
of dyestuii' ?xed. especially if dyestuffs are used
which by themselves do . not dye the gelatine.
Sometimes it may be desirable to add the precipi
tating agent only after pouring the layer and 15 '
then a solution of the precipitating agent may
be applied prior'to the treatment with the dye
stuif solution.
-
r
r
"
The addition of the precipitating agent to the
gelatine or gelatine-layer and the subsequent dye- 2,0
ing with a dyestu?, which is‘ precipitated by the
'
agent present within the layer, may be used for
selectively dyeing a plurality of layers poured one
on top of the'other or for dyeing di?erent strata
of a single layer. Even a layer not situated at the 26
surface of a multilayer-material-can be selectively
dyed and the coloration so obtained does not diif~
fuse or bleed. Therefore the exposure of the part
layers of. a multi-layer light-sensitive material
may occur while these layers’ are colorless‘ and the‘ 30 '
dyestu?’s necessary for the color reproduction may '
be applied after‘exposure. Thereafter the dye
stuffs uniformly applied to and precipitated with
in the layers or part-layers. may be locally de
stroyed at the exposed or unexposed parts of the ‘35 >_
layer by the use of the well-known dyestuil' de
layer containing diphenyl-guanidine acetate al
stroying processes. A plurality of superimposed
lows penetration of a solution of 1% strength of layers may be dyed a different color, either by
Diamine Pure Blue (Schultz Farbsto?tabelien 5th’ , using in each layer a precipitating agent which
40 Ed. No.‘ 426). " An insoluble'diphenyl-guanidine
salt is formed at the surface/of the layer, but
nevertheless the penetration of the dissolved dye
stu? is not inhibited and further quantities of the
.dyestu? are precipitated within the deeper strata
45 of the gelatine. When interrupting the treat
ment with the solution of the blue dyestu?' and
continuing for example with a solution of Xylene
Light Yellow 2G (Schultz, l. c. No. 22) the deepest
stratum of the gelatine will be dyed yellow. These
50 phenomena may be used for dyeing and especially
selectively, dyeing of gelatine layers for photo
graphic purposes which layers may contain light
sensitive silver salts or already exposed and de
veloped silver images.
55,
.
.
According to the invention the gelatine layers
only precipitates one of the two di?erent dye- 40 I
stuifs, or by using two dyestu?' solutions in suc
cession, of‘ which solutions the second forms a
dyestu?’ deposit in the deepest part-layer, in which =
the precipitating agent is still present, whereas
the superimposed layer is unaffected, the precipi- 45
tating agent having been- already'consumed by
the ?rst treatment with the dyestu? solution.
When using a plurality of precipitating agents
the agent for‘ the deeper layer is applied to the
gelatine or emulsion prior to coating. The pre- ‘50
cipitating' agent for the top-layer, may be applied -
after dyeing the deeper layer and the second dye
stuii’ solution is applied thereafter.
Example 1.-A solution of 5 g. gelatine in 80
com. water is mixed with a solution oi’ 1 g. beta-y 55_
2,187,386
' 2
naphthoquinolinium-N-ethyl sulphate and poured
tive emulsion being applied after drying of the
layers dyestuffs are used which do not dye the
upper layer already colored but can be removed
from the upper layer by washing. For dyeing
of the surface layer acid and substantive dye
stuffs are preferred and therefore precipitating
agents are used which form insoluble salts by
double decomposition with acid or substantive
dyestuffs. There may be used, for example,
the salts of organic bases, such as naphthoquino
colored layer.
line, triphenyl-guanidine, quinine, cinchonine, 10
on to a support.
The layer is treated with an
aqueous solution of 1% strength of Dlamine Pure
BlueFF (Schultz, l. c. No. 424).
‘
Example 2.-—A layer as described in Example
1 is treated with a solution of 1/2% strength of
Diamine Fast Red F (Schultz l. c. No. 343) . vThe
layer is used as an antihalation layer, a light sensi
-10
>
Example 3.—A"silver-bromide gelatine emulsio
aminoquinoline. The salts formed by these bases
is colored yellow by adding 2-phenyl-4-amino
quinolin hydrochloride and Metanil Yellow
with organic acids or the quaternary salts de
rived from the amines may be used. Other pre
(Schultz l. c. No. 134). The emulsion is a sensi
15 tized emulsion, containing pinacyanol. After
coating a colorless silver bromide gelatine emul
sion containing 3 g. diphenyl-guanidin-acetate
per sq. m. is coated on top of the yellow layer.
After exposure'and development and ?xing the
20 ?lm is treated by a solution of 1% strength of
Diamine Pure Blue FF.
. Example 4.—On to a yellow layer as described
in Example 3 a colorless silver halide emulsion
without the addition of a precipitating agent is
25 poured.
cipitating agents which may be used are in
organic bases or salts, such as barium carbonate 15
or magnesium carbonate. For the precipitation
of basic dyestuffs, such as chrysoidine (Schultz
l. c. 33) or Janus-red-B (Schultz l. c. 240)
antimony salts or zinc-ferrocyanide may be used
or acids, such as tannic acids which form in
soluble salts with basic dyestuffs. The amount
of the precipitating agent and the sequence may
be chosen according to the properties of dyestuff
and precipitating agent or the desired result.
Instead of the dyestufi.I solutions described 25
After exposure development and ?xing
a solution of 3% strength of betanaphthoquino 1 there may be used solutions which do not con
linium-N-ethyl sulphate is applied and the mm tain a dyestu? itself, but which form a dyestuif
is treated for about 10 minutes. Thereafter a by interaction with dyestuff-forming substances
dyestuif solution, as described in Example 3, is present in the material. For example, a layer
30 used for dyeing during about 4 minutes. The may be- used which contains a leuco-derivatlve 30
vfilm then shows a blank silver image in the of a vat-dyestuff and a precipitating agent for
yellow dyed layer and a silver image in the blue the vat-dyestuifs. When such a layer is treated
dyed layer. The silver images are treated with with an oxidizing agent ‘the dyestu? is precipi
a solution of 5% thiocarbamide and 1% citric tated in situ by the precipitating agent and there
35 acid which, in a known manner, destroys the ‘is no possibility for bleeding or diffusion of the
dyesturl's at the points where silver is present.
The ?lm described may be used as a front
?lm of a bipack, the rear ?lm being a. colorless
or colored ?lm sensitive for grr en. In this case
the blue sensitive layer of the double coated
?lm faces the objective in the camera during
exposure.
sion is poured on a support and on top of the
yellow layer a colorless silver bromide gelatine
50 emulsion containing 3 g. of cinchonine hydro
chloride per sq. m. is poured.‘ The yellow layer
may contain a sensitizer for red light or for
green light, the top layer being an ordinary blue
sensitive emulsion. layer. After ‘exposure the
surface layer is treated with a solution of 1%
strength of Diamine Pure Blue or with a solu
tion of Diamine Fast Pink BBF. The ?lm is then
developed and ?xed and the dyestu? destroyed‘
by a thiocarbamide solution at the points where
silver is present.
Example 6.—A silver halide emulsion contain
ing 0.3% of the sodium salt of salicylic acid is
poured on to a support of Celluloid.
On top
of this colorless layer a layer is poured contain
ing Diamine Pure Blue precipitated by triphenyl
guanldine acetate. The composite ?lm is treated
after exposure by. an aqueous solution of 1/4%
strength of auramine (Schultz l. c.‘ 493) and
washed in water until the upper layer has be
70 come pure blue.
Example 7.-A silver bromide gelatine emul
sion which contains 20 g. silver bromide in one
liter of emulsion and sensitized to red light with
pinacyanol is coated onto a support of Celluloid.
To this emulsion is added before the coating
operation either:
Example 5.-A silver bromide gelatine emul
‘sion is dyed with chlorantinlichtgelb, (a dyestu?
45 furnished by the Gesellschaft fiir Chemlsche
Industrie, Basel, Switzerland) the dyestu?.’ be
ing precipitated by barium nitrate. The emul
05
- dyestuff.
The ?lm as a whole appears
green.
Instead of the dyestuffs used in the preced
ing examples other dyestuffs may be used which
are precipitated by the precipitating agent con
75 tained in the layer. For dyeing of the deeper
-
A. 5 g. of the beta-naphthothiazolium salt of
diazo light yellow G dissolved in 100 cc. alcohol;
or
B. 5 g. of the beta-naphthoquinolinium-salt of
‘7-, 7-, dioxy- 2-, 2'- dinaphthylurea 5-, 5' disul
fonic acid dissolved in 100 cc. alcohol; or
C. 5 g. of the cinchonin salt of the sulfuric
acid ester of leucohexabromindigo.
On top of the ?rst layer another colorless
silver-bromide emulsion is coated which contains
2 g. diphenylquanidin acetate in a liter of emul
sion.
This emulsion may be sensitized to green
light.
65
The ?lm is thereafter exposed in a camera or
in a printing machine, and subsequently de
veloped and ?xed in the usual manner.
After that the ?lm is treated by immersing
it into an aqueous solution containing either:
I. Diamine ‘Pure Blue FF (Schultz l. c. No.
424); or
.
II. 1% solution of the sodium salt of the sul
furic acid-ester of leucodibrombisthionaphthen
indigo.
The dyestuil' in the deeper layer is formed
diffusely if using a ?lm according to Example A
by diazotizing with ay 1% solution of nitrous acid
and subsequent coupling with a solution of 70
naphthylaminchlorhydrate. Thus a red azo-dye-.
stuffis formed.
'
Using a ?lm as described in Example B by
treating the ?lm with a 0.5% solution of hydro
bromic acid and sodium bichromate.
76
3
9,187,886
3. The method of producing a colored photo
The above described treatment refers to the
' The further treatment of the film indicated
graphic‘ image in a gelatine layer of a‘photo
graphic material, which comprises incorporating
in this Example AI and BI is continued in the
in a light sensitive silver halide emulsion, a pre-
same way as in Example 4 indicated with an
cipitating agent adapted to react with the dye- 5
stu? to be used in coloring said layer, said pre
cipitating agent ‘being such as will not be ad
forming of dyestu?s in the' deeper layer.
acidic solution of thiocarbamide thus a two
color image is formed by local dye destruction
of the dyestu?' in each- layer.
' versely affected by ordinary photographic treat
'
The ?lm as made according to this Example 0
10 and treated as in this example under II indicated
is treated with a 1% solution of hydrochloric
‘acid and sodium bichromate and thus a two
color image is formed.
-
‘
ing baths, pouring‘ said ‘silver halide gelatine
emulsion having said precipitating agent incor- H)
porated therein to form a layer, exposing said
layer to light to form a silver image therein,
treating the layer throughout its depth after ex
posure, wlth‘an aqueous solution of said dyestu?
In the deeper layer a blue and in the upper
' to form a dyestu? precipitate only in said layer 15
15 layer a red image is formed locally.
_ It is already known to have a precipitating
agent within a layer to be printed upon, but in
this case only the small amounts of dyestu? of
the matrix are transferred locallywto the layer.
In the present process the dyestu?f is uniformly
applied from aqueous solutions and by the pres
ence of precipitating agents determination of
the amount of dyestu? and the selective dyeing
of diiIerent strata of the material is rendered
25
possible.
7
and treating said layer-with a‘dyestu? destroy
ing bath which destroys the dyestu? locally in
proportion to the silver image in said layer.
4. The method of producing a colored photo
graphic image in a gelatine emulsion layer of a 20,
multi-layer. light sensitive silver halide material,
which comprises incorporating in said layer prior
to exposure of said material to light, a precipi
tating agent adapted to react with the dyestu?
to be used in coloring said layer, said precipi- 5;
In the annexed drawing Figure 1 shows two - tating agent being such as will not be adversely
differently ‘sensitized silver halide layers I and
II coated on to a support III.
_
Figure 2 shows two differently sensitized silver
30 halide layers II and I on a support III. In each
case layer I is uncolored and contains a pre
cipitating agent for the dyestui’f to be applied
afterwards.
Layer II is a colored layer.
The
layers containing the precipitating agent for the
35 dyestu?' to be applied’ afterwards may contain a
dyestuif which is not precipitated by the pre
cipitating agent, but only acts as a ?lte dye
affected by ordinary'photographic treating baths,
exposing said material to light to form a silver'
image, treating said material after exposure with
'an aqueous solution ofssaid dyestu‘? to form a .,'
dyestuiI precipitate only in said layer and treat
ing said material with a dyestu? destroying bath
which destroys the dyestuil' locally in proportion
to the silver image in said material.
.
v
5. The method of producing a colored photo
graphic image in a gelatine emulsion layer ofa
multi-layer light sensitive photographic material,
which comprises incorporating in a light sensi
tive silver halide emulsion a precipitating agent
during exposure and can be washed out after'
exposure, if desired.
adapted to react with the dyestu? to be used in 40
What I claim is:
40
1. The method of producing a colored photo , coloring saidlayer, said precipitating agent being
graphic image in a colloid layer of a photographic
material including a light sensitive silver halide,
which comprises incorporatingin the colloid to be
colored prior to exposure of the photographic ma
terial to light, a precipitating agent adapted to
such as will hot be adversely affected by ordinary
photographic treating baths, pouring said silver
halide gelatine'emulsion having said precipitat
ing agent incorporated therein to form a layer 45
along with the other layers of said material,
react with the dyestuii to be used in coloring the ' exposing said material to light to form a silver
said colloid, said precipitating agent being such
as will not be adversely affected by ordinary
50 ‘photographic treating baths, exposing said ma
terial to light to form 'a silver image therein,
treating the layer'througho'ut its depth after
exposure, with an aqueous solution of said dye
stu? to form a dyestu? precipitate only in said
55 layer and treating‘ said layer with a dyestuil'
destroying bath which destroys the dyes-tuft’ lo
cally in'proportion to the silver image in said
image therein, treating said.»material after ex
posure with an aqueous solution of said dyestuif
to form a dyestuff precipitate only in said layer
and treating said material with a dyestui‘f de
in proportion to the silver image in said material.
6. The method of producing a colored photo~
graphic image in the layers of a multi-layer 55
light sensitive silver halide material comprising
graphic material, which comprises incorporating
a predyed layer and a layer to be-colored, whichv
comprises incorporating'in the gelatine of the
layer to_be colored prior to exposure of vsaid
material to light, a precipitating agent adapted
to react with the dyestu?‘ to be used in coloring
in a light sensitive silver halide gelatine emulsion -
said layer, said precipitating agent being such
layer.
'
=
"
-
.
2. The method of producing a colored photo
graphic image in a gelatine layer of a photo
so
straying bath which destroys the dyestu? locally
used to form said layer, prior to exposure to light,
a precipitating agent adapted to react with the
as will notice adversely affected by ordinary
photographic treating baths, exposing said ma
65 dyestuii' to be‘ used in coloring said layer, said ‘ terial to light to form silver images therein,
precipitating agent being such as will not be- ' treating said material after exposure with an, 2
adversely affected by ordinary photographic
70
treating baths, exposing said layer to light to
aqueous solution of said dyestuii to form a dyestuff precipitate only in said layer to be colored
form a silver image therein; treating the layer
throughout its depth‘ after exposure, with an
stroying bath which destroys the dyestuff locally
' aqueous solution of said dyestu? to form a dye
stuff precipitate only in said layer and treating
said layer with a dyestuff destroying bath which
destroys the dyestu?‘ locally in proportion to the
75 silver image in said layer.
'
'
'
and treating said material with a dyestu? de;
in said layers in proportion to the silver images
in said material.
‘
. 7. The method of producing a colored photo
graphic image in the layers of a multi-layer
light sensitive silver halide material compris- 75'
4
2,187,838
ing a predyed layer and a layer to be colored,
photographic treating baths coated on top of a
which, comprises incorporating in the gelatine
gelatine layer to be colored, which comprises in
of the layer to be colored prior to exposure oi
said material to light, a basic precipitating agent
adapted to react with an acid dyestuif to be used
corporating in the gelatine of the layer to be
colored prior to exposure of said material to light,
a precipitating agent adapted to react with the
dyestu? to be used in coloring said layer, said
precipitating agent being such as will not be
in coloring said layer, said precipitating agent
being such as will not be adversely ail’ected by
ordinary photographic treating baths, exposing
adversely affected by ordinary photographic
said material to light to form silver images there
10 in, treating said material after exposure with
an aqueous solution of said dyestu? to form a
' dyestuii precipitate only in said layer to be col
treating baths, exposing the multi-layer ma
terial to light to form silver images therein,
ored and treating said material with a dyestu?
destroying bath which destroys the dyestu? lo
ll cally in said layers inproportion to the silver
images in said materiaL.
.
8. The method of producing a colored photo
graphic image in the layers of a multi-layer light
sensitive silver halide material comprising a pre
dyed layer and a layer to be colored, which com
developing and ?xing said silver images, treating
said material after exposure with an aqueous
solution of said dyestuii~ to form a dyestu? pre
cipitate only in said layer to be colored, washing
out the excess of said dyestuif from said material 15
and treating said material with a dyestuii' de
stroying bath which destroys the dyestu? locally
in said layers in proportion to the silver images
in said material.
-
11. The method of producing multi-color pho
prises incorporating in the gelatine of the layer
tographic images which comprises incorporating
to be colored prior to exposure of said material
to light, a precipitating agent comprising a salt
of an organic base adapted to react with an acid
in at least one layer of a multi-layer light sensi-'
‘tive silver halide material, prior to exposure of
dyestuii to be used in coloring said layer, said
said material to light, a precipitating agent
adapted to react with the dyestuii to be used in
precipitating agent being such as will not‘ be
adversely a?ected by ordinary photographic
ing such as will not be adversely affected by ordi
treating baths, exposing said material to light to
form silver images therein, treating said material
after exposure with an aqueous solution of said
dyestu?f to form a dyestu? precipitate only in
said layer to be colored and treating said ma
terial with a dyestu? destroying bath . which
destroys the dyestu? locally‘ in said layers in
proportion to the silver images in said material.
9. The method of producinga colored photo
io_
coloring said layer, said precipitating agent be
nary photographic treating baths, exposing said
material to light to form metallic silver images
therein, applying an aqueous solution of said
dyestuif to said material to produce a uniformly
dyed silver image in said layer and treating said
material with a dyestuff destroying bath which
locally destroys the dyestu? in said layer in pro
portion to the metallic silver image therein.
graphic image in the layers of a multi-layer light
12. A multi-layer photographic material com
prising a predyed silver halide layer sensitized -
sensitive silver halide material comprising a pre
dyed layer and a layer to be colored, which com
stantially colorless silver halide layer sensitized
prises incorporating in the gelatine of the layer'
to be colored prior to exposure of said material
to light, a precipitating agent comprising an acid
adapted to react with a basic dyestuii' to be used
to a predetermined spectral range and a‘sub
to a di?erent spectral range, said substantially 40
colorless layer having incorporated therein a
dyestuif precipitating agent selected from the
in coloring said layer, said precipitating agent
group consisting of organic bases and salts of
such bases which will not be adversely a?ected
being such as will not‘ be adversely airected by
by ordinary photographic treating baths.
ordinary photographic treating baths, exposing
said material to light to form silver images there
in, treating said material after exposure with an
aqueous solution of said dyestuif to form a dye
50 stuff precipitate only in said layer to be colored
and treating. said material with a dyestu? de
13. A multi-layer photographic material com
prising a substantially colorless silver halide layer
containing a dye-forming substance and sensi
tized to a predetermined spectral range, and a
substantially colorless silver halide layer sensi
tized to a di?erent spectral range, said substan
stroying bath which destroys the dyestu? local
tially colorless layer having incorporated therein
ly in said layers in proportion to the silver
images in said material.
10. The method of producing a colored photo
graphic image in a layer of a multi-layer light
sensitive silver- halide material comprising a
layer colored by a dyestu?f resistant to ordinary
a dyestu? precipitating agent selected from the
group consisting of organic bases and salts of
such bases which will not be adversely affected
by ordinary photographic treating baths.
BELA GASPAR.
45
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